Curable composition, film, optical filter, image display device, and optical sensor

Abstract

This curable composition contains: a coloring material that contains a pigment; a photopolymerization initiator; a polymerizable compound; at least one selected from among a compound A1, a compound A2, and a compound A3; and a solvent. The photopolymerization initiator contains a glyoxylate compound. The compound A1 is at least one selected from among a compound A1-1 that comprises a basic group and a graft chain and has a weight average molecular weight of 2,000 to 30,000 inclusive, and a block copolymer A1-2 that comprises a basic group and has a weight average molecular weight of 2,000 to 30,000 inclusive. The compound A2 comprises a dye structure or the like and a basic group, and has a molecular weight of not less than 100 but less than 2,000. The compound A3 is a polyalkylene imine. Also provided are a film, an optical filter, an image display device, and an optical sensor, each of which uses the curable composition.

Description

Curable composition, film, optical filter, image display device and optical sensor

[0001] This invention relates to a curable composition comprising a colorant, a photopolymerization initiator, and a polymerizable compound. Furthermore, this invention relates to films, optical filters, image display devices, and optical sensors using the curable composition.

[0002] In recent years, the demand for solid-state image sensors, such as charge-coupled (CCD) image sensors, has grown significantly due to the widespread use of digital cameras and camera-equipped mobile phones. Optical filters, such as color filters, are used as key devices in displays and optical elements.

[0003] Optical filters, such as color filters, have a film pattern (pixels) containing colorants such as pigments. Conventionally, such patterns (pixels) have been manufactured by forming the pattern using a photolithography method with a curable composition containing colorants such as pigments, a photopolymerization initiator, and a polymerizable compound (for example, Patent Document 1).

[0004] Japanese Patent Publication No. 2022-063556

[0005] When forming pixels by pattern formation using photolithography with a curable composition containing a colorant, a photopolymerization initiator, and a polymerizable compound, curable compositions that have been stored for a long period of time are sometimes used. However, these curable compositions tend to experience a decrease in sensitivity over time due to factors such as the decomposition of the photopolymerization initiator during storage.

[0006] Furthermore, when using colorants containing pigments, the pigments sometimes leached out of the film during development.

[0007] Therefore, an object of the present invention is to provide a curable composition that can form a film with excellent temporal stability of sensitivity and suppression of pigment loss during development. Another object of the present invention is to provide a film, an optical filter, an image display device, and an optical sensor using the curable composition.

[0008] The present invention provides the following:

[0009] <1> A curable composition comprising: a colorant containing a pigment; a photopolymerization initiator; a polymerizable compound; at least one selected from compound A1, compound A2, and compound A3; and a solvent, wherein the photopolymerization initiator comprises a glyoxylate compound; compound A1 is at least one selected from compound A1-1, which has a basic group and a graft chain and a weight-average molecular weight of 2,000 to 30,000, and block copolymer A1-2, which has a basic group and a weight-average molecular weight of 2,000 to 30,000; compound A2 is a compound having at least one structure selected from a dye structure, an aromatic ring, and a heteroaromatic ring, and a basic group, and a molecular weight of 100 to less than 2,000; and compound A3 is a polyalkylene imine. <2> The curable composition according to <1>, wherein the curable composition comprises compound A1, and further comprises compound B1 having at least one structure selected from a dye structure, an aromatic ring, and a heteroaromatic ring, and an acid group, and having a molecular weight of 100 or more and less than 2000. <3> The curable composition according to <2>, wherein the basic group of compound A1 is an amino group, and the amine value of compound A1 is 15 mg KOH / g or more. <4> The curable composition according to any one of <1> to <3>, wherein compound A1 is a compound further having an acid group. <5> The curable composition according to <1>, wherein the curable composition comprises at least one selected from compound A2 and compound A3, and further comprises compound B2 having an acid group and a graft chain, and having a weight-average molecular weight of 2000 or more and 30000 or less. <6> The curable composition according to any one of <1> to <5>, wherein the polymerizable compound comprises a polymerizable compound having an amino group and an ethylenically unsaturated bond-containing group. <7> The curable composition according to any one of <1> to <6>, wherein the photopolymerization initiator comprises a compound different from the glyoxylate compound. <8> The curable composition according to any one of <1> to <7>, wherein the glyoxylate compound comprises a compound represented by formula (1) or formula (2); In formula (1), Ar １R represents an m1+n1 valent group containing at least one selected from the group consisting of aromatic rings and heteroaromatic rings, １ R represents an alkyl group. ２ represents a halogen atom, nitro group, cyano group, or acyl group, n1 represents an integer from 1 to 4, and m1 represents an integer from 0 to 2; in formula (2), Ar １１ R represents an m²+1 valent group containing at least one selected from the group consisting of aromatic rings and heteroaromatic rings, １１ R represents an n-2 valent organic group. １２ n2 represents a halogen atom, a nitro group, a cyano group, or an acyl group, n2 represents an integer from 2 to 6, and m2 represents an integer from 0 to 2. <9> A film obtained using the curable composition described in any one of <1> to <8>. <10> An optical filter having the film described in <9>. <11> An image display device having the film described in <9>. <12> An optical sensor having the film described in <9>.

[0010] The present invention provides a curable composition that can form a film with excellent temporal stability of sensitivity and suppression of pigment loss during development. Furthermore, the present invention can provide a film, an optical filter, an image display device, and an optical sensor using the curable composition.

[0011] The present invention will be described in detail below. In this specification, "~" is used to mean that the numerical values ​​before and after it are included as the lower and upper limits. In the notation of groups (atomic groups) in this specification, notations that do not specify substituted or unsubstituted include both groups (atomic groups) with substituents and groups (atomic groups) without substituents. For example, "alkyl group" includes not only alkyl groups without substituents (unsubstituted alkyl groups) but also alkyl groups with substituents (substituted alkyl groups). In this specification, unless otherwise specified, "exposure" includes not only exposure using light but also drawing using particle beams such as electron beams and ion beams. In addition, examples of light used for exposure include the emission line spectrum of mercury lamps, far ultraviolet light represented by excimer lasers, extreme ultraviolet (EUV) light, X-rays, electron beams, and other active light or radiation. In this specification, "(meth)acrylate" refers to both acrylate and methacrylate, or either of them; "(meth)acrylic" refers to both acrylic and methacrylic, or either of them; and "(meth)acryloyl" refers to both acryloyl and methacryloyl, or either of them. In this specification, Me in structural formulas represents a methyl group, Et represents an ethyl group, Bu represents a butyl group, and Ph represents a phenyl group. In this specification, weight-average molecular weight and number-average molecular weight are polystyrene equivalent values ​​measured by GPC (gel permeation chromatography). In this specification, total solids refer to the total mass of components of a composition excluding the solvent. In this specification, pigment refers to a colorant that is poorly soluble in solvents. In this specification, the term "process" includes not only independent processes, but also processes that cannot be clearly distinguished from other processes, as long as the intended function of that process is achieved.

[0012] <Curable Composition> The curable composition of the present invention comprises a colorant containing a pigment, a photopolymerization initiator, a polymerizable compound, at least one selected from compound A1, compound A2, and compound A3, and a solvent, wherein the photopolymerization initiator contains a glyoxylate compound, compound A1 is at least one selected from compound A1-1, which has a basic group and a graft chain and a weight-average molecular weight of 2000 to 30000, and block copolymer A1-2, which has a basic group and a weight-average molecular weight of 2000 to 30000, compound A2 is a compound having at least one structure selected from a dye structure, an aromatic ring, and a heteroaromatic ring, and a basic group, and a molecular weight of 100 to less than 2000, and compound A3 is a polyalkyleneimine.

[0013] The curable composition of the present invention can form a film that exhibits excellent sensitivity stability over time and suppresses pigment loss during development. The reasons for these effects are presumed to be as follows.

[0014] Glyoxylate compounds are easily hydrolyzed materials. Therefore, in curable compositions using glyoxylate compounds as photopolymerization initiators, the sensitivity of the curable composition tends to decrease over time due to hydrolysis of the glyoxylate compounds during storage, caused by factors such as proximity of bases and water to the glyoxylate compounds. The curable composition of the present invention contains the above-mentioned compounds A1 to A3, and it is presumed that these compounds interact with the pigments and exist in the vicinity of the pigments in the curable composition. For this reason, it is presumed that the glyoxylate compounds do not easily come into contact with compounds A1 to A3 in the curable composition, and as a result, the decomposition of the glyoxylate compounds during storage can be suppressed. This phenomenon is presumed to be observed in liquids where the density of the material is low and the degree of freedom of movement is high. On the other hand, glyoxylate compounds can generate radicals more efficiently by a hydrogen abstraction mechanism in the presence of a base, which can further promote the curing reaction of polymerizable compounds. Compounds A1 to A3 described above are materials that interact with pigments and tend to exist near them. Since all of these compounds have basic groups, it is presumed that exposure can efficiently generate radicals from the glyoxylate compounds, allowing the curing reaction of polymerizable compounds present near the pigment in the exposed area to proceed sufficiently. This phenomenon is presumed to occur only in films where the density of the material is high and the mobility is low. Furthermore, since this phenomenon occurs near the pigment, the curing reaction near the pigment due to exposure is particularly likely to occur sufficiently, and it is presumed that the pigment will not leach out of the composition layer in the exposed area due to the developer during development. For these reasons, it is presumed that the curable composition of the present invention can form a film with excellent temporal stability of sensitivity and suppression of pigment leaching during development.

[0015] A preferred first embodiment of the curable composition of the present invention is an embodiment in which the curable composition comprises compound A1, and further comprises compound B1 having at least one structure selected from a dye structure, an aromatic ring, and a heteroaromatic ring, and an acid group, and having a molecular weight of 100 or more and less than 2000.

[0016] A preferred second embodiment of the curable composition of the present invention is an embodiment in which the curable composition comprises at least one selected from compound A2 and compound A3, and further comprises compound B2 having an acid group and a graft chain, and having a weight-average molecular weight of 2000 or more and 30000 or less.

[0017] The curable composition of the present invention is preferably used as a curable composition for optical filters. Examples of optical filters include color filters, infrared transmission filters, and infrared cut filters, with color filters being preferred.

[0018] Examples of color filters include filters having colored pixels that transmit light of a specific wavelength. Examples of colored pixels include red pixels, green pixels, blue pixels, magenta pixels, cyan pixels, and yellow pixels. The colored pixels of a color filter can be formed using a curable composition containing chromatic pigments.

[0019] The maximum absorption wavelength of the infrared cut filter is preferably in the range of 700 to 1800 nm, more preferably in the range of 700 to 1300 nm, and even more preferably in the range of 700 to 1000 nm. Furthermore, the transmittance of the infrared cut filter over the entire range of wavelengths from 400 to 650 nm is preferably 70% or more, more preferably 80% or more, and even more preferably 90% or more. Furthermore, the transmittance at at least one point in the range of wavelengths from 700 to 1800 nm is preferably 20% or less. In addition, the ratio of the absorbance Amax at the maximum absorption wavelength of the infrared cut filter to the absorbance A550 at a wavelength of 550 nm (absorbance Amax / absorbance A550) is preferably 20 to 500, more preferably 50 to 500, even more preferably 70 to 450, and particularly preferably 100 to 400. The infrared cut filter can be formed using a curable composition containing an infrared absorbing pigment.

[0020] An infrared transmission filter is a filter that transmits at least a portion of infrared light. Preferably, an infrared transmission filter is a filter that blocks at least a portion of visible light and transmits at least a portion of infrared light. Preferred infrared transmission filters include filters that satisfy spectral characteristics such as a maximum transmittance of 20% or less (preferably 15% or less, more preferably 10% or less) in the wavelength range of 400 to 640 nm and a minimum transmittance of 70% or more (preferably 75% or more, more preferably 80% or more) in the wavelength range of 1100 to 1300 nm. Preferably, an infrared transmission filter is a filter that satisfies any of the following spectral characteristics (1) to (5): (1): A filter in which the maximum transmittance in the wavelength range of 400 to 640 nm is 20% or less (preferably 15% or less, more preferably 10% or less) and the minimum transmittance in the wavelength range of 800 to 1500 nm is 70% or more (preferably 75% or more, more preferably 80% or more). (2) A filter having a maximum transmittance of 20% or less (preferably 15% or less, more preferably 10% or less) in the wavelength range of 400 to 750 nm, and a minimum transmittance of 70% or more (preferably 75% or more, more preferably 80% or more) in the wavelength range of 900 to 1500 nm. (3) A filter having a maximum transmittance of 20% or less (preferably 15% or less, more preferably 10% or less) in the wavelength range of 400 to 830 nm, and a minimum transmittance of 70% or more (preferably 75% or more, more preferably 80% or more) in the wavelength range of 1000 to 1500 nm. (4) A filter having a maximum transmittance of 20% or less (preferably 15% or less, more preferably 10% or less) in the wavelength range of 400 to 950 nm, and a minimum transmittance of 70% or more (preferably 75% or more, more preferably 80% or more) in the wavelength range of 1100 to 1500 nm. (5) A filter having a maximum transmittance of 20% or less (preferably 15% or less, more preferably 10% or less) in the wavelength range of 400 to 1050 nm, and a minimum transmittance of 70% or more (preferably 75% or more, more preferably 80% or more) in the wavelength range of 1200 to 1500 nm.

[0021] The solid content 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 still more preferably 15% by mass or less.

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

[0023] <<Colorant>> (Pigment) The curable composition of the present invention contains a colorant. As the colorant, those containing a pigment are used. Examples of the pigment include colored pigments, infrared absorbing pigments, white or colorless pigments, black pigments, and the like. The pigment may be either an inorganic pigment or an organic pigment, but an organic pigment is preferred.

[0024] The average primary particle diameter of the pigment 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 still more preferably 100 nm or less. In this specification, the primary particle diameter of the pigment can be obtained from a photograph obtained by observing the primary particles of the pigment with a transmission electron microscope. Specifically, the projected area of the primary particles of the pigment is determined, and the equivalent circle diameter corresponding thereto is calculated as the primary particle diameter of the pigment. The average primary particle diameter in the present invention is the arithmetic average value of the primary particle diameters of 400 primary particles of the pigment. The primary particles of the pigment refer to independent particles without aggregation.

[0025] The crystallite size of the pigment is preferably 0.1 to 50 nm, more preferably 0.5 to 30 nm, and still more preferably 1 to 15 nm. The crystallite size can be determined from the half-value width of the peak of the diffraction angle using an X-ray diffractometer and is calculated using Scherrer's formula. The crystallite size of the pigment can be adjusted by known methods such as adjusting the production conditions and pulverizing after production.

[0026] The specific surface area of the pigment is preferably 1 to 300 m ２ / g. The lower limit is preferably 10 m ２ / g or more, more preferably 30 m ２ / g or more. The upper limit is 250 m２ It is preferable that the amount is less than or equal to 200m ２ It is more preferable that the value be less than or equal to / g. The specific surface area can be measured according to the BET (Brunauer, Emmett, and Teller) method and DIN 66131: determination of the specific surface area of ​​solids by gas adsorption.

[0027] - Chromatic Pigments - Examples of chromatic pigments include pigments that have a maximum absorption wavelength in the range of 400 to 700 nm. Examples include yellow pigments, orange pigments, red pigments, green pigments, purple pigments, and blue pigments. Specific examples of chromatic pigments are listed below.

[0028] Examples of red pigments include diketopyrrolopyrrole pigments, anthraquinone pigments, azo pigments, naphthol pigments, azomethine pigments, xanthene pigments, quinacridone pigments, perylene pigments, and thioindigo pigments. Diketopyrrolopyrrole pigments, anthraquinone pigments, or azo pigments are preferred, and diketopyrrolopyrrole pigments are more preferred.

[0029] Specific examples of red pigments include C.I. (Color Index) Pigment Red 1, 2, 3, 4, 5, 6, 7, 9, 10, 14, 17, 22, 23, 31, 38, 41, 48:1, 48:2, 48:3, 48:4, 49, 49:1, 49:2, 52:1, 52:2, 53:1, 57:1, 60:1, 63:1, 66, 67, 81:1, 81:2, 81:3, 83, 88, 90, 105, 112, 119, 122, 123, 144, 146, 149, Examples of red pigments include 150, 155, 166, 168, 169, 170, 171, 172, 175, 176, 177, 178, 179, 184, 185, 187, 188, 190, 200, 202, 206, 207, 208, 209, 210, 216, 220, 224, 226, 242, 246, 254, 255, 264, 269, 270, 272, 279, 291, 294, 295, 296, and 297. Additionally, as red pigments, compounds described in paragraph 0034 of International Publication No. 2022 / 085485 and brominated diketopyrrolopyrrole compounds described in Japanese Patent Publication No. 2020-085947 can also be used.

[0030] Examples of green pigments include phthalocyanine pigments and squarylium pigments, with phthalocyanine pigments being preferred.

[0031] Specific examples of green pigments include C.I. Pigment Green 7, 10, 36, 37, 58, 59, 62, 63, 64, 65, and 66. Alternatively, zinc phthalocyanine halides, which have an average of 10 to 14 halogen atoms, 8 to 12 bromine atoms, and 2 to 5 chlorine atoms per molecule, can be used as green pigments. Specific examples include the compounds described in International Publication No. 2015 / 118720. Furthermore, compounds described in paragraph 0029 of International Publication No. 2022 / 085485, aluminum phthalocyanine compounds described in Japanese Patent Publication No. 2020-070426, and diarylmethane compounds described in Japanese Patent Publication No. 2020-504758 can also be used as green pigments.

[0032] Examples of orange pigments include diketopyrrolopyrrole pigments and azo pigments, with diketopyrrolopyrrole pigments being preferred. Specific examples of orange pigments include C.I. Pigment Orange 2, 5, 13, 16, 17:1, 31, 34, 36, 38, 43, 46, 48, 49, 51, 52, 55, 59, 60, 61, 62, 64, 71, 73, etc.

[0033] Examples of yellow pigments include azo pigments, azomethine pigments, isoindoline pigments, pteridine pigments, quinophthalone pigments, and perylene pigments. Preferably, the yellow pigment is at least one selected from isoindoline pigments, quinophthalone pigments, and azo pigments. Specific examples of yellow pigments 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, Examples include 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, etc.

[0034] As a yellow pigment, a nickel azobarbiturate complex with the following structure can also be used.

[0035] As a yellow pigment, compounds described in paragraphs 0031 to 0033 of International Publication No. 2022 / 085485 can be used.

[0036] Examples of purple pigments include oxazine pigments, quinacridone pigments, perylene pigments, and indigo pigments, with oxazine pigments being preferred. Specific examples of purple pigments include C.I. Pigment Violet 1, 19, 23, 27, 32, 37, 42, 60, and 61.

[0037] Examples of blue pigments include phthalocyanine pigments and squarylium pigments, with phthalocyanine pigments being preferred. Specific examples of blue pigments include 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. Aluminum phthalocyanine compounds having a phosphorus atom can also be used as blue pigments. Specific examples include the compounds described in paragraphs 0022 to 0030 of Japanese Patent Publication No. 2012-247591 and paragraph 0047 of Japanese Patent Publication No. 2011-157478.

[0038] Chromatic pigments may be used in combination of two or more types. Furthermore, when chromatic pigments are used in combination of two or more types, black may be formed by the combination of two or more chromatic pigments. Examples of such combinations include the following embodiments (1) to (7). When the composition contains two or more types of chromatic pigments and exhibits black in combination of two or more chromatic pigments, the composition of the present invention can be preferably used as a composition for forming an infrared transmission filter. (1) Embodiment containing a red pigment and a blue pigment. (2) Embodiment containing a red pigment, a blue pigment and a yellow pigment. (3) Embodiment containing a red pigment, a blue pigment, a yellow pigment and a purple pigment. (4) Embodiment containing a red pigment, a blue pigment, a yellow pigment, a purple pigment and a green pigment. (5) Embodiment containing a red pigment, a blue pigment, a yellow pigment and a green pigment. (6) Embodiment containing a red pigment, a blue pigment and a green pigment. (7) Embodiment containing a yellow pigment and a purple pigment.

[0039] - White or colorless pigments (white pigments) - Examples of white or colorless pigments (hereinafter also referred to as white pigments) include inorganic pigments such as titanium dioxide, strontium titanate, barium titanate, zinc oxide, magnesium oxide, zirconium oxide, aluminum oxide, barium sulfate, silica, talc, mica, aluminum hydroxide, calcium silicate, aluminum silicate, and zinc sulfide. White colorants can be those white pigments described in paragraphs 0040 to 0043 of International Publication No. 2022 / 085485.

[0040] White pigments are preferably silica particles. Examples of silica particles include silica particles in which multiple spherical silica particles are linked together in a bead-like manner, silica particles in which multiple spherical silica particles are linked together in a planar manner, silica particles with a hollow structure, and solid silica particles.

[0041] -Black Pigment- The black pigment is not particularly limited and any known pigment can be used. The black pigment may be an inorganic black pigment or an organic black pigment. In this specification, the term "black pigment" refers to a pigment that exhibits absorption over the entire wavelength range of 400 to 700 nm.

[0042] Examples of inorganic black pigments include carbon black, titanium black, and graphite, with carbon black and titanium black being preferred, and titanium black being more preferred. Titanium black refers to black particles containing titanium atoms, with lower-order titanium oxide and titanium oxynitride being preferred. The titanium black used can be the titanium black described in paragraph 0044 of International Publication No. 2022 / 085485. Zirconium nitride powder described in Japanese Patent Application Publication No. 2023-048173 can also be used as the inorganic black pigment.

[0043] Examples of organic black pigments include bisbenzofuranone pigments, azomethine pigments, perylene pigments, and azo pigments, with bisbenzofuranone pigments and perylene pigments being preferred. The organic black pigment can be a compound described in paragraph 0166 of International Publication No. 2022 / 065215. Alternatively, perylene black (Lumogen Black FK4280, etc.) described in paragraphs 0016-0020 of Japanese Patent Publication No. 2017-226821, black azo pigments described in Japanese Patent Publication No. 2022-121935, diketopyrrolopyrrole compounds described in Japanese Patent Publication No. 2021-172735, and bipyrrolinone compounds described in Japanese Patent Publication No. 2024-530550 may also be used as organic black pigments.

[0044] - Infrared Absorbing Pigments - Infrared absorbing pigments are preferably compounds having a maximum absorption wavelength longer than 700 nm. They are preferably compounds having a maximum absorption wavelength in the range of 700 nm to 1800 nm, more preferably compounds having a maximum absorption wavelength in the range of 700 nm to 1400 nm, even more preferably compounds having a maximum absorption wavelength in the range of 700 nm to 1200 nm, and particularly preferably compounds having a maximum absorption wavelength in the range of 700 nm to 1000 nm. Furthermore, the absorbance A of the infrared absorbing pigment at a wavelength of 500 nm is also specified. １ and absorbance A at the maximum absorption wavelength ２ Ratio A １ / A ２ It is preferable that the ratio is 0.08 or less, and more preferably 0.04 or less. Furthermore, the infrared absorbing pigment is preferably a pigment, and more preferably an organic pigment.

[0045] Examples of infrared-absorbing pigments include pyrrolopyrrole pigments, cyanine pigments, squarylium pigments, phthalocyanine pigments, naphthalocyanine pigments, quaterylene pigments, merocyanine pigments, crokonium pigments, oxonol pigments, iminium pigments, dithiol pigments, triarylmethane pigments, pyromethene pigments, azomethine pigments, anthraquinone pigments, dibenzofuranone pigments, dithiolene metal complex pigments, metal oxides, and metal borides. Specific examples of these include the compounds described in paragraph 0114 of International Publication No. 2022 / 065215. Furthermore, as infrared absorbing colorants, the compounds described in paragraph 0121 of International Publication No. 2022 / 065215, the squarylium compounds described in Japanese Patent Publication No. 2020-075959, the copper complex described in Korean Patent Publication No. 10-2019-0135217, the croconic acid compounds described in Japanese Patent Publication No. 2021-195515, the infrared absorbing dyes described in Japanese Patent Publication No. 2022-022070, and International Publication No. 2019 / 02 Croconium compounds described in Patent Publication No. 1767, compounds described in Japanese Patent Publication No. 2019-127549, compounds described in International Publication No. 2022 / 059619, compounds described in Japanese Patent Publication No. 2022-151682, squarylium compounds described in Japanese Patent Publication No. 2022-188858, compounds described in Japanese Patent Publication No. 2022-184710, compounds described in Japanese Patent Publication No. 2022-189736, Japanese Patent Publication No. 2023-004570 The squarylium compounds described in publication No. 2019 / 230660, the squarylium compounds described in International Publication No. 2020 / 218615, the diiminium compounds described in Japanese Patent Publication No. 2023-068643, the squarylium compounds described in Japanese Patent Publication No. 2023-052770, the phthalocyanine compounds described in Korean Patent Publication No. 10-2022-0163680, Japanese Patent Publication No. 2023- Indigo monoboron complex described in Japanese Patent Publication No. 073064, phthalocyanine compound described in Japanese Patent Application Publication No. 2023-066025, phthalocyanine compound described in Japanese Patent Application Publication No. 2020-041127, indigo compound described in Japanese Patent Application Publication No. 2023-073064, indigo compound described in Korean Published Patent No. 10-2023-0016355, squarylium compound described in International Publication No. 2019 / 230570,Diiminium compounds described in Japanese Patent Publication No. 2023-095824, compounds described in Japanese Patent Publication No. 2023-159964, compounds described in Japanese Patent Publication No. 2023-176615, compounds described in Japanese Patent Publication No. 2024-500537, phthalocyanine compounds described in Japanese Patent Publication No. 2024-019936, compounds described in Korean Registered Patent No. 10-2575190, and poly compounds described in Japanese Patent Publication No. 2024-017061 Methine compounds, boron derivatives described in Chinese Patent Application Publication No. 116715690, phthalocyanine compounds described in Japanese Patent Publication No. 2024-020454, compounds described in Chinese Patent Application Publication No. 116891482, compounds described in Japanese Patent Publication No. 2024-511242, near-infrared absorbing dyes described in Japanese Patent Publication No. 2024-047265, compounds described in Japanese Patent Publication No. 2024-043503, Japanese Patent Publication No. 2021- The extended phthalocyanine described in Japanese Patent Publication No. 047255, the compound described in International Publication No. 2024 / 058103, the compound described in Japanese Patent Application Publication No. 2024-071077, the infrared absorber described in U.S. Patent Application Publication No. 2021 / 036251, the absorber described in Japanese Patent Application Publication No. 2024-079641, the cyanine compound described in International Publication No. 2024 / 106293, and the Korean Registered Patent No. 10-2622663 are described in Japanese Patent Application Publication No. 10-2622663. The squarylium compounds listed, the squarylium compounds described in Japanese Patent Publication No. 2024-071077, the cyanine compounds described in International Publication No. 2024 / 128016, the anthraquinone dyes described in International Publication No. 2024 / 041944, the xanthene compounds described in U.S. Patent Application Publication No. 2024 / 0124714, and the tropylium compounds described in Japanese Patent Publication No. 2024-126341 can also be used.

[0046] (Dyes) The colorant used in the curable composition of the present invention may further contain dyes. The dye content is preferably 100 parts by mass or less, more preferably 80 parts by mass or less, and even more preferably 70 parts by mass or less, per 100 parts by mass of pigment. Only one type of dye may be used, or two or more types may be used in combination.

[0047] Examples of dyes include chromatic dyes, black dyes, and infrared-absorbing dyes. There are no particular restrictions on chromatic 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 pyromethene dyes. Examples of black dyes include bisbenzofuranone dyes, azomethine dyes, perylene dyes, and azo dyes. Examples of infrared-absorbing dyes include pyrrolopyrrole dyes, cyanine dyes, squarylium dyes, phthalocyanine dyes, naphthalocyanine dyes, quaterylene dyes, merocyanine dyes, croconium dyes, oxonol dyes, iminium dyes, dithiol dyes, triarylmethane dyes, pyromethene dyes, azomethine dyes, anthraquinone dyes, and dibenzofuranone dyes.

[0048] A pigment polymer can also be used as the dye. The pigment polymer has two or more pigment structures in one molecule, preferably three or more. There is no particular upper limit, but it can be 100 or less. The multiple pigment structures in one molecule may be the same pigment structure or different pigment structures. The weight-average molecular weight (Mw) of the pigment polymer is preferably 2000 to 50000. The lower limit is more preferably 3000 or more, and even more preferably 6000 or more. The upper limit is more preferably 30000 or less, and even more preferably 20000 or less. The pigment polymer can also be a compound described in Japanese Patent Publication No. 2011-213925, Japanese Patent Publication No. 2013-041097, Japanese Patent Publication No. 2015-028144, Japanese Patent Publication No. 2015-030742, International Publication No. 2016 / 031442, etc.

[0049] As chromatic dyes or the chromatic pigments mentioned above, the following are used: the triarylmethane dye polymer described in Korean Published Patent No. 10-2020-0028160, the xanthene compound described in Japanese Patent Application Publication No. 2020-117638, the phthalocyanine compound described in International Publication No. 2020 / 174991, the isoindoline compound described in Japanese Patent Application Publication No. 2020-160279 or salts thereof, the compound represented by Formula 1 described in Korean Published Patent No. 10-2020-0069442, the compound represented by Formula 1 described in Korean Published Patent No. 10-2020-0069730, and the compound described in Korean Published Patent No. 10-2020-0069070. The following compounds can be used: the compound represented by formula 1 described in [translate], the compound represented by formula 1 described in Korean Published Patent No. 10-2020-0069067, the compound represented by formula 1 described in Korean Published Patent No. 10-2020-0069062, the zinc halide phthalocyanine pigment described in Japanese Patent No. 6809649, the isoindoline compound described in Japanese Patent Application Publication No. 2020-180176, the phenothiazine compound described in Japanese Patent Application Publication No. 2021-187913, the zinc halide phthalocyanine described in International Publication No. 2022 / 004261, and the zinc halide phthalocyanine described in International Publication No. 2021 / 250883. Other colorants may be rotaxanes, and the pigment skeleton may be used in the cyclic structure of the rotaxane, in the rod-shaped structure, or in both structures. Other colorants include the quinophthalone compound represented by Formula 1 in Korean Published Patent No. 10-2020-0030759, the polymer dye described in Korean Published Patent No. 10-2020-0061793, the colorant described in Japanese Patent Publication No. 2022-029701, the isoindoline compound described in International Publication No. 2022 / 014635, and the aluminum phthalocyanine compound described in International Publication No. 2022 / 024926. The substance, the compound described in Japanese Patent Publication No. 2022-045895, the compound described in International Publication No. 2022 / 050051, the compound described in Japanese Patent Publication No. 2020-090676, the compound described in Japanese Patent Publication No. 2020-055956, the compound described in Japanese Patent Publication No. 2021-031681, the compound described in Japanese Patent Publication No. 2022-056354, the compound described in U.S. Patent Application Publication No. 2021 / 0355327,Compounds described in International Publication No. 2022 / 065357, compounds described in Japanese Patent Publication No. 2020-045436, compounds described in Korean Patent Publication No. 10-2021-0146726, compounds described in Japanese Patent Publication No. 2018-178039, compounds described in Chinese Patent Application Publication No. 113881244, compounds described in Chinese Patent Application Publication No. 113881245, compounds described in Chinese Patent Application Publication No. 113881246, compounds described in Japanese Patent Publication No. 2022-104822, compounds described in Japanese Patent Publication No. 2022-096701, Japanese Patent Publication No. 20 The compound described in Japanese Patent Publication No. 20-023652, the green pigment described on pages 80-84 of the Journal of the Color Materials Association (published in 2022), the compound described in Japanese Patent Application Publication No. 2022-143135, the compound described in Japanese Patent Application Publication No. 2022-140287, the compound described in International Publication No. 2022 / 136308, the perylene compound described in Chinese Patent Application Publication No. 113061349, the cyan pigment described in Korean Patent Application Publication No. 10-2017-0018993, the isoindoline compound described in Japanese Patent Application Publication No. 2020-180176, the compound described in Japanese Patent Application Publication No. 2023-013209, Compounds described in Japanese Patent Publication No. 2023-013166, xanthene compounds described in International Publication No. 2023 / 286526, compounds described in Japanese Patent Publication No. 2021-155746, compounds described in Japanese Patent Publication No. 2021-155747, compounds described in Japanese Patent Publication No. 2021-155748, compounds described in Japanese Patent Publication No. 2021-155749, compounds described in International Publication No. 2018 / 051876, compounds described in Japanese Patent Publication No. 2020-083981, compounds described in Japanese Patent Publication No. 2023-056463, compounds described in Japanese Patent Publication No. 2023-515473, Japanese Patent Publication Compounds described in Japanese Patent Publication No. 2024-043497, compounds described in Japanese Patent Application Publication No. 2021-157040, azo pigments described in Japanese Patent Application Publication No. 2024-063075, compounds described in Japanese Patent Application Publication No. 2022-018967, quinophthalone pigments described in Japanese Patent Application Publication No. 2024-057558, compounds described in International Publication No. 2020 / 170957, compounds described in Chinese Patent Application Publication No. 117209388, isoindoline compounds described in Japanese Patent Application Publication No. 2024-079043, phthalocyanine dyes described in Korean Patent Publication No. 10-2022-0026920,Compounds described in International Publication No. 2020 / 203514, squarylium compounds described in Japanese Patent Publication No. 2020-183510, squarylium compounds described in Korean Patent Publication No. 10-2024-0030438, dyes described in Chinese Patent Application Publication No. 115947727, phthalocyanine compounds described in Chinese Patent Application Publication No. 117700418, xanthene compounds described in Japanese Patent Application Publication No. 2024-144198, xanthene compounds described in Japanese Patent Application Publication No. 2020-125455, acidic dyes described in Japanese Patent Application Publication No. 2024-132917, triarylmethane compounds described in Japanese Patent Application Publication No. 2024-132927, etc., can also be used.

[0050] The colorant content in the total solids of the curable composition is preferably 1 to 70% by mass. The upper limit is preferably 65% ​​by mass or less, and more preferably 60% by mass or less. The lower limit is preferably 10% by mass or more, more preferably 20% by mass or more, even more preferably 30% by mass or more, even more preferably 40% by mass or more, and particularly preferably 50% by mass or more. Only one type of colorant may be used, or two or more types may be used in combination.

[0051] The pigment content in the total solids of the curable composition is preferably 1 to 70% by mass. The upper limit is preferably 65% ​​by mass or less, and more preferably 60% by mass or less. The lower limit is preferably 10% by mass or more, more preferably 20% by mass or more, even more preferably 30% by mass or more, even more preferably 40% by mass or more, and particularly preferably 50% by mass or more. Only one type of pigment may be used, or two or more types may be used in combination.

[0052] <<Photopolymerization Initiator>> The curable composition of the present invention contains a photopolymerization initiator. The photopolymerization initiator is preferably a photoradical polymerization initiator.

[0053] (Glyoxylate compound) The photopolymerization initiator included in the curable composition of the present invention is one that contains a glyoxylate compound.

[0054] Examples of glyoxylate compounds include the compound represented by formula (1) and the compound represented by formula (2), with the compound represented by formula (1) being preferred.

[0055]

[0056] In formula (1), Ar １ R represents an m1+n1 valent group containing at least one selected from the group consisting of aromatic rings and heteroaromatic rings, １ R represents an alkyl group. ２ represents a halogen atom, nitro group, cyano group, or acyl group, n1 represents an integer from 1 to 4, and m1 represents an integer from 0 to 2; in formula (2), Ar １１ R represents an m²+1 valent group containing at least one selected from the group consisting of aromatic rings and heteroaromatic rings, １１ R represents an n-2 valent organic group. １２ n² represents a halogen atom, nitro group, cyano group, or acyl group, n² represents an integer from 2 to 6, and m² represents an integer from 0 to 2.

[0057] -Ar １ Regarding - In equation (1), Ar １ This represents an m1+n1 valent group containing at least one selected from the group consisting of aromatic rings and heteroaromatic rings.

[0058] Ar １ Examples of m1+n1 valent groups represented by include m1+n1 valent aromatic ring groups, m1+n1 valent heterocyclic groups, groups in which two or more aromatic ring groups are linked by a single bond or linking group, groups in which two or more heterocyclic groups are linked by a single bond or linking group, and groups in which an aromatic ring group and a heterocyclic group are linked by a single bond or linking group. Examples of linking groups that link aromatic rings together, heterocyclic groups together, or aromatic ring groups and heterocyclic groups include -CH ２ -, -O-, -CO-, -S-, -NR ｘ - And combinations thereof, etc. are examples. ｘ This represents a hydrogen atom, alkyl group, alkenyl group, alkynyl group, aryl group, or heterocyclic group.

[0059] Ar in equation (1)１ It is preferable that the group is represented by any of the formulas (Ar1-1) to (Ar1-14), more preferably by the formula (Ar1-1), (Ar1-6), or (Ar1-8), and even more preferably by the formula (Ar1-1).

[0060] In the formula, * represents the bond with the glyoxylate group in formula (1), and the wavy line represents R in formula (1). ２ This represents a combination of n1 and m1, where n1 is an integer from 1 to 4, m1 is an integer from 0 to 2, and Ar Ａ１ R represents an arylene group or a heteroarylene group. Ａ１ ~R Ａ９ Each of these independently represents a hydrogen atom or a monovalent organic group.

[0061] R Ａ１ ~R Ａ９Examples of monovalent organic groups represented by include alkyl groups, alkenyl groups, alkynyl groups, aryl groups, and heterocyclic groups. The number of carbon atoms in an alkyl group is preferably 1 to 15, and more preferably 1 to 10. The alkyl group may be linear, branched, or cyclic. The alkyl group may have substituents. Examples of substituents include halogen atoms, aryl groups, and heterocyclic groups. The number of carbon atoms in an alkenyl group is preferably 2 to 15, and more preferably 2 to 10. The alkenyl group may be linear, branched, or cyclic. The alkenyl group may have substituents. Examples of substituents include halogen atoms, aryl groups, and heterocyclic groups. The number of carbon atoms in an alkynyl group 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 substituents. Examples of substituents include halogen atoms, aryl groups, and heterocyclic groups. The aryl group has 6 to 20 carbon atoms, more preferably 6 to 12, even more preferably 6 to 10, and particularly preferably 6 carbon atoms. The aryl group may have substituents. Examples of substituents include halogen atoms, alkyl groups, alkenyl groups, alkynyl groups, and heterocyclic groups. The heterocyclic group is preferably a 5-membered or 6-membered ring. The heteroatoms of the heterocyclic group are preferably oxygen, nitrogen, and sulfur atoms. The number of heteroatoms of the heterocyclic group is preferably 1 to 3. The heterocyclic group may have substituents. Examples of substituents include halogen atoms, alkyl groups, alkenyl groups, alkynyl groups, and aryl groups.

[0062] Ar Ａ１ The symbol represents an arylene group or a heteroarylene group, and an arylene group is preferred. The number of carbon atoms in the arylene group is preferably 6 to 20, more preferably 6 to 12, even more preferably 6 to 10, and particularly preferred to be 6. The heteroarylene group is preferably a 5-membered ring or a 6-membered ring. The heteroatoms in the heteroarylene group are preferably oxygen, nitrogen, and sulfur atoms. The number of heteroatoms in the heteroarylene group is preferably 1 to 3.

[0063] n1 and m1 in equations (Ar1-1) to (Ar1-14) are equivalent to n1 and m1 in equation (1).

[0064] -R １ Regarding - R in equation (1) １ R represents an alkyl group. １ The alkyl group represented by is preferably 1 to 15 carbon atoms, more preferably 1 to 10, and even more preferably 1 to 5 carbon atoms. The alkyl group may be linear, branched, or cyclic, but is preferably linear or branched, and more preferably linear. １ The alkyl group represented by may have substituents, but it is preferable that it be an unsubstituted alkyl group. Examples of substituents include aryl groups, heteroaryl groups, alkoxy groups, alkylthio groups, alkylamino groups, aryloxy groups, arylthio groups, arylamino groups, heteroaryloxy groups, heteroarylthio groups, heteroarylamino groups, cyano groups, nitro groups, hydroxyl groups, carboxyl groups, halogen atoms, and acyl groups.

[0065] -R ２ Regarding - R in equation (1) ２ This represents a halogen atom, a nitro group, a cyano group, or an acyl group, preferably a nitro group or an acyl group, and more preferably an acyl group.

[0066] R ２ Examples of halogen atoms represented by this symbol include fluorine, chlorine, bromine, and iodine.

[0067] R ２ The acyl group represented by is -COR ２０１ It is preferable that the group is represented by R. ２０１ R represents an alkyl group, an aryl group, or a heteroaryl group, and is preferably an aryl group. ２０１The 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 substituents. Examples of substituents include aryl groups, heteroaryl groups, alkoxy groups, alkylthio groups, alkylamino groups, aryloxy groups, arylthio groups, arylamino groups, heteroaryloxy groups, heteroarylthio groups, heteroarylamino groups, cyano groups, nitro groups, hydroxyl groups, carboxyl groups, halogen atoms, and acyl groups. ２０１ The aryl group represented by is preferably 6 to 20 carbon atoms, more preferably 6 to 12, even more preferably 6 to 10, and particularly preferably 6 carbon atoms. The aryl group may have substituents. Examples of substituents include alkyl groups, aryl groups, heteroaryl groups, alkoxy groups, alkylthio groups, alkylamino groups, aryloxy groups, arylthio groups, arylamino groups, heteroaryloxy groups, heteroarylthio groups, heteroarylamino groups, cyano groups, nitro groups, hydroxyl groups, carboxyl groups, halogen atoms, and acyl groups, with alkyl groups being preferred. ２０１ The number of carbon atoms constituting the ring of the heteroaryl group represented by is preferably 1 to 15, and more preferably 1 to 10. Examples of heteroatoms constituting the ring of the heteroaryl group include nitrogen atoms, oxygen atoms, and sulfur atoms. The number of heteroatoms constituting the ring of the heteroaryl group is preferably 1 to 3, and more preferably 1 to 2. The heteroaryl group may be a monoring or a fused ring. The heteroaryl group may have substituents. Examples of substituents include alkyl groups, aryl groups, heteroaryl groups, alkoxy groups, alkylthio groups, alkylamino groups, aryloxy groups, arylthio groups, arylamino groups, heteroaryloxy groups, heteroarylthio groups, heteroarylamino groups, cyano groups, nitro groups, hydroxyl groups, carboxyl groups, halogen atoms, and acyl groups, with alkyl groups being preferred.

[0068] -Regarding n1- In equation (1), n1 represents an integer from 1 to 4, and is preferably 1 or 2, and more preferably 1.

[0069] -Regarding m1- In equation (1), m1 represents an integer between 0 and 2, preferably 0 or 1, and more preferably 1.

[0070] -Ar １１ Regarding - Ar in equation (2) １１ This represents an m²+1 valent group containing at least one selected from the group consisting of aromatic rings and heteroaromatic rings.

[0071] Ar １１ Examples of m²+1 valent groups represented by include m²+1 valent aromatic ring groups, m²+1 valent heterocyclic groups, groups in which two or more aromatic ring groups are linked by a single bond or a linking group, groups in which two or more heterocyclic groups are linked by a single bond or a linking group, and groups in which an aromatic ring group and a heterocyclic group are linked by a single bond or a linking group. Examples of linking groups that link aromatic rings together, heterocyclic groups together, or aromatic ring groups and heterocyclic groups include -CH ２ -, -O-, -CO-, -S-, -NR ｘ - And combinations thereof, etc. are examples. ｘ This represents a hydrogen atom, alkyl group, alkenyl group, alkynyl group, aryl group, or heterocyclic group.

[0072] Ar in equation (2) １１ It is preferable that the group is represented by any of the formulas (Ar2-1) to (Ar2-14), more preferably by the formula (Ar2-1), (Ar2-6), or (Ar2-8), and even more preferably by the formula (Ar2-1).

[0073] In the formula, * represents the bond with the glyoxylate group in formula (2), and the wavy line represents R in formula (2). １２ This represents a combination with, where m² represents an integer between 0 and 2, and Ar Ｂ１ R represents an arylene group or a heteroarylene group. Ｂ１ ~R Ｂ９ Each of these independently represents a hydrogen atom or a monovalent organic group.

[0074] R Ｂ１ ~R Ｂ９Examples of monovalent organic groups represented by include alkyl groups, alkenyl groups, alkynyl groups, aryl groups, and heterocyclic groups. The number of carbon atoms in an alkyl group is preferably 1 to 15, and more preferably 1 to 10. The alkyl group may be linear, branched, or cyclic. The alkyl group may have substituents. Examples of substituents include halogen atoms, aryl groups, and heterocyclic groups. The number of carbon atoms in an alkenyl group is preferably 2 to 15, and more preferably 2 to 10. The alkenyl group may be linear, branched, or cyclic. The alkenyl group may have substituents. Examples of substituents include halogen atoms, aryl groups, and heterocyclic groups. The number of carbon atoms in an alkynyl group 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 substituents. Examples of substituents include halogen atoms, aryl groups, and heterocyclic groups. The aryl group has 6 to 20 carbon atoms, more preferably 6 to 12, even more preferably 6 to 10, and particularly preferably 6 carbon atoms. The aryl group may have substituents. Examples of substituents include halogen atoms, alkyl groups, alkenyl groups, alkynyl groups, and heterocyclic groups. The heterocyclic group is preferably a 5-membered or 6-membered ring. The heteroatoms of the heterocyclic group are preferably oxygen, nitrogen, and sulfur atoms. The number of heteroatoms of the heterocyclic group is preferably 1 to 3. The heterocyclic group may have substituents. Examples of substituents include halogen atoms, alkyl groups, alkenyl groups, alkynyl groups, and aryl groups.

[0075] Ar Ｂ１ The symbol represents an arylene group or a heteroarylene group, and an arylene group is preferred. The number of carbon atoms in the arylene group is preferably 6 to 20, more preferably 6 to 12, even more preferably 6 to 10, and particularly preferred to be 6. The heteroarylene group is preferably a 5-membered ring or a 6-membered ring. The heteroatoms in the heteroarylene group are preferably oxygen, nitrogen, and sulfur atoms. The number of heteroatoms in the heteroarylene group is preferably 1 to 3.

[0076] In equations (Ar2-1) to (Ar2-14), m1 is equivalent to m2 in equation (2).

[0077] -R １１ Regarding R in equation (2) １１ This represents an n-divalent organic group. Examples of n-divalent organic groups include hydrocarbon groups; two or more hydrocarbon groups bonded together by a single bond, -O-, -S-, -CO-, -COO-, -OCO-, -SO- ２ Examples include groups bonded via -, -NH-, -NHCO-, -CONH-, -NHCONH-, -NHCOO-, or -OCONH-.

[0078] The hydrocarbon groups mentioned above include aliphatic hydrocarbon groups and aromatic hydrocarbon groups, with aliphatic hydrocarbon groups being preferred. The number of carbon atoms in the aliphatic hydrocarbon group is preferably 1 to 30, more preferably 1 to 20, and even more preferably 1 to 15. The aliphatic hydrocarbon group may be linear, branched, or cyclic. The cyclic aliphatic hydrocarbon group may be monocyclic or fused. The cyclic aliphatic hydrocarbon group may also have a crosslinking structure. The number of carbon atoms in the aromatic hydrocarbon group is preferably 6 to 30, more preferably 6 to 20, and even more preferably 6 to 10. The hydrocarbon group may have substituents. Examples of substituents include alkyl groups, aryl groups, heteroaryl groups, alkoxy groups, alkylthio groups, alkylamino groups, aryloxy groups, arylthio groups, arylamino groups, heteroaryloxy groups, heteroarylthio groups, heteroarylamino groups, cyano groups, nitro groups, hydroxyl groups, carboxyl groups, halogen atoms, and acyl groups.

[0079] -R １２ Regarding R in equation (2) １２ R represents a halogen atom, a nitro group, a cyano group, or an acyl group, preferably a nitro group or an acyl group, and more preferably an acyl group. １２ For details of the above base represented by, see R in equation (1) ２ The content is the same as explained earlier, and the preferred range is also the same.

[0080] -Regarding n2- In equation (2), n2 represents an integer between 2 and 6, preferably between 2 and 4, and more preferably 2.

[0081] -Regarding m²- In equation (2), m² represents an integer between 0 and 2, preferably 0 or 1, and more preferably 1.

[0082] The glyoxylate compound is preferably a compound represented by formula (3).

[0083] In formula (3), R １０１ R represents an alkyl group. １１１ ~R １１５ Each of these independently represents a hydrogen atom, an alkyl group, an aryl group, a heteroaryl group, an alkoxy group, an alkylthio group, an alkylamino group, an aryloxy group, an arylthio group, an arylamino group, a heteroaryloxy group, a heteroarylthio group, a heteroarylamino group, a cyano group, a nitro group, a hydroxyl group, a carboxyl group, a halogen atom, or an acyl group.

[0084] R in equation (3) １０１ R in equation (1) １ This is synonymous with the following, and the preferred range is also similar. １１１ ~R １１５ It is preferable that it be a hydrogen atom.

[0085] Specific examples of glyoxylate compounds include compounds I-1 to I-3 described in the examples below. A commercially available example of a glyoxylate compound is Esacure 563 (manufactured by IGM Resins B.V.).

[0086] (Other Photopolymerization Initiators) The photopolymerization initiator contained in the curable composition of the present invention may include a compound different from the glyoxylate compound (hereinafter also referred to as "other photopolymerization initiator"). By using the glyoxylate compound and other photopolymerization initiators in combination, it is possible to suppress pigment loss while mitigating the decrease in stability over time due to bases. When using the glyoxylate compound and other photopolymerization initiators in combination, the content of the other photopolymerization initiator is preferably 10 to 90 parts by mass per 100 parts by mass of the glyoxylate compound. The upper limit is preferably 80 parts by mass or less, and more preferably 70 parts by mass or less. The lower limit is preferably 20 parts by mass or more, and more preferably 30 parts by mass or more. Furthermore, it is also preferable that the photopolymerization initiator used in the present invention is substantially only the glyoxylate compound. According to this embodiment, the occurrence of discoloration caused by the photopolymerization initiator can be further suppressed. The term "substantially consisting of a glyoxylate compound" means that the glyoxylate compound content in the photopolymerization initiator is 99% by mass or more, preferably 99.9% by mass or more, and more preferably consisting solely of a glyoxylate compound.

[0087] Other photopolymerization initiators include halogenated hydrocarbon derivatives (e.g., compounds having a triazine skeleton, compounds having an oxadiazole skeleton, etc.), acylphosphine compounds, hexaarylbiimidazole compounds, oxime compounds, organic peroxides, thio compounds, ketone compounds, aromatic onium salts, α-hydroxyketone compounds, and α-aminoketone compounds. Other photopolymerization initiators are preferably trihalomethyltriazine compounds, benzyldimethylketal compounds, α-hydroxyketone compounds, α-aminoketone compounds, acylphosphine compounds, phosphine oxide compounds, metallocene compounds, oxime compounds, hexaarylbiimidazole compounds, onium compounds, benzothiazole compounds, benzophenone compounds, acetophenone compounds, cyclopentadiene-benzene-iron complexes, halomethyloxadiazole compounds, or 3-aryl-substituted coumarin compounds, more preferably oxime compounds, α-hydroxyketone compounds, α-aminoketone compounds, or acylphosphine compounds, even more preferably α-aminoketone compounds or oxime compounds, and particularly preferably oxime compounds.

[0088] Other photopolymerization initiators include the compounds described in paragraphs 0065 to 0111 of Japanese Patent Publication No. 2014-130173, the compounds described in Japanese Patent Publication No. 6301489, and MATERIAL STAGE 37-60p, vol. 19, No. 3. Peroxide-based photopolymerization initiators described in 2019, photopolymerization initiators described in International Publication No. 2018 / 221177, photopolymerization initiators described in International Publication No. 2018 / 110179, photopolymerization initiators described in JP 2019-043864, photopolymerization initiators described in JP 2019-044030, peroxide-based initiators described in JP 2019-167313, aminoacetophenone-based initiators having an oxazolidine group described in JP 2020-055992, JP 2013- Oxime-based photopolymerization initiator described in Japanese Patent Publication No. 190459, polymer described in Japanese Patent Application Publication No. 2020-172619, compound represented by formula 1 described in International Publication No. 2020 / 152120, compound described in Japanese Patent Application Publication No. 2021-181406, photopolymerization initiator described in Japanese Patent Application Publication No. 2022-013379, compound represented by formula (1) described in Japanese Patent Application Publication No. 2022-015747, fluorine-containing fluorene oxime ester-based photoinitiator described in Japanese Patent Application Publication No. 2021-507058, Chinese Patent Application Publication No. 11 Initiators described in Specification No. 0764367, initiators described in Japanese Patent Publication No. 2022-518535, initiators described in International Publication No. 2021 / 175855, compounds described in Taiwan Patent Application Publication No. 202200534, compounds described in Japanese Patent Application Publication No. 2022-078550, compounds described in Korean Published Patent No. 10-2017-0087330, compounds described in International Publication No. 2022 / 075452, oxime ester compounds described in Chinese Patent Application Publication No. 110066225, Korean Compounds described in Japanese Patent Publication No. 10-2022-0076157, compounds described in paragraphs 0042-0062 of International Publication No. 2019 / 013112 having a triarylamine or N-arylcarbazole skeleton, oxime ester-based photopolymerization initiators described in Japanese Patent Publication No. 7219378, photopolymerization initiators described in Korean Published Patent No. 10-2021-0146174, photopolymerization initiators described in International Publication No. 2019 / 013112, photopolymerization initiators described in Japanese Patent Publication No. 2023-033731,Initiators described in Japanese Patent Publication No. 2022-515524, initiators described in Japanese Patent Publication No. 2023-517304, initiators described in Chinese Patent Application Publication No. 114149517, aminoketone compounds described in Chinese Patent Application Publication No. 115925596, compounds described in Japanese Patent Application Publication No. 2023-159489, compounds described in Japanese Patent Application Publication No. 2023-159487, Taiwan Patent Application Publication No. 2 Compounds described in Patent Publication No. 02336003, compounds described in Chinese Patent Application Publication No. 113527138, organosilicon compounds described in Japanese Patent Publication No. 2022-502526, oxime compounds described in Korean Published Patent No. 10-2017-0009794, photopolymerization initiators described in Korean Published Patent No. 10-2023-0033862, oxime compounds described in Japanese Patent Publication No. 2019-519518 Oxime ester compounds, photopolymerization initiators of polyfunctional polymers described in JP 2024-517534, photopolymerization initiators described in International Publication No. 2024 / 085227, compounds described in JP 2024-521379, photopolymerization initiators described in JP 2024-523053, oxime ester initiators described in Chinese Patent Application Publication No. 117510396, Chinese Patent Application Publication No. 111 Examples include oxime compounds described in Japanese Patent Publication No. 752099, photopolymerization initiators described in Japanese Patent Application Publication No. 2024-124479, photopolymerization initiators described in Japanese Patent Publication No. 2024-537185, photopolymerization initiators described in Japanese Patent Publication No. 2024-535245, aminoketone compounds described in Japanese Patent Publication No. 2024-534719, and oxime ester compounds described in Japanese Patent Application Publication No. 2024-149305.

[0089] Specific examples of hexaarylbiimidazole compounds include 2,2',4-tris(2-chlorophenyl)-5-(3,4-dimethoxyphenyl)-4,5-diphenyl-1,1'-biimidazole.

[0090] Commercially available α-hydroxyketone compounds include Omnirad 184, Omnirad 1173, Omnirad 2959, and Omnirad 127 (all manufactured by IGM Resins B.V.), and Irgacure 184, Irgacure 1173, Irgacure 2959, and Irgacure 127 (all manufactured by BASF). Commercially available α-aminoketone compounds include Omnirad 907, Omnirad 369, Omnirad 369E, and Omnirad 379EG (all manufactured by IGM Resins B.V.), and Irgacure 907, Irgacure 369, Irgacure 369E, and Irgacure 379EG (all manufactured by BASF). Commercially available acylphosphine compounds include Omnirad 819 and Omnirad TPO (both manufactured by IGM Resins B.V.), and Irgacure 819 and Irgacure TPO (both manufactured by BASF).

[0091] Examples of oxime compounds include the compounds described in paragraph 0142 of International Publication No. 2022 / 085485, the compounds described in Japanese Patent No. 5430746, the compounds described in Japanese Patent No. 5647738, the compounds represented by general formula (1) and the compounds described in paragraphs 0022 to 0024 of Japanese Patent Publication No. 2021-173858, and the compounds represented by general formula (1) and the compounds described in paragraphs 0117 to 0120 of Japanese Patent Publication No. 2021-170089. Specific examples of oxime compounds include 3-benzoyloxyiminobutan-2-one, 3-acetoxyiminobutan-2-one, 3-propionyloxyiminobutan-2-one, 2-acetoxyiminopentan-3-one, 2-acetoxyimino-1-phenylpropane-1-one, 2-benzoyloxyimino-1-phenylpropane-1-one, 3-(4-toluenesulfonyloxy)iminobutan-2-one, 2-ethoxycarbonyloxyimino-1-phenylpropane-1-one, and 1-[4-(phenylthio)phenyl]-3-cyclohexyl-propane-1,2-dione-2-(O-acetyloxime). Commercially available products include Irgacure OXE01, Irgacure OXE02, Irgacure OXE03, Irgacure OXE04, Irgacure OXE05 (all manufactured by BASF), TR-PBG-301, TR-PBG-304, TR-PBG-305, TR-PBG-309, TR-PBG-3054, TR-PBG-3057, TR-PBG-314, TR-PBG-327, TR-PBG-345, TR-PBG-346, TR- Examples include PBG-358, TR-PBG-365, TR-PBG-380, TR-PBG-610, TR-PBG-A, TR-PBG-B (all manufactured by TRONLY), and ADEKA Optomer N-1919 (manufactured by ADEKA Corporation, photopolymerization initiator 2 described in Japanese Patent Publication No. 2012-014052). Furthermore, it is also preferable to use compounds that do not produce color or compounds that are highly transparent and resistant to discoloration as oxime compounds. Examples of commercially available products include ADEKA Arclus NCI-730, NCI-831, NCI-831E, and NCI-930 (all manufactured by ADEKA Corporation).

[0092] As other photoinitiators, 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 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 having a substituent having a hydroxy group bonded to a carbazole skeleton, and a compound described in paragraphs 0143 to 0149 of International Publication No. 2022 / 085485 can also be used.

[0093] As other photoinitiators, a compound represented by formula (OX-1) can also be used.

[0094] In formula (OX-1), X １ａ represents a divalent linking group containing at least one selected from the group consisting of an aromatic ring and a heterocyclic ring, R 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 represent a hydrogen atom or an alkyl group, Alk １ and Alk ２ each independently represent an alkyl group, R ３ａ and R ４ａ may combine to form a ring, Alk １ and Alk ２ may combine to form a ring, and n represents 0 or 1.

[0095] As the divalent linking group represented by X in formula (OX-1), a divalent aromatic ring group, a divalent heterocyclic ring group, a divalent group in which two or more aromatic ring groups are bonded via a single bond or a linking group, a divalent group in which two or more heterocyclic ring groups are bonded via a single bond or a linking group, and a divalent group in which an aromatic ring group and a heterocyclic ring group are bonded via a single bond or a linking group can be mentioned. As the linking group for bonding the aromatic ring groups, the heterocyclic ring groups, or the aromatic ring group and the heterocyclic ring group, -CH １ａ -, -O-, -CO-, -S-, -NR ２ -, - and groups combining these can be mentioned. R ｘ - and R ｘrepresents a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group, an aryl group or a heterocyclic group.

[0096] X in formula (OX-1) １ａ is preferably a group represented by any of formulas (X-1) to (X-13), more preferably a group represented by formula (X-1), formula (X-2), formula (X-4), formula (X-6) or formula (X-8), and even more preferably a group represented by formula (X-2) or formula (X-6).

[0097] In the formula, R Ｘ１ to R Ｘ９ each independently represents a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group, an aryl group or a heteroaryl group, and * represents a bond.

[0098] R Ｘ１ to R Ｘ９ The alkyl group represented by R preferably has 1 to 15 carbon atoms, 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, a heteroaryl group, etc.

[0099] R Ｘ１ to R Ｘ９ The alkenyl group represented by R preferably has 2 to 15 carbon atoms, more preferably 2 to 10 carbon atoms. 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, a heteroaryl group, etc.

[0100] R Ｘ１ to R Ｘ９ The alkynyl group represented by R preferably has 2 to 15 carbon atoms, more preferably 2 to 10 carbon atoms. 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, a heteroaryl group, etc.

[0101] R Ｘ１ to R Ｘ９The number of carbon atoms in the aryl group represented by is preferably 6 to 20, more preferably 6 to 12, even more preferably 6 to 10, and particularly preferably 6. The aryl group may have substituents. Examples of substituents include halogen atoms, alkyl groups, alkenyl groups, alkynyl groups, and heteroaryl groups.

[0102] R Ｘ１ ~R Ｘ９ The heteroaryl group represented by is preferably a five-membered or six-membered ring. The heteroatoms of the heteroaryl group are preferably oxygen, nitrogen, and sulfur atoms. The number of heteroatoms of the heteroaryl group is preferably 1 to 3. The heteroaryl group may have substituents. Examples of substituents include halogen atoms, alkyl groups, alkenyl groups, alkynyl groups, and aryl groups.

[0103] R in equation (OX-1) １ａ represents a hydrogen atom or an acyl group, and an acyl group is preferred.

[0104] R in equation (OX-1) ２ａ R represents an alkyl group or an aryl group, and is preferably an alkyl group because the generated radical is highly reactive. ２ａ The number of carbon atoms in the alkyl group represented by is preferably 1 to 15, more preferably 1 to 10, even more preferably 1 to 5, and even more preferably 1 to 3. The alkyl group may be linear, branched, or cyclic, but is preferably linear or branched, and more preferably linear. The alkyl group may have substituents, but is preferably an unsubstituted alkyl group. ２ａ The alkyl group represented by is preferably an unsubstituted linear or branched alkyl group, and more preferably an unsubstituted linear alkyl group. ２ａ The number of carbon atoms in the aryl group represented by is preferably 6 to 20, more preferably 6 to 12, even more preferably 6 to 10, and particularly preferably 6. The aryl group may have substituents, but it is preferably an unsubstituted aryl group.

[0105] R in equation (OX-1) ３ａ and R ４ａEach of these independently represents a hydrogen atom or an alkyl group, and a hydrogen atom is preferred. ３ａ and R ４ａ The number of carbon atoms in the alkyl group represented by is preferably 1 to 15, more preferably 1 to 10, even more preferably 1 to 5, and even more preferably 1 to 3. The alkyl group may be linear, branched, or cyclic, but is preferably linear or branched, and more preferably linear. The alkyl group may have substituents, but is preferably an unsubstituted alkyl group. ３ａ and R ４ａ These may be bonded together to form a ring. The formed ring is preferably a five-membered or six-membered ring, and more preferably a five-membered or six-membered aliphatic hydrocarbon ring.

[0106] Alk in equation (OX-1) １ and Alk ２ Each of these independently represents an alkyl group. The number of carbon atoms in the alkyl group is preferably 1 to 15, more preferably 1 to 10, even more preferably 1 to 5, and even more preferably 1 to 3. The alkyl group may be linear, branched, or cyclic, but is preferably linear or branched, and more preferably linear. The alkyl group may have substituents, but is preferably an unsubstituted alkyl group. Alk １ and Alk ２ The elements may be bonded together to form a ring, and it is preferable that a ring is formed. The formed ring is preferably a five-membered or six-membered ring, more preferably a five-membered or six-membered aliphatic hydrocarbon ring, and even more preferably a cyclopentane ring or a cyclohexane ring.

[0107] In formula (OX-1), n ​​represents either 0 or 1, and is preferably 0.

[0108] Specific examples of compounds represented by formula (OX-1) include the compounds described in paragraphs 0092 to 0096 of Japanese Patent Publication No. 2012-113104 and the compounds described in paragraph 0041 of Japanese Patent Publication No. 2012-189997.

[0109] As an alternative photopolymerization initiator, the compound represented by formula (OX-2) can also be used.

[0110]

[0111] In formula (OX-2), R １ｂ and R ２ｂ Each of these independently represents a substituent, R ３ｂ ~R ７ｂ Each of these independently represents a hydrogen atom or a substituent, and Ar １ｂ represents an optionally substituted aryl group or an optionally substituted heteroaryl group, and n represents 0 or 1.

[0112] R １ｂ and R ２ｂ The substituents represented by include alkyl groups and aryl groups, with alkyl groups being preferred. The number of carbon atoms in the alkyl group is preferably 1 to 15, and more preferably 1 to 10. The alkyl group may be linear, branched, or cyclic. The alkyl group may have substituents. Examples of substituents include halogen atoms, aryl groups, alkenyl groups, alkynyl groups, and heteroaryl groups. The number of carbon atoms in the aryl group is preferably 6 to 20, more preferably 6 to 12, even more preferably 6 to 10, and particularly preferably 6. The aryl group may have substituents. Examples of substituents include halogen atoms, alkyl groups, alkenyl groups, alkynyl groups, and heteroaryl groups.

[0113] R ３ｂ ~R ７ｂ The substituents represented by include halogen atoms, alkyl groups, and aryl groups. Examples of alkyl groups and aryl groups are those mentioned above. ３ｂ ~R ７ｂ It is preferable that it is a hydrogen atom.

[0114] Ar １ｂ Ar represents an optionally substituted aryl group or an optionally substituted heteroaryl group. １ｂIt is preferable that the group is an aryl group which may have substituents. The number of carbon atoms in the aryl group is preferably 6 to 20, more preferably 6 to 12, even more preferably 6 to 10, and particularly preferably 6. Examples of substituents include halogen atoms, alkyl groups, alkoxy groups, aryl groups, aryloxy groups, alkylthio groups, arylthio groups, nitro groups, and acyl groups, with acyl groups being preferred.

[0115] As an alternative photopolymerization initiator, the compound represented by formula (OX-3) can also be used.

[0116]

[0117] In formula (OX-3), Ar １ｃ Ar represents an aromatic ring group with (k+m+1) valency or a heterocyclic ring group with (k+m+1) valency. ２ｃ R represents a (k+2) valent aromatic ring group or a (k+2) valent heterocyclic group, １ｃ ~R ３ｃ Each of these independently represents a substituent, L １ｃ is a single bond or CR １１ｃ R １２ｃ Represents R １１ｃ and R １２ｃ Each of these independently represents a hydrogen atom, an alkyl group, or an aryl group, X １ｃ ha-CH ２ It represents -, -N-, -O-, or -S-, where k represents 0 or 1, m represents an integer from 0 to 4, and n represents 0 or 1.

[0118] R １ｃ and R ２ｃThe substituents represented by include alkyl groups and aryl groups, with alkyl groups being preferred. The number of carbon atoms in the alkyl group is preferably 1 to 15, and more preferably 1 to 10. The alkyl group may be linear, branched, or cyclic. The alkyl group may have substituents. Examples of substituents include halogen atoms, aryl groups, alkenyl groups, alkynyl groups, and heteroaryl groups. The number of carbon atoms in the aryl group is preferably 6 to 20, more preferably 6 to 12, even more preferably 6 to 10, and particularly preferably 6. The aryl group may have substituents. Examples of substituents include halogen atoms, alkyl groups, alkenyl groups, alkynyl groups, and heteroaryl groups. ２ｃ It is preferable that the alkyl group has a branched or cyclic structure.

[0119] R ３ｃ Examples of substituents represented by include halogen atoms, alkyl groups, alkoxy groups, aryl groups, aryloxy groups, and acyl groups, with acyl groups being preferred.

[0120] L １ｃ is a single bond or CR １１ｃ R １２ｃ Represents R １１ｃ and R １２ｃ Each of these independently represents a hydrogen atom, an alkyl group, or an aryl group. １１ｃ and R １２ｃ The alkyl and aryl groups in R １ｃ and R ２ｃ This is synonymous with alkyl and aryl groups in [the given context]. When k is 1, L １ｃ It is preferable that the bond is a single bond.

[0121] X １ｃ is, -CH ２ It represents -, -N-, -O-, or -S-, with -O- or -S- being preferred.

[0122] Ar １ｃrepresents a (k+m+1) valent aromatic ring group or a (k+m+1) valent heterocyclic group, and is preferably a (k+m+1) valent aromatic ring group. The aromatic ring group is preferably a benzene ring group or a naphthalene ring group, and more preferably a benzene ring group.

[0123] Ar ２ｃ represents a (k+2) valent aromatic ring group or a (k+2) valent heterocyclic group, and is preferably a (k+2) valent aromatic ring group. The aromatic ring group is preferably a benzene ring group or a naphthalene ring group, and more preferably a benzene ring group.

[0124] k represents 0 or 1, preferably 0. m represents an integer from 0 to 4, preferably 0 or 1, more preferably 1. n represents 0 or 1, preferably 0.

[0125] Other photopolymerization initiators that can be suitably used include ketoxime ester compounds having an allyl oil oxy group at the ortho position, represented by formula (OX-4). Examples of such compounds include those described in Chinese Patent Application Publication No. 117342977.

[0126] In formula (OX-4), R １ｄ and R ２ｄ Each of these independently represents an alkyl group, an aryl group, or a heterocyclic group; R ３ｄ , R ４ｄ , R ５ｄ , R ６ｄ These are, independently, hydrogen atoms, halogen atoms, CN, and NO. ２ CF ３ ,R,OR,SR,SOR,SO ２ R represents R or NRR', where R and R' each independently represent an alkyl group or an aryl group, and when R and R' are present together, R and R' may be bonded to form a ring, and one or more -CH groups in the alkyl group or aryl group represented by R and R' ２ Each of the hyphens may be independently substituted with -O-, -N-, -S-, -CO-, -COO-, -OCO-, or a benzene ring; R ７ｄ , R８ｄ and R ９ｄ Each of these independently represents either a hydrogen atom or a methyl group.

[0127] Other photopolymerization initiators that can be suitably used include compounds represented by formula (OX-5). Examples of such compounds include those described in International Publication No. 2024 / 101219.

[0128] In formula (OX-5), R １ｅ ~R ５ｅ Each of these independently represents a hydrocarbon group which may have substituents, and n represents an integer from 0 to 4.

[0129] Specific examples of oxime compounds include the following compounds.

[0130]

[0131]

[0132]

[0133]

[0134]

[0135] Other photopolymerization initiators may be used, including bifunctional or trifunctional or more functional photopolymerization initiators. Specific examples of bifunctional or trifunctional or more functional photopolymerization initiators include the compounds described in paragraph 0148 of International Publication No. 2022 / 065215.

[0136] The content of the photopolymerization initiator in the total solids of the curable composition is preferably 1 to 20% by mass. The lower limit is preferably 1.5% by mass or more, and more preferably 2% by mass or more. The upper limit is preferably 15% by mass or less, more preferably 10% by mass or less, and even more preferably 8% by mass or less.

[0137] The content of the glyoxylate compound in the photopolymerization initiator is preferably 10% by mass or more, more preferably 20% by mass or more, and even more preferably 30% by mass or more. The upper limit can be 100% by mass or less.

[0138] In the photocurable composition of the present invention, one photopolymerization initiator may be used alone, or two or more may be used. When two or more are used, it is preferable that their total amount is within the above range.

[0139] <<Polymerizable Compounds>> The curable composition of the present invention contains polymerizable compounds. Examples of polymerizable compounds include compounds having an ethylenically unsaturated bond-containing group. Examples of ethylenically unsaturated bond-containing groups include vinyl groups, (meth)allyl groups, and (meth)acryloyl groups. The polymerizable compound used in the present invention is preferably a radical polymerizable compound.

[0140] The polymerizable compound may be in any chemical form, such as monomer, prepolymer, or oligomer, but monomer is preferred. The molecular weight of the polymerizable compound is preferably 100 to 3000. The upper limit is more preferably 2000 or less, and even more preferably 1500 or less. The lower limit is more preferably 150 or more, and even more preferably 250 or more.

[0141] The polymerizable compound is preferably a compound containing two or more ethylenically unsaturated bond-containing groups, more preferably a compound containing two to fifteen ethylenically unsaturated bond-containing groups, and even more preferably a compound containing two to six ethylenically unsaturated bond-containing groups. Furthermore, the polymerizable compound is preferably a (meth)acrylate compound with 2 to 15 functions, and more preferably a (meth)acrylate compound with 2 to 6 functions. Specific examples of polymerizable compounds include the compounds described in paragraphs 0075 to 0083 of International Publication No. 2022 / 065215 and the compounds described in Taiwan Patent Application Publication No. 201832008.

[0142] Preferred polymerizable compounds include dipentaerythritol tri(meth)acrylate (commercially available as KAYARAD D-330; manufactured by Nippon Kayaku Co., Ltd.), dipentaerythritol tetra(meth)acrylate (commercially available as KAYARAD D-320; manufactured by Nippon Kayaku Co., Ltd.), dipentaerythritol penta(meth)acrylate (commercially available as KAYARAD D-310; manufactured by Nippon Kayaku Co., Ltd.), dipentaerythritol hexa(meth)acrylate (commercially available as KAYARAD DPHA; manufactured by Nippon Kayaku Co., Ltd., NK Ester A-DPH-12E; manufactured by Shin Nakamura Chemical Industry Co., Ltd.), and compounds in which the (meth)acryloyl groups of these compounds are linked via ethylene glycol and / or propylene glycol residues (for example, SR454 and SR499, commercially available from Sartomer).Furthermore, polymerizable compounds include diglycerin EO (ethylene oxide) modified (meth)acrylate (commercially available as M-460; manufactured by Toagosei), pentaerythritol tetraacrylate (manufactured by Shin-Nakamura Chemical Industry Co., Ltd., NK Ester A-TMMT), and 1,6-hexanediol diacrylate (manufactured by Nippon Kayaku Co., Ltd., KAYARAD). HDDA), RP-1040 (manufactured by Nippon Kayaku Co., Ltd.), Aronix TO-2349 (manufactured by Toagosei Co., Ltd.), NK Oligo UA-7200 (manufactured by Shin-Nakamura Chemical Industry Co., Ltd.), DPHA-40H (manufactured by Nippon Kayaku Co., Ltd.), UA-306H, UA-306T, UA-306I, AH-600, T-600, AI-600, LINC-202UA (manufactured by Kyoeisha Chemical Co., Ltd.), 8UH-1 006, 8UH-1012 (both manufactured by Taisei Fine Chemical Co., Ltd.), Light Acrylate POB-A0 (manufactured by Kyoeisha Chemical Co., Ltd.), Arronix MT-3041, 3042 (manufactured by Toagosei Co., Ltd., polymerizable compound containing amine), Arronix M-510, 520 (manufactured by Toagosei Co., Ltd., polymerizable compound having an acidic group), Etercure 6361-100 (Eternal Materials Inc. (a polymerizable compound with a hyperbranched structure), EBECRYL80 (a tetrafunctional monomer containing an amine, manufactured by Daicel-Orkenes Corporation), EBECRYL7100 (a difunctional monomer containing an amine, manufactured by Daicel-Orkenes Corporation), CN371NS (a difunctional monomer containing an amine, manufactured by Arkema Corporation), HOA-MPL (2-acryloyloxyethyl phthalate, manufactured by Kyoeisha Chemical Co., Ltd.), HOA-MPE (2-acryloyloxyethyl-2-hydroxyethyl phthalate, manufactured by Kyoeisha Chemical Co., Ltd.) Other polymerizable compounds that can be used include those described in Japanese Patent Publication No. 2023-043479 (manufactured by Daicel Ornex Co., Ltd.), polymerizable compounds that have a dendrimer structure or a hyperbranch structure, those described in Japanese Patent Publication No. 2023-529984, polymerizable compounds that contain a urethane bond as described in Japanese Patent Publication No. 2024-070237, EBECRYL 5129 (manufactured by Daicel Ornex Co., Ltd.), EBECRYL 220 (manufactured by Daicel Ornex Co., Ltd.), KUA-9N (manufactured by KSM Co., Ltd.), and polymerizable compounds described in Japanese Patent Publication No. 2024-085753.

[0143] As polymerizable compounds, polymerizable compounds having a fluorene skeleton can also be used. The polymerizable compound having a fluorene skeleton is preferably a bifunctional polymerizable compound. Examples of commercially available polymerizable compounds having a fluorene skeleton include Ogusol EA-0200 and EA-0300 (manufactured by Osaka Gas Chemical Co., Ltd., (meth)acrylate monomers having a fluorene skeleton).

[0144] As polymerizable compounds, polymerizable compounds having an amino group and an ethylenically unsaturated bond-containing group (hereinafter also referred to as amine monomers) can also be used. By using amine monomers, the effects of the present invention are exhibited more significantly.

[0145] The amine monomer is preferably a compound containing 1 to 10 ethylenically unsaturated bond-containing groups, more preferably a compound containing 2 to 10 groups, and even more preferably a compound containing 3 to 10 groups.

[0146] The pKaH of the amine monomer is preferably 5.5 or higher, more preferably 6.5 or higher, and even more preferably 7.5 or higher, because this enhances the inhibitory effect of the amine on oxygen inhibition and further increases the sensitivity of the curable composition. Note that pKaH is a value representing the pKa of the conjugate acid of the base. In this specification, the pKaH value of the amine monomer is calculated according to the method described in A Web Server for Small Molecular pKa Prediction Using a Graph-Convolutional Neural Network J. Chem. Inf. Model. 2021, 61, 7, 3159-3165.

[0147] The ethylenically unsaturated bond content value (C=C value) of the amine monomer is preferably 0.5 to 11 mmol / g. The upper limit is preferably 10 mmol / g or less, and more preferably 9 mmol / g or less. The lower limit is preferably 1 mmol / g or more, and more preferably 2 mmol / g or more. The ethylenically unsaturated bond content value of the amine monomer is a numerical value representing the molar amount of ethylenically unsaturated bond-containing groups per gram of solid content of the amine monomer.

[0148] The amine value of the amine monomer is preferably 1 to 150 mg KOH / g. The lower limit of the amine value is preferably 2.5 mg KOH / g or higher, and more preferably 5 mg KOH / g or higher. The upper limit of the amine value is preferably 125 mg KOH / g or lower, and more preferably 100 mg KOH / g or lower.

[0149] The hydroxyl value of the amine monomer is preferably 75 mg KOH / g or less, more preferably 50 mg KOH / g or less, and even more preferably 30 mg KOH / g or less.

[0150] The molecular weight of the amine monomer is preferably 100 to 5000, and more preferably 200 to 3000.

[0151] The content of polymerizable compounds 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. The curable composition of the present invention may contain only one polymerizable compound or two or more polymerizable compounds. When two or more polymerizable compounds are included, it is preferable that their total amount falls within the above range.

[0152] <<Specific Compounds>> The curable composition of the present invention contains at least one selected from compound A1, compound A2, and compound A3. Hereinafter, compound A1, compound A2, and compound A3 will be referred to as the specific compounds.

[0153] The curable composition of the present invention may contain only one specific compound, or it may contain two or more specific compounds. If it contains two or more specific compounds, it may contain two or more compounds A1, two or more compounds A2, two or more compounds A3, or two or more compounds selected from compounds A1, A2, and A3.

[0154] (Compound A1) Compound A1 used in the curable composition of the present invention is at least one selected from compound A1-1 (hereinafter also referred to as compound A1-1), which has a basic group and a graft chain and a weight-average molecular weight of 2,000 to 30,000, and block copolymer A1-2 (hereinafter also referred to as block copolymer A1-2), which has a basic group and a weight-average molecular weight of 2,000 to 30,000.

[0155] The weight-average molecular weight of compound A1 is between 2,000 and 30,000. The lower limit is preferably 5,000 or more, and more preferably 7,500 or more. The upper limit is preferably 25,000 or less, and more preferably 22,500 or less.

[0156] The basic group of compound A1 is preferably an amino group. Furthermore, the amine value of compound A1 is preferably 15 mg KOH / g or more, more preferably 30 mg KOH / g or more, and even more preferably 40 mg KOH / g or more. The upper limit is preferably 250 mg KOH / g or less, more preferably 200 mg KOH / g or less, and even more preferably 150 mg KOH / g or less.

[0157] Compound A1 preferably further contains an acidic group. Examples of acidic groups include a carboxyl group, a sulfo group, and a phosphate group.

[0158] If compound A1 has an acid group, the acid value of compound A1 is preferably 10 to 200 mg KOH / g. The lower limit is preferably 20 mg KOH / g or more, and more preferably 25 mg KOH / g or more. The upper limit is preferably 150 mg KOH / g or less, and more preferably 100 mg KOH / g or less.

[0159] Compound A1 may also preferably have a crosslinkable group. Examples of crosslinkable groups include ethylenically unsaturated bond-containing groups and cyclic ether groups. Examples of ethylenically unsaturated bond-containing groups include vinyl groups, (meth)allyl groups, (meth)acryloyl groups, and styrene groups. Examples of cyclic ether groups include epoxy groups and oxetanyl groups.

[0160] -Regarding Compound A1-1- Compound A1-1 has graft chains. In this specification, a graft chain means a polymer chain that branches off from the main chain of repeating units. The graft chain preferably has 40 to 10,000 atoms excluding hydrogen atoms, more preferably 50 to 2,000 atoms excluding hydrogen atoms, and even more preferably 60 to 500 atoms excluding hydrogen atoms.

[0161] The graft chain preferably contains repeating units of at least one structure selected from the group consisting of polyester structures, polyether structures, poly(meth)acrylic structures, polystyrene structures, polyurethane structures, polyurea structures, and polyamide structures; more preferably contains repeating units of at least one structure selected from the group consisting of polyester structures, polyether structures, poly(meth)acrylic structures, and polystyrene structures; even more preferably contains repeating units of polyester structures or polyether structures; and particularly preferably contains repeating units of polyester structures.

[0162] Examples of repeating units for polyester structures include those represented by formulas (G-1), (G-4), or (G-5). Examples of repeating units for polyether structures include those represented by formula (G-2). Examples of repeating units for poly(meth)acrylic structures include those represented by formula (G-3). Examples of repeating units for polystyrene structures include those represented by formula (G-6).

[0163] In the above formula, R Ｇ１ and R Ｇ２ Each of these independently represents an alkylene group. Ｇ１ The number of carbon atoms in the alkylene group represented by is preferably 1 to 20, more preferably 2 to 16, and even more preferably 2 to 12. The alkylene group is preferably linear or branched, and more preferably linear. Ｇ２ The number of carbon atoms in the alkylene group represented by is preferably 1 to 10, more preferably 1 to 5, even more preferably 2 to 5, and even more preferably 2 or 3. The alkylene group is preferably linear or branched, and more preferably linear.

[0164] In the above formula, R Ｇ３ Q represents a hydrogen atom or a methyl group. Ｇ１ represents -O- or -NH-, L Ｇ１ R represents a single bond or a divalent linking group. Ｇ４ L represents a hydrogen atom or substituent. Ｇ１ The divalent linking groups represented by include alkylene groups (preferably alkylene groups having 1 to 12 carbon atoms), alkylene oxy groups (preferably alkylene oxy groups having 1 to 12 carbon atoms), oxyalkylene carbonyl groups (preferably oxyalkylene carbonyl groups having 1 to 12 carbon atoms), arylene groups (preferably arylene groups having 6 to 20 carbon atoms), -NH-, -SO-, and -SO ２ Examples include -, -CO-, -O-, -COO-, -OCO-, -S-, and combinations of two or more of these groups. Ｇ４ Examples of substituents represented by include hydroxyl groups, carboxyl groups, alkyl groups, aryl groups, heterocyclic groups, alkoxy groups, aryloxy groups, heterocyclic oxy groups, alkylthioether groups, arylthioether groups, and heterocyclic thioether groups.

[0165] R Ｇ５ R represents a hydrogen atom or a methyl group. Ｇ６ R represents an aryl group. Ｇ６The number of carbon atoms in the aryl group represented by is preferably 6 to 30, more preferably 6 to 20, and even more preferably 6 to 12. Ｇ６ The aryl group represented by may have substituents. Examples of substituents include hydroxyl groups, carboxyl groups, alkyl groups, aryl groups, heterocyclic groups, alkoxy groups, aryloxy groups, heterocyclic oxy groups, alkylthioether groups, arylthioether groups, and heterocyclic thioether groups.

[0166] The terminal structure of the graft chain is not particularly limited. It may be a hydrogen atom or a substituent. Examples of substituents include hydroxyl groups, carboxyl groups, alkyl groups, aryl groups, heterocyclic groups, alkoxy groups, aryloxy groups, heterocyclic oxy groups, alkylthioether groups, arylthioether groups, and heterocyclic thioether groups. Among these, groups having a steric repulsion effect are preferred, and alkyl or alkoxy groups having 5 to 24 carbon atoms are preferred. The alkyl and alkoxy groups may be linear, branched, or cyclic, with linear or branched being preferred.

[0167] The graft chain is preferably structured as represented by formula (G-1a), formula (G-2a), formula (G-3a), formula (G-4a), formula (G-5a), or formula (G-6a), and more preferably as represented by formula (G-1a), formula (G-4a), or formula (G-5a).

[0168] In the above formula, R Ｇ１ and R Ｇ２ Each of these represents an alkylene group, R Ｇ３ Q represents a hydrogen atom or a methyl group. Ｇ１ represents -O- or -NH-, L Ｇ１ R represents a single bond or a divalent linking group. Ｇ４ R represents a hydrogen atom or substituent. Ｇ５ R represents a hydrogen atom or a methyl group. Ｇ６ represents an aryl group, W １００ R represents a hydrogen atom or substituent, and n1 to n6 each independently represent an integer of 2 or more. Ｇ１ ~R Ｇ６ Q Ｇ１ , LＧ１ For this, see R explained in equations (G-1) to (G-6). Ｇ１ ~R Ｇ６ Q Ｇ１ , L Ｇ１ This is synonymous with the same thing, and the preferred range is also similar.

[0169] In equations (G-1a) to (G-6a), W １００ It is preferable that the substituent is a substituent. Examples of substituents include hydroxyl groups, carboxyl groups, alkyl groups, aryl groups, heterocyclic groups, alkoxy groups, aryloxy groups, heterocyclic oxy groups, alkylthioether groups, arylthioether groups, and heterocyclic thioether groups. Among these, groups having a steric repulsion effect are preferred, and alkyl or alkoxy groups having 5 to 24 carbon atoms are preferred. The alkyl and alkoxy groups may be linear, branched, or cyclic, with linear or branched being preferred.

[0170] In formulas (G-1a) to (G-6a), n1 to n6 are preferably integers from 2 to 100, more preferably integers from 2 to 80, and even more preferably integers from 8 to 60.

[0171] In formula (G-1a), when n1 is 2 or more, R in each repeating unit Ｇ１ The same elements may be identical or different. Also, R Ｇ１ When it contains two or more different repeating units, the arrangement of each repeating unit is not particularly limited and may be random, alternating, or block. The same applies to formulas (G-2a) to (G-6a). Furthermore, the graft chain has a structure represented by formula (G-1a), formula (G-4a), or formula (G-5a), and R Ｇ１ It is also preferable that the structure includes two or more different repeating units.

[0172] Compound A1-1 is preferably a compound (basic graft resin) having repeating units with a basic group and repeating units with a graft chain.

[0173] In compound A1-1, the content of repeating units having a basic group is preferably 10 to 90 mol% of the total repeating units of compound A1-1. The upper limit is preferably 70 mol% or less, and more preferably 50 mol% or less. The lower limit is preferably 15 mol% or more, and more preferably 20 mol% or more.

[0174] Examples of repeating units having graft chains include the repeating unit represented by formula (b1-2).

[0175] In the formula, A ｂ１２ represents a trivalent linking group, L ｂ１２ represents a single bond or a divalent linking group, Y ｂ１２ This represents a graft chain.

[0176] A ｂ１２ Examples of trivalent linking groups represented by include poly(meth)acrylic linking groups, polyalkyleneimine linking groups, polyester linking groups, polyurethane linking groups, polyurea linking groups, polyamide linking groups, polyether linking groups, and polystyrene linking groups. It is preferable that the linking group be a poly(meth)acrylic linking group or a polyalkyleneimine linking group, and more preferably a poly(meth)acrylic linking group.

[0177] L ｂ１２ The divalent linking groups represented by include alkylene groups (preferably alkylene groups having 1 to 12 carbon atoms), arylene groups (preferably arylene groups having 6 to 20 carbon atoms), -NH-, -SO-, and -SO ２ Examples include -, -CO-, -O-, -COO-, -OCO-, -S-, and groups formed by combining two or more of these groups.

[0178] Y ｂ１２ The graft chains represented by this include the graft chains mentioned above.

[0179] The weight-average molecular weight of the repeating unit having a graft chain is preferably 1000 or more, more preferably 1000 to 10000, and even more preferably 1000 to 7500. In this specification, the weight-average molecular weight of the repeating unit having a graft chain is the value calculated from the weight-average molecular weight of the raw material monomers used in the polymerization of the repeating unit. For example, a repeating unit having a graft chain can be formed by polymerizing a macromonomer. Here, a macromonomer means a polymer compound in which polymerizable groups are introduced at the polymer ends. When a repeating unit having a graft chain is formed using a macromonomer, the weight-average molecular weight of the macromonomer corresponds to the repeating unit having a graft chain.

[0180] In compound A1-1, the content of repeating units having graft chains is preferably 1 to 80 mol% of the total repeating units of compound A1-1.

[0181] If compound A1-1 has an acidic group, it is preferable that compound A1-1 is a compound containing repeating units having an acidic group. The content of repeating units having an acidic group is preferably 1 to 80 mol% of the total repeating units of compound A1-1.

[0182] If compound A1-1 has a crosslinking group, it is preferable that compound A1-1 contains repeating units having the crosslinking group. In compound A1-1, the content of repeating units having the crosslinking group is preferably 1 to 80 mol% of the total repeating units of compound A1-1. The upper limit is preferably 70 mol% or less, and more preferably 60 mol% or less. The lower limit is preferably 2 mol% or more, and more preferably 5 mol% or more.

[0183] - About Block Copolymer A1-2 - The above block copolymer A1-2 is a block copolymer having a basic group. In this specification, a block copolymer means a copolymer having blocks of multiple polymers.

[0184] Examples of block copolymers having basic groups include block copolymers comprising a polymer block having repeating units having basic groups (hereinafter also referred to as block a1) and a polymer block not having basic groups (hereinafter also referred to as block a2). Examples of block a2 include polymer blocks having repeating units having acidic groups and polymer blocks having repeating units having crosslinkable groups. Block a1 and block a2 may consist of only one type or two or more types.

[0185] The block copolymer A1-2 preferably contains repeating units of at least one structure selected from the group consisting of polyester structure, polyether structure, poly(meth)acrylic structure, polystyrene structure, polyurethane structure, polyurea structure, and polyamide structure, and more preferably contains repeating units of poly(meth)acrylic structure. Examples of repeating units of polyester structure include repeating units of the structure represented by formula (G-1), formula (G-4), or formula (G-5) described above. Examples of repeating units of polyether structure include repeating units of the structure represented by formula (G-2) described above. Examples of repeating units of poly(meth)acrylic structure include repeating units of the structure represented by formula (G-3) described above. Examples of repeating units of polystyrene structure include repeating units of the structure represented by formula (G-6) described above.

[0186] A preferred embodiment of block copolymer A1-2 is a block copolymer in which block a1 is a polymer block having repeating units of a poly(meth)acrylic structure having a basic group.

[0187] Specific examples of block copolymer A1-2 include the dispersion resin D-6 described in the examples below, and the basic dispersants B1-1 to B1-7 described in paragraphs 0237 to 0240 of Japanese Patent Application Publication No. 2023-090171.

[0188] When the curable composition of the present invention contains compound A1, the content of compound A1 in the total solid content of the curable composition is preferably 1 to 50% by mass. The upper limit is preferably 40% by mass or less, and more preferably 30% by mass or less. The lower limit is preferably 5% by mass or more, and more preferably 10% by mass or more. Furthermore, the ratio of pigment to compound A1 is preferably 10 to 100 parts by mass of compound A1 per 100 parts by mass of pigment. The lower limit is preferably 15 parts by mass or more, and more preferably 20 parts by mass or more. The upper limit is preferably 90 parts by mass or less, and more preferably 80 parts by mass or less. Furthermore, the ratio of glyoxylate compound to compound A1 is preferably 10 to 2500 parts by mass of compound A1 per 100 parts by mass of glyoxylate compound. The lower limit is preferably 50 parts by mass or more, and more preferably 100 parts by mass or more. The upper limit is preferably 2000 parts by mass or less, and more preferably 1500 parts by mass or less. Compound A1 may be used alone or in combination of two or more types. If two or more types are used, it is preferable that their total amount is within the above range.

[0189] (Compound A2) Compound A2 used in the curable composition of the present invention is a compound having at least one structure selected from a dye structure, an aromatic ring, and a heteroaromatic ring, and a basic group, and having a molecular weight of 100 or more and less than 2000.

[0190] The lower limit of the molecular weight of compound A2 is preferably 200 or more, and more preferably 300 or more. The upper limit is preferably 1000 or less, and more preferably 1500 or less. If the molecular weight of compound A2 can be calculated from its structural formula, then the molecular weight of compound A2 is the value calculated from the structural formula.

[0191] Examples of the pigment structures possessed by compound A2 include quinoline pigment structure, benzimidazolone pigment structure, benzoisoindole pigment structure, benzothiazole pigment structure, iminium pigment structure, squarylium pigment structure, crokonium pigment structure, oxonol pigment structure, pyrrolopyrrole pigment structure, diketopyrrolopyrrole pigment structure, azo pigment structure, azomethine pigment structure, phthalocyanine pigment structure, naphthalocyanine pigment structure, anthraquinone pigment structure, quinacridone pigment structure, dioxazine pigment structure, perinone pigment structure, perylene pigment structure, thiaidine indigo pigment structure, thioindigo pigment structure, isoindoline pigment structure, isoindolinone pigment structure, quinophthalone pigment structure, dithiol pigment structure, triarylmethane pigment structure, pyromethene pigment structure, and the like.

[0192] Examples of the aromatic rings in compound A2 include benzene rings and naphthalene rings. These rings may further have substituents. The heteroaromatic rings in compound A2 may be monocyclic or polycyclic. The heteroatoms constituting the heteroaromatic ring preferably include at least one selected from nitrogen, oxygen, and sulfur atoms, and more preferably include nitrogen atoms. The number of heteroatoms constituting the heteroaromatic ring is preferably 1 to 4, and more preferably 1 to 3. Specific examples of heteroaromatic rings include triazine rings and naphthalene rings, with triazine rings being preferred.

[0193] Basic groups of compound A2 include amino groups, pyridinyl groups and their salts, ammonium groups, and phthalimidomethyl groups. Atoms or groups of atoms that make up the salts include hydroxide ions, halogen ions, carboxylate ions, sulfonate ions, and phenoxide ions.

[0194] As for the amino group, -NR ｘ１１ R ｘ１２ Examples include the group represented by and the cyclic amino group.

[0195] -NR ｘ１１ R ｘ１２ In the group represented by R ｘ１１ and Rｘ１２ Each of these independently represents a hydrogen atom, an alkyl group, or an aryl group, and is preferably an alkyl group. That is, the amino group is preferably a dialkylamino group. The number of carbon atoms in the alkyl group is preferably 1 to 10, more preferably 1 to 5, and even more preferably 1 to 3. The alkyl group may be linear, branched, or cyclic, but linear or branched is preferred, and linear is more preferred. The alkyl group may have substituents. The number of carbon atoms in the aryl group is preferably 6 to 30, more preferably 6 to 20, and even more preferably 6 to 12. The aryl group may have substituents.

[0196] Examples of cyclic amino groups include pyrrolidine, piperidine, piperazine, and morpholine groups. These groups may also have substituents.

[0197] Compound A2 is preferably a compound having at least one structure selected from a dye structure and a triazine ring, and a basic group.

[0198] Compound A2 may have acidic groups, but it is preferable that the number of acidic groups in one molecule is less than the number of basic groups. It is particularly preferable that compound A2 does not have acidic groups.

[0199] Specific examples of compound A2 include compounds Syn-2, Syn-4, Syn-5, Syn-6, Syn-7, Syn-8, Syn-12, Syn-102 to Syn-107 described in the examples below, the compound described in paragraph 0124 of International Publication No. 2022 / 085485, the benzimidazolone compound or salt thereof described in Japanese Patent Application Publication No. 2018-168244, the compound having an isoindoline skeleton described in general formula (1) of Japanese Patent No. 6996282, the compound described in Japanese Patent Application Publication No. 2019-172968, and the compound described in Chinese Patent Application Publication No. 115124889.

[0200] When the curable composition of the present invention contains compound A2, the ratio of pigment to compound A2 is preferably 1 to 50 parts by mass of compound A2 per 100 parts by mass of pigment. The lower limit is preferably 1 part by mass or more, more preferably 3 parts by mass or more, and even more preferably 5 parts by mass or more. The upper limit is preferably 40 parts by mass or less, and more preferably 30 parts by mass or less. Compound A2 may be used alone or two or more types. When two or more types are used, it is preferable that their total amount is within the above range.

[0201] (Compound A3) Compound A3 used in the curable composition of the present invention is a polyalkyleneimine, which is a polymer obtained by ring-opening polymerization of 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 number of carbon atoms in the alkyleneimine is preferably 2 to 6, more preferably 2 to 4, even more preferably 2 or 3, and particularly preferably 2.

[0202] The molecular weight of the polyalkyleneimine is preferably 200 or more, and more preferably 250 or more. The upper limit is preferably 100,000 or less, more preferably 50,000 or less, even more preferably 10,000 or less, and particularly preferably 2,000 or less. When the molecular weight of the polyalkyleneimine can be calculated from the structural formula, the molecular weight of the polyalkyleneimine is the value calculated from the structural formula. On the other hand, when the molecular weight of a specific amine compound cannot be calculated from the structural formula, or when it is difficult to calculate, the number-average molecular weight measured by the boiling point elevation method is used. Furthermore, when it cannot be measured by the boiling point elevation method, or when it is difficult to measure, the number-average molecular weight measured by the viscosity method is used. Furthermore, when it cannot be measured by the viscosity method, or when it is difficult to measure by the viscosity method, the number-average molecular weight in polystyrene equivalent values ​​measured by GPC (gel permeation chromatography) is used.

[0203] 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.

[0204] Specific examples of alkyleneimines include ethyleneimine, propyleneimine, 1,2-butyleneimine, and 2,3-butyleneimine, with ethyleneimine or propyleneimine being preferred, and ethyleneimine being more preferred. Polyalkyleneimines are particularly preferably polyethyleneimine. Furthermore, polyethyleneimine preferably contains 10 mol% or more of primary amino groups relative to the total of primary, secondary, and tertiary amino groups, more preferably 20 mol% or more, and even more preferably 30 mol% or more. Commercially available polyethyleneimines include Epomin SP-003, SP-006, SP-012, SP-018, SP-200, and P-1000 (all manufactured by Nippon Shokubai Co., Ltd.).

[0205] When the curable composition of the present invention contains compound A3, the ratio of pigment to compound A3 is preferably 0.5 to 20 parts by mass of compound A3 per 100 parts by mass of pigment. The lower limit is preferably 0.6 parts by mass or more, more preferably 1 part by mass or more, and even more preferably 2 parts by mass or more. The upper limit is preferably 10 parts by mass or less, and more preferably 8 parts by mass or less. Compound A3 may be used alone or two or more types. When two or more types are used, it is preferable that their total amount is within the above range.

[0206] <<Compound B1>> The curable composition of the present invention may further contain compound B1 (hereinafter also referred to as compound B1), which has at least one structure selected from a dye structure, an aromatic ring, and a heteroaromatic ring, and an acid group, and has a molecular weight of 100 or more and less than 2000.

[0207] If the curable composition of the present invention contains compound A1 as described above, it is preferable that it further contains compound B1. In this embodiment, the effects of the present invention are more pronounced.

[0208] The lower limit of the molecular weight of compound B1 is preferably 200 or more, and more preferably 300 or more. The upper limit is preferably 1000 or less, and more preferably 1500 or less. If the molecular weight of compound B1 can be calculated from its structural formula, then the molecular weight of compound B1 is the value calculated from the structural formula.

[0209] Examples of the pigment structures possessed by compound B1 include quinoline pigment structure, benzimidazolone pigment structure, benzoisoindole pigment structure, benzothiazole pigment structure, iminium pigment structure, squarylium pigment structure, crokonium pigment structure, oxonol pigment structure, pyrrolopyrrole pigment structure, diketopyrrolopyrrole pigment structure, azo pigment structure, azomethine pigment structure, phthalocyanine pigment structure, naphthalocyanine pigment structure, anthraquinone pigment structure, quinacridone pigment structure, dioxazine pigment structure, perinone pigment structure, perylene pigment structure, thiaidine indigo pigment structure, thioindigo pigment structure, isoindoline pigment structure, isoindolinone pigment structure, quinophthalone pigment structure, dithiol pigment structure, triarylmethane pigment structure, pyromethene pigment structure, and the like.

[0210] Examples of the aromatic rings in compound B1 include benzene rings and naphthalene rings. These rings may further have substituents. The heteroaromatic rings in compound B1 may be monocyclic or polycyclic. The heteroatoms constituting the heteroaromatic ring preferably include at least one selected from nitrogen, oxygen, and sulfur atoms, and more preferably include nitrogen atoms. The number of heteroatoms constituting the heteroaromatic ring is preferably 1 to 4, and more preferably 1 to 3. Specific examples of heteroaromatic rings include triazine rings and naphthalene rings, with triazine rings being preferred.

[0211] Examples of acidic groups in compound B1 include carboxyl groups, sulfo groups, phosphate groups, boronic acid groups, imido acid groups, and salts thereof. Examples of atoms or groups of atoms constituting the salt include alkali metal ions (Li ＋ Na ＋ _K ＋(Ca) ２＋ Mg ２＋ Examples include ammonium ions, imidazolium ions, pyridinium ions, and phosphonium ions. Examples of imido acid groups include -SO ２ NHSO ２ R x２１ , -CONHSO ２ R x２２ , -CONHCOR x２３ or -SO ２ NHCOR x２４ Preferably, -SO ２ NHSO ２ R x２１ , -CONHSO ２ R x２２ , or -SO ２ NHCOR x２４ More preferably, -SO ２ NHSO ２ R x２１ or -CONHSO ２ R x２２ This is even more preferable. x２１ ~R x２４ Each of these independently represents an alkyl group or an aryl group. x２１ ~R x２４ The alkyl and aryl groups represented by may have substituents. The substituents are preferably halogen atoms, and more preferably fluorine atoms. x２１ ~R x２４ Each of these is preferably an alkyl group containing a fluorine atom or an aryl group containing a fluorine atom, and more preferably an alkyl group containing a fluorine atom. The alkyl group containing a fluorine atom has 1 to 10 carbon atoms, more preferably 1 to 5, and even more preferably 1 to 3. The aryl group containing a fluorine atom has 6 to 20 carbon atoms, more preferably 6 to 12, and even more preferably 6.

[0212] Compound B1 is preferably a compound having at least one structure selected from a dye structure and a triazine ring, and an acid group.

[0213] Compound B1 is preferably a compound that does not have a basic group.

[0214] Specific examples of compound B1 include compounds Syn-1, Syn-3, and Syn-4 described in the examples below, the compound described in paragraph 0124 of International Publication No. 2022 / 085485, the benzimidazolone compound or salts thereof described in Japanese Patent Application Publication No. 2018-168244, the compound having an isoindoline skeleton described in general formula (1) of Japanese Patent No. 6996282, the compound described in Japanese Patent Application Publication No. 2019-172968, and the compound described in Chinese Patent Application Publication No. 115124889.

[0215] When the curable composition of the present invention contains compound B1, the ratio of pigment to compound B1 is preferably 1 to 50 parts by mass of compound B1 per 100 parts by mass of pigment. The lower limit is preferably 1 part by mass or more, more preferably 3 parts by mass or more, and even more preferably 5 parts by mass or more. The upper limit is preferably 40 parts by mass or less, and more preferably 35 parts by mass or less. The curable composition of the present invention may contain only one type of compound B1, or it may contain two or more types. When two or more types of compound B1 are included, it is preferable that their total amount falls within the above range.

[0216] <<Compound B2>> The curable composition of the present invention may contain compound B2 (hereinafter also referred to as compound B2), which has an acid group and a graft chain and has a weight-average molecular weight of 2,000 or more and 30,000 or less.

[0217] If the curable composition of the present invention contains at least one selected from the above-mentioned compounds A2 and A3, it is preferable that it further contains compound B2. In this embodiment, the effects of the present invention are more pronounced.

[0218] The weight-average molecular weight of compound B2 is between 2,000 and 30,000. The lower limit is preferably 5,000 or more, and more preferably 7,500 or more. The upper limit is preferably 25,000 or less, and more preferably 22,500 or less.

[0219] The acidic groups that compound B2 may have include carboxyl groups, sulfol groups, and phosphate groups, with carboxyl groups being preferred.

[0220] The acid value of compound B2 is preferably 20 to 200 mg KOH / g. The lower limit is preferably 30 mg KOH / g or more, and more preferably 40 mg KOH / g or more. The upper limit is preferably 150 mg KOH / g or less, and more preferably 125 mg KOH / g or less.

[0221] The graft chain of compound B2 preferably contains repeating units of at least one structure selected from the group consisting of polyester, polyether, poly(meth)acrylic, polystyrene, polyurethane, polyurea, and polyamide structures; more preferably contains repeating units of at least one structure selected from the group consisting of polyester, polyether, poly(meth)acrylic, and polystyrene structures; even more preferably contains repeating units of at least one structure selected from the group consisting of polyester, polyether, and poly(meth)acrylic structures; particularly preferably contains polyether and poly(meth)acrylic structures; and most preferably contains polyether structures. Details of the graft chain can be found in the graft chain of compound A1 described above.

[0222] Compound B2 is preferably a compound (acidic graft resin) having repeating units having acidic groups and repeating units having graft chains. Examples of repeating units having graft chains include the repeating units represented by formula (b1-2) described in the section on compound A1 above.

[0223] In compound B2, the content of repeating units having an acid group is preferably 20 to 99 mol% of the total repeating units of compound B2. The upper limit is preferably 97 mol% or less, and more preferably 95 mol% or less. The lower limit is preferably 25 mol% or more, and more preferably 30 mol% or more.

[0224] In compound B2, the content of repeating units having graft chains is preferably 1 to 80 mol% of the total repeating units of compound B2. The upper limit is preferably 75 mol% or less, and more preferably 70 mol% or less. The lower limit is preferably 3 mol% or more, and more preferably 5 mol% or more.

[0225] Compound B2 may also preferably have a crosslinkable group. Examples of crosslinkable groups include ethylenically unsaturated bond-containing groups and cyclic ether groups. Examples of ethylenically unsaturated bond-containing groups include vinyl groups, (meth)allyl groups, (meth)acryloyl groups, and styrene groups. Examples of cyclic ether groups include epoxy groups and oxetanyl groups.

[0226] If compound B2 has a crosslinking group, it is preferable that compound B2 contains repeating units having the crosslinking group. In compound B2, the content of repeating units having the crosslinking group is preferably 1 to 80 mol% of the total repeating units of compound B2. The upper limit is preferably 70 mol% or less, and more preferably 60 mol% or less. The lower limit is preferably 2 mol% or more, and more preferably 5 mol% or more.

[0227] Compound B2 can also be a compound containing a repeating unit represented by formula (Ac-2). In formula (Ac-2), Ar １０ L represents a group containing an aromatic carboxyl group. １１ represents -COO- or -CONH-, L １２ represents a trivalent linking group, P １０ represents a polymer chain.

[0228] Ar in equation (Ac-2) １０ Groups containing aromatic carboxyl groups represented by include structures derived from aromatic tricarboxylic acid anhydrides and structures derived from aromatic tetracarboxylic acid anhydrides. Examples of aromatic tricarboxylic acid anhydrides and aromatic tetracarboxylic acid anhydrides include compounds with the following structures.

[0229] In the above formula, Q１ These are single bonds, -O-, -CO-, -COOCH ２ CH ２ OCO-, -SO ２ -, -C(CF ３ ) ２ - represents a group represented by the following formula (Q-1) or a group represented by the following formula (Q-2).

[0230] Ar １０ The group containing the aromatic carboxyl group represented by Ar may also have a crosslinking group. １０ Specific examples of groups containing aromatic carboxyl groups represented by include the group represented by formula (Ar-11), the group represented by formula (Ar-12), and the group represented by formula (Ar-13).

[0231] In formula (Ar-11), n1 represents an integer from 1 to 4, preferably 1 or 2, and more preferably 2. In formula (Ar-12), n2 represents an integer from 1 to 8, preferably 1 to 4, more preferably 1 or 2, and even more preferably 2. In formula (Ar-13), n3 and n4 each independently represent an integer from 0 to 4, preferably 0 to 2, more preferably 1 or 2, and even more preferably 1. However, at least one of n3 and n4 is an integer of 1 or more. In formula (Ar-13), Q １ These are single bonds, -O-, -CO-, -COOCH ２ CH ２ OCO-, -SO ２ -, -C(CF ３ ) ２ - represents the group represented by formula (Q-1) or the group represented by formula (Q-2). In formulas (Ar-11) to (Ar-13), *1 is L １０ This indicates the connection point with [the other element].

[0232] L in equation (Ac-2) １１ This represents -COO- or -CONH-, and is preferably -COO-.

[0233] L in equation (Ac-2) １２The trivalent linking group represented by includes hydrocarbon groups, -O-, -CO-, -COO-, -OCO-, -NH-, -S-, and groups combining two or more of these. Hydrocarbon groups include aliphatic hydrocarbon groups and aromatic hydrocarbon groups. The number of carbon atoms in the aliphatic hydrocarbon group is preferably 1 to 30, more preferably 1 to 20, and even more preferably 1 to 15. The aliphatic hydrocarbon group may be linear, branched, or cyclic. The number of carbon atoms in the aromatic hydrocarbon group is preferably 6 to 30, more preferably 6 to 20, and even more preferably 6 to 10. The hydrocarbon group may have substituents. Examples of substituents include hydroxyl groups. １２ The trivalent linking group represented by is preferably the group represented by formula (L12-1), and more preferably the group represented by formula (L12-2).

[0234] In formula (L12-1), L １２ｂ represents a trivalent linking group, X １ represents S, and *1 is L in equation (Ac-2). １１ This indicates the bonding position, and *2 is P in equation (Ac-2). １０ This indicates the connection position with L. １２ｂ Examples of trivalent linking groups represented by include hydrocarbon groups; groups formed by combining a hydrocarbon group with at least one selected from -O-, -CO-, -COO-, -OCO-, -NH-, and -S-, and it is preferable that the group is a hydrocarbon group or a group formed by combining a hydrocarbon group with -O-.

[0235] In formula (L12-2), L １２ｃ represents a trivalent linking group, X １ represents S, and *1 is L in equation (Ac-2). １１ This indicates the bonding position, and *2 is P in equation (Ac-2). １０ This indicates the connection position with L. １２ｃ Examples of the trivalent linking group represented by include hydrocarbon groups; and groups formed by combining a hydrocarbon group with at least one selected from -O-, -CO-, -COO-, -OCO-, -NH-, and -S-, with hydrocarbon groups being preferred.

[0236] P in equation (Ac-2) １０The polymer chain represented by [formula] includes polymer chains containing repeating units of at least one structure selected from the group consisting of polyester structures, polyether structures, poly(meth)acrylic structures, polystyrene structures, polyurethane structures, polyurea structures, and polyamide structures. Examples of repeating units of polyester structures include repeating units of structures represented by formulas (G-1), (G-4), or (G-5) above. Examples of repeating units of polyether structures include repeating units of structures represented by formula (G-2) above. Examples of repeating units of poly(meth)acrylic structures include repeating units of structures represented by formula (G-3) above. Examples of repeating units of polystyrene structures include repeating units of structures represented by formula (G-6) above.

[0237] P １０ The polymer chain represented by may include repeating units having crosslinkable groups. １０ If the polymer chain represented by contains repeating units having crosslinkable groups, P １０ The proportion of repeating units having crosslinkable groups among all repeating units constituting the structure is preferably 1 mol% or more, and more preferably 1 to 80 mol%. The upper limit is preferably 70 mol% or less, and more preferably 60 mol% or less. The lower limit is preferably 2 mol% or more, and more preferably 5 mol% or more.

[0238] P １０ The polymer chain represented by may contain repeating units containing acid groups. Examples of acid groups include carboxyl groups, phosphate groups, sulfo groups, and phenolic hydroxyl groups. １０ If the polymer chain represented by contains repeating units having acidic groups, P １０ The proportion of repeating units having acid groups in the total repeating units constituting the material is preferably 1 to 80 mol%, more preferably 5 to 80 mol%, and even more preferably 10 to 80 mol%.

[0239] P １０The weight-average molecular weight of the polymer chain represented by is preferably 500 to 20000. The lower limit is preferably 1000 or more. The upper limit is preferably 10000 or less, more preferably 5000 or less, and even more preferably 3000 or less.

[0240] When the curable composition of the present invention contains compound B2, the ratio of pigment to compound B2 is preferably 10 to 80 parts by mass of compound B2 per 100 parts by mass of pigment. The lower limit is preferably 15 parts by mass or more, and more preferably 20 parts by mass or more. The upper limit is preferably 70 parts by mass or less, and more preferably 60 parts by mass or less. Furthermore, the ratio of compound A2 to compound B2 is preferably 100 to 800 parts by mass of compound B1 per 100 parts by mass of compound A2. The lower limit is preferably 150 parts by mass or more, and more preferably 200 parts by mass or more. The upper limit is preferably 700 parts by mass or less, and more preferably 600 parts by mass or less. Furthermore, the ratio of compound A3 to compound B2 is preferably 200 to 1400 parts by mass of compound B1 per 100 parts by mass of compound A3. The lower limit is preferably 300 parts by mass or more, and more preferably 400 parts by mass or more. The upper limit is preferably 1,200 parts by mass or less, and more preferably 1,000 parts by mass or less. The curable composition of the present invention may contain only one type of compound B2, or it may contain two or more types. If it contains two or more types of compound B2, it is preferable that their total amount is within the above range.

[0241] <<Solvent>> The curable composition of the present invention contains a solvent. Examples of solvents include organic solvents. The type of solvent is not particularly limited as long as it satisfies the solubility of each component and the applicability of the composition. Examples of organic solvents include ester solvents, ketone solvents, alcohol solvents, amide solvents, ether solvents, and hydrocarbon solvents. For further details, please refer to paragraph 0223 of International Publication No. 2015 / 166779, which is incorporated herein by reference. In addition, ester solvents and ketone solvents substituted with cyclic alkyl groups can also be preferably used. Specific examples of organic solvents include polyethylene glycol monomethyl ether, dichloromethane, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, ethyl cellosolve acetate, ethyl lactate, diethylene glycol dimethyl ether, butyl acetate, methyl 3-methoxypropionate, 2-heptanone, 2-pentanone, 3-pentanone, 4-heptanone, cyclohexanone, 2-methylcyclohexanone, 3-methylcyclohexanone, 4-methylcyclohexanone, cycloheptanone, cyclooctanone, cyclohexyl acetate, cyclopentanone, cyclopentyl methyl ether, dipropylene glycol monomethyl ether, 2-methyltetrahydrofuran, 4-methyltetrahydropyran, ethyl carbitol acetate, and butyl carbitol. Examples include toll acetate, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, 3-methoxy-N,N-dimethylpropanamide, 3-butoxy-N,N-dimethylpropanamide, propylene glycol diacetate, 3-methoxybutanol, methyl ethyl ketone, gamma butyrolactone, sulfolane, anisole, 1,4-diacetoxybutane, diethylene glycol monoethyl ether acetate, butane-1,3-diyl diacetate, dipropylene glycol methyl ether acetate, diacetone alcohol (also known as diacetone alcohol, 4-hydroxy-4-methyl-2-pentanone), 2-methoxypropyl acetate, 2-methoxy-1-propanol, and isopropyl alcohol.However, the amount of aromatic hydrocarbons used as organic solvents (benzene, toluene, xylene, ethylbenzene, etc.) may be reduced for environmental reasons (for example, it may be reduced to 50 ppm by mass (parts per million) or less, 10 ppm by mass or less, or 1 ppm by mass or less relative to the total amount of organic solvent).

[0242] Organic solvents may be used alone or in combination of two or more. When two or more organic solvents are included, a main solvent accounting for 50% or more by mass of the organic solvent and a secondary solvent accounting for 50% or less by mass may be used. The main solvent is preferably 60% or more by mass of the organic solvent, and more preferably 70% or more by mass. Two or more secondary solvents may be included, and their total amount is preferably 40% or less by mass, and more preferably 30% or less by mass. The type of main solvent is not particularly limited, and preferred examples include preferred solvents described in paragraph 0224 of International Publication No. 2015 / 166779, ester solvents substituted with cyclic alkyl groups, and ketone solvents substituted with cyclic alkyl groups. The type of secondary solvent is not particularly limited and can be selected from the solvents described above.

[0243] It is preferable that the metal content of the organic solvent be low. The metal content of the organic solvent is preferably, for example, 10 ppb (parts per billion) or less by mass. If necessary, an organic solvent with a metal content at the ppt (parts per trillion) level by mass may be used; such organic solvents are provided, for example, by Toyo Gosei Co., Ltd. (Chemical Daily, November 13, 2015).

[0244] Methods for removing impurities such as metals from organic solvents include, for example, distillation (molecular distillation, thin-film distillation, etc.) and filtration using a filter. The pore size of the filter used for filtration is preferably 10 μm or less, more preferably 5 μm or less, and even more preferably 3 μm or less. The material of the filter is preferably polytetrafluoroethylene, polyethylene, or nylon.

[0245] Organic solvents may contain isomers (compounds with the same number of atoms but different structures). Furthermore, they may contain only one type of isomer or multiple types.

[0246] It is preferable that the peroxide content in the organic solvent is 0.8 mmol / L or less, and more preferably that it is substantially peroxide-free.

[0247] The solvent content in the curable composition is preferably 10 to 95% by mass, more preferably 20 to 90% by mass, and even more preferably 30 to 90% by mass.

[0248] From the viewpoint of environmental regulations, the curable composition of the present invention preferably contains substantially no environmentally regulated substances. In this invention, "substantially free of environmentally regulated substances" means that the content of environmentally regulated 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 regulated substances include benzene; alkylbenzenes such as toluene and xylene; halogenated benzenes such as chlorobenzene, etc. These substances are registered as environmentally regulated substances under the REACH (Registration Evaluation Authorization and Restriction of Chemicals) regulations, the PRTR (Pollutant Release and Transfer Register) law, and the VOC (Volatile Organic Compounds) regulations, and their usage and handling methods are strictly regulated. These compounds may be used as solvents when manufacturing the various components used in curable compositions, and may be mixed into the curable composition as residual solvents. From the standpoint of human safety and environmental considerations, it is preferable to reduce these substances as much as possible. One method for reducing environmentally regulated substances is to heat or reduce the pressure in the system to above the boiling point of the environmentally regulated substance and distillate it off the system. Furthermore, when removing small amounts of environmentally regulated substances by distillation, it is useful to azeotrope with a solvent having a boiling point equivalent to that of the solvent in question in order to improve efficiency. In addition, if the mixture contains compounds that exhibit radical polymerization, polymerization inhibitors may be added during reduced-pressure distillation to suppress the progression of radical polymerization reactions and the resulting crosslinking between molecules. These distillation methods can be implemented at any stage, including the raw material stage, the product stage (e.g., the polymerized resin solution or polyfunctional monomer solution), or the stage of the curable composition prepared by mixing these compounds.

[0249] <<Resin>> The curable composition of the present invention may contain resins other than the specific compounds and compound B2 described above. Resins are used, for example, to disperse pigments and the like in the curable composition, or as binders. Resins used mainly to disperse pigments and the like in the curable composition are also called dispersants. However, such uses of resins are just examples, and resins can also be used for purposes other than those described above. The curable composition of the present invention preferably contains a resin as a binder.

[0250] The weight-average molecular weight (Mw) of the resin is preferably between 3,000 and 2,000,000. The upper limit is preferably 1,000,000 or less, and more preferably 500,000 or less. The lower limit is preferably 4,000 or more, and more preferably 5,000 or more.

[0251] Examples of resins include (meth)acrylic resins, epoxy resins, (meth)acrylamide resins, ene-thiol resins, polycarbonate resins, polyether resins, polyarylate resins, polysulfone resins, polyethersulfone resins, polyphenylene resins, polyarylene etherphosphine oxide resins, polyimide resins, polyamide-imide resins, polyolefin resins, cyclic olefin resins, polyester resins, styrene resins, siloxane resins, and urethane resins. Urethane resin is a polymer compound formed by the reaction of an isocyanate group and an alcohol group. Specifically, it is a polymer compound having a urethane bond (or carbamate bond) formed by reacting a compound having an isocyanate group (polyisocyanate) with a compound having an alcohol group (polyol). The urethane value of the urethane resin is preferably 0.5 to 6.0 mmol / g. The lower limit is preferably 1.0 mmol / g or more, more preferably 1.5 mmol / g or more, and even more preferably 2.0 mmol / g or more. The upper limit is preferably 5.0 mmol / g or less, more preferably 4.5 mmol / g or less, and even more preferably 4.0 mmol / g or less. The urethane value of the urethane resin is particularly preferably 2.0 to 4.0 mmol / g. The urethane value of the urethane resin is a numerical value that represents the molar amount of urethane bonds per gram of solid content of the urethane resin.

[0252] Furthermore, the resins include the resins described in paragraphs 0091 to 0099 of International Publication No. 2022 / 065215, the blocked polyisocyanate resin described in Japanese Patent Publication No. 2016-222891, the resin described in Japanese Patent Publication No. 2020-122052, the resin described in Japanese Patent Publication No. 2020-111656, the resin described in Japanese Patent Publication No. 2020-139021, and the resin described in Japanese Patent Publication No. 2017-138503. A resin comprising a structural unit having a ring structure in the main chain and a structural unit having a biphenyl group in the side chain; the resin described in paragraphs 0199 to 0233 of Japanese Patent Publication No. 2020-186373; the alkali-soluble resin described in Japanese Patent Publication No. 2020-186325; the resin represented by formula 1 described in Korean Published Patent No. 10-2020-0078339; and a copolymer containing epoxy groups and acid groups described in International Publication No. 2022 / 030445. , the resin described in Japanese Patent Publication No. 2018-135514, the copolymer described in Japanese Patent Publication No. 2020-041046, the resin described in Japanese Patent Publication No. 2023-033156, the resin described in Japanese Patent Publication No. 2023-030386, the resin described in Japanese Patent Publication No. 2023-027753, the resin described in Japanese Patent Publication No. 2020-139021, the resin described in Japanese Patent Publication No. 2023-074038, Japanese Patent Publication No. 2023-079666 The resins described in the publication, the cardo resin described in Chinese Patent Application Publication No. 115947929, the copolymer described in Japanese Patent Application Publication No. 2024-014141, the resin described in Japanese Patent Application Publication No. 2024-050148, the copolymer described in International Publication No. 2024 / 134926, the resin described in Japanese Patent Application Publication No. 2024-088596, and the compound represented by formula (1) described in Japanese Patent Application Publication No. 2024-128953 can also be used.

[0253] It is preferable to use a resin having acidic groups. Examples of acidic groups include carboxyl groups, phosphate groups, sulfo groups, and phenolic hydroxyl groups.

[0254] The acid value of the resin having acid groups is preferably 30 to 500 mg KOH / g. The lower limit is preferably 40 mg KOH / g or more, and more preferably 50 mg KOH / g or more. The upper limit is preferably 400 mg KOH / g or less, more preferably 300 mg KOH / g or less, and even more preferably 200 mg KOH / 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.

[0255] Resins having acidic groups preferably contain repeating units having acidic groups in their side chains, and more preferably contain repeating units having acidic groups in their side chains in an amount of 5 to 70 mol% of the total repeating units of the resin. The upper limit of the content of repeating units having acidic groups in their side chains is preferably 50 mol% or less, and more preferably 30 mol% or less. The lower limit of the content of repeating units having acidic groups in their side chains is preferably 10 mol% or more, and more preferably 20 mol% or more.

[0256] Regarding resins having acid groups, reference can be made to paragraphs 0558-0571 of Japanese Patent Application Publication No. 2012-208494 (paragraphs 0685-0700 of the corresponding US Patent Application Publication No. 2012 / 0235099) and paragraphs 0076-0099 of Japanese Patent Application Publication No. 2012-198408, the contents of which are incorporated herein by reference. Furthermore, commercially available resins having acid groups can also be used. There are no particular restrictions on the method of introducing acid groups into the resin, but for example, the method described in Japanese Patent No. 6349629 can be cited. In addition, as a method of introducing acid groups into the resin, a method can be cited in which an acid anhydride is reacted with a hydroxyl group produced by a ring-opening reaction of an epoxy group to introduce an acid group.

[0257] It is also preferable to use a resin having crosslinkable groups. Examples of crosslinkable groups include ethylenically unsaturated bond-containing groups and cyclic ether groups. Examples of ethylenically unsaturated bond-containing groups include vinyl groups, allyl groups, (meth)acryloyl groups, and styrene groups. Examples of cyclic ether groups include epoxy groups and oxetanyl groups. When using a resin having crosslinkable groups, the content of the resin having crosslinkable groups 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.

[0258] The resin content in the total solids of the curable composition is preferably 1 to 50% by mass. The upper limit is preferably 40% by mass or less, and more preferably 30% by mass or less. The lower limit is preferably 5% by mass or more, and more preferably 10% by mass or more.

[0259] The curable composition of the present invention may contain only one type of resin, or it may contain two or more types of resins. When it contains two or more types of resins, it is preferable that their total amount is within the above range.

[0260] <<Chain Transfer Agent>> The curable composition of the present invention may contain a chain transfer agent. Examples of chain transfer agents include thiol compounds, thiocarbonylthio compounds, and dimers of aromatic α-methylalkenyls, with thiol compounds being preferred. Examples of chain transfer agents include those described in paragraphs 0093 to 0113 of International Publication No. 2019 / 188652.

[0261] The thiol compound used as a chain transfer agent is a compound having one or more thiol groups, and preferably a compound having two or more thiol groups. The upper limit of the number of thiol groups contained in the thiol compound is preferably 10 or less, more preferably 6 or less, and even more preferably 4 or less. It is particularly preferable that the thiol compound is a compound having two thiol groups.

[0262] The thiol compound is preferably a compound represented by the following formula (SH-1). Ｓ１ - (SH)ｎ ...Formula (SH-1) (wherein SH represents a thiol group, L １ (This represents an n-valence base, where n is an integer greater than or equal to 1.)

[0263] L in equation (SH-1) Ｓ１ The n-valent groups represented by include hydrocarbon groups, heterocyclic groups, -O-, -S-, and -NR Ｓ１ -, -CO-, -COO-, -OCO-, -SO ２ - Or, a group consisting of a combination of these. R Ｓ１ The group represents a hydrogen atom, an alkyl group, or an aryl group, with a hydrogen atom being preferred. The hydrocarbon group may be an aliphatic hydrocarbon group or an aromatic hydrocarbon group. The aliphatic hydrocarbon group may be cyclic or acyclic. The aliphatic hydrocarbon group may be a saturated aliphatic hydrocarbon group or an unsaturated aliphatic hydrocarbon group. The hydrocarbon group may have substituents or may not have substituents. The cyclic aliphatic hydrocarbon group and the aromatic hydrocarbon group may be monocyclic or fused rings. The heterocyclic group may be monocyclic or fused rings. A five-membered ring or a six-membered ring is preferred for the heterocyclic group. The heterocyclic group may be an aliphatic heterocyclic group or an aromatic heterocyclic group. Examples of heteroatoms constituting the heterocyclic group include nitrogen atoms, oxygen atoms, and sulfur atoms. １ The number of carbon atoms constituting the compound is preferably 3 to 100, and more preferably 6 to 50.

[0264] In formula (SH-1), n ​​represents an integer greater than or equal to 1. The upper limit of n is preferably 10 or less, more preferably 6 or less, and even more preferably 4 or less. The lower limit of n is preferably 2 or greater.

[0265] Specific examples of thiol compounds include those described in paragraphs 0100-0103 of International Publication No. 2019 / 188652. Commercially available thiol compounds include PEMP (manufactured by SC Organic Chemicals Co., Ltd.), Suncellar M (manufactured by Sanshin Chemical Industry Co., Ltd.), Karenz MTBD1, Karenz MTPE1, Karenz MTNR1, and Karenz MTTPMB (all manufactured by Resonac Co., Ltd.). Thiol compounds described in Japanese Patent Publication No. 2020-109068 can also be used as chain transfer agents.

[0266] As a chain transfer agent, ether-bonded thiol compounds, Multiol Y-2, Y-3, and Y-4 (manufactured by Sakai Chemical Industry Co., Ltd.), described in International Publication No. 2020 / 170944, can also be used.

[0267] The molecular weight of the chain transfer agent is preferably 200 or more. The upper limit is preferably 1000 or less, more preferably 800 or less, and even more preferably 600 or less, because it can increase the SH valency per unit weight.

[0268] The content of the chain transfer agent in the total solid content of the curable composition is preferably 0.001 to 5% by mass. The upper limit is preferably 3% by mass or less, and more preferably 1% by mass or less. The lower limit is preferably 0.05% by mass or more, and more preferably 0.01% by mass or more. Only one type of chain transfer agent may be used, or two or more types may be used. When two or more types are used, it is preferable that their total amount is within the above range.

[0269] <<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 means 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 the epoxy compound include compounds having one or more epoxy groups in one molecule, and compounds having two or more epoxy groups are preferred. The epoxy compound preferably has 1 to 100 epoxy groups in one molecule. The upper limit of the epoxy groups contained in the epoxy compound can be, for example, 10 or less, or 5 or less. The lower limit of the epoxy groups contained in the epoxy compound is preferably 2 or more.

[0270] As the compound having a cyclic ether group, the compounds described in paragraphs 0034 to 0036 of JP-A-2013-011869, paragraphs 0147 to 0156 of JP-A-2014-043556, paragraphs 0085 to 0092 of JP-A-2014-089408, the compounds described in JP-A-2017-179172, the xanthene-type epoxy resin described in JP-A-2021-195421, and the xanthene-type epoxy resin described in JP-A-2021-195422 can be used.

[0271] The compound having a cyclic ether group may be a low molecular weight compound (for example, having a molecular weight of less than 2000, and further having a molecular weight of less than 1000), or a high molecular weight compound (macromolecule) (for example, having a molecular weight of 1000 or more, and in the case of a polymer, having a weight average molecular weight of 1000 or more). The weight average molecular weight of the compound having a cyclic ether group is preferably from 200 to 100000, more preferably from 500 to 50000. The upper limit of the weight average molecular weight is preferably 10000 or less, more preferably 5000 or less, and still more preferably 3000 or less.

[0272] Examples of commercially available compounds having a cyclic ether group include, for example, 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, G-01758 (above, manufactured by NOF Corporation, epoxy group-containing polymers), and the like.

[0273] 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 preferably 0.5% by mass or more, more preferably 1% by mass or more. The upper limit is preferably 15% by mass or less, more preferably 10% by mass or less. Only one kind of the compound having a cyclic ether group may be used, or two or more kinds may be used. When two or more kinds are used, the total amount thereof is preferably within the above range.

[0274] <<Ultraviolet Absorbent>> The curable composition of the present invention can contain an ultraviolet absorbent. Examples of the ultraviolet absorbent include conjugated diene compounds, aminodiene compounds, salicylate compounds, benzophenone compounds, benzotriazole compounds, acrylonitrile compounds, hydroxyphenyltriazine compounds, indole compounds, triazine compounds, dibenzoyl compounds, and the like. Specific examples of such compounds include the compounds described in paragraph 0179 of International Publication No. 2022 / 085485, the reactive triazine ultraviolet absorbent described in JP-A No. 2021-178918, the ultraviolet absorbent described in JP-A No. 2022-007884, the compounds described in Korean Patent Publication No. 10-2022-0014454, the compounds described in JP-A No. 2023-013321, the compounds described in JP-A No. 20

[0275] <<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, cerium salts, etc.). Among 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% by mass. There may be only one type of polymerization inhibitor, or there may be two or more types. If there are two or more types, it is preferable that the total amount is within the above range.

[0276] <<Silane Coupling Agent>> The curable composition of the present invention may contain a silane coupling agent. Examples of silane coupling agents include silane compounds having a hydrolyzable group, and it is preferable that the silane compound has a hydrolyzable group and other functional groups. A hydrolyzable group is a substituent that is directly bonded to a silicon atom and can form a siloxane bond by at least one of a hydrolysis reaction and a condensation reaction. Examples of hydrolyzable groups include halogen atoms, alkoxy groups, and acyloxy groups, with alkoxy groups being preferred. That is, the silane coupling agent is preferably a compound having an alkoxysilyl group. Examples of functional groups other than hydrolyzable groups include vinyl groups, (meth)allyl groups, (meth)acryloyl groups, thiol groups, epoxy groups, oxetanyl groups, amino groups, ureido groups, sulfide groups, isocyanate groups, and phenyl groups, with amino groups, (meth)acryloyl groups, and epoxy groups being preferred. Specific examples of silane coupling agents include the compound described in paragraph 0177 of International Publication No. 2022 / 085485 and the compound described in Japanese Patent Publication No. 2019-183020. The content of the silane coupling agent in the total solid content of the curable composition is preferably 0.1 to 15% by mass. The upper limit is preferably 10% by mass or less, and more preferably 5% by mass or less. The lower limit is preferably 0.5% by mass or more, and more preferably 1% by mass or more. There may be only one type of silane coupling agent, or there may be two or more types. If there are two or more types, it is preferable that the total amount is within the above range.

[0277] <<Surfactants>> The curable composition of the present invention may contain a surfactant. Various surfactants can be used, such as fluorinated surfactants, nonionic surfactants, cationic surfactants, anionic surfactants, and silicone surfactants. The surfactant is preferably a silicone surfactant or a fluorinated surfactant, and more preferably a silicone surfactant. For surfactants, refer to the surfactants described in paragraphs 0238 to 0245 of International Publication No. 2015 / 166779, which are incorporated herein by reference.

[0278] As fluorinated surfactants, compounds described in paragraphs 0167-0173 of International Publication No. 2022 / 085485 can be used.

[0279] Examples of nonionic surfactants include the compounds described in paragraph 0174 of International Publication No. 2022 / 085485.

[0280] Examples of silicone-based surfactants include DOWSIL SH8400, SH8400 FLUID, FZ-2122, 67 Additive, 74 Additive, M Additive, and SF 8419. Examples include OIL (manufactured by Dow Toray Industries, Inc.), TSF-4300, TSF-4445, TSF-4460, TSF-4452 (manufactured by Momentive Performance Materials), KP-341, KF-6000, KF-6001, KF-6002, KF-6003 (manufactured by Shin-Etsu Chemical Co., Ltd.), BYK-307, BYK-322, BYK-323, BYK-330, BYK-333, BYK-3760, BYK-UV3510 (manufactured by Bic Chemie, Inc.), etc. Furthermore, compounds with the following structure can also be used as silicone-based surfactants.

[0281] As surfactants, polymers described in International Publication No. 2021 / 131726, silicone-containing copolymers described in International Publication No. 2024 / 024440, silicone-containing copolymers described in International Publication No. 2024 / 024441, and leveling agents described in International Publication No. 2025 / 018168 can also be used.

[0282] The surfactant content in the total solids of the curable composition is preferably 0.001% to 5.0% by mass, and more preferably 0.005% to 3.0% by mass. The surfactant may be one type or two or more types. If two or more types are used, the total amount is preferably within the above range.

[0283] <<Antioxidants>> The curable composition of the present invention may contain antioxidants. Examples of antioxidants include phenolic antioxidants, amine-based antioxidants, phosphorus-based antioxidants, and sulfur-based antioxidants. Examples of phenolic antioxidants include hindered phenol compounds. Phenolic antioxidants are preferably compounds having a substituent at the ortho position adjacent to the phenolic hydroxyl group. As the substituents, substituted or unsubstituted alkyl groups having 1 to 22 carbon atoms are preferred. Antioxidants are also preferably compounds having a phenol group and a phosphite ester group in the same molecule. Examples of phosphorus-based antioxidants include tris[2-[[2,4,8,10-tetrakis(1,1-dimethylethyl)dibenzo[d,f][1,3,2]dioxaphosfepin-6-yl]oxy]ethyl]amine, tris[2-[(4,6,9,11-tetra-tert-butyldibenzo[d,f][1,3,2]dioxaphosfepin-2-yl)oxy]ethyl]amine, ethylbis(2,4-di-tert-butyl-6-methylphenyl) phosphate, and tris(2,4-di-tert-butylphenyl) phosphite. Examples of commercially available antioxidants include ADEKA stab AO-20, ADEKA stab AO-30, ADEKA stab AO-40, ADEKA stab AO-50, ADEKA stab AO-50F, ADEKA stab AO-60, ADEKA stab AO-60G, ADEKA stab AO-80, and ADEKA stab AO-330 (all manufactured by ADEKA Corporation), and JP-650 (manufactured by Johoku Chemical Industry Co., Ltd.). The antioxidants can also be compounds described in paragraphs 0023-0048 of Japanese Patent No. 6268967, compounds described in International Publication No. 2017 / 006600, compounds described in International Publication No. 2017 / 164024, and compounds described in Korean Published Patent No. 10-2019-0059371. The antioxidant content in the total solid content of the curable composition is preferably 0.01 to 20% by mass, and more preferably 0.3 to 15% by mass. Only one type of antioxidant may be used, or two or more types may be used. If two or more types are used, it is preferable that their total amount falls within the above range.

[0284] <<Other Components>> The curable composition of the present invention may optionally contain sensitizers, plasticizers, and other auxiliary agents (e.g., conductive particles, fillers, defoamers, flame retardants, leveling agents, peel accelerators, fragrances, surface tension modifiers, chain transfer agents, etc.). By appropriately including these components, properties such as film properties can be adjusted. These components can be compounds described in paragraph 0182 of International Publication No. 2022 / 085485, compounds having two or more triethoxysilyl groups described in Japanese Patent Application Publication No. 2023-180607, and the like. In addition, other components that can be used include compounds having two or more triethoxysilyl groups as described in Japanese Patent Publication No. 2023-180607, metal compounds as described in Japanese Patent Publication No. 2024-129722, metal compounds as described in Japanese Patent Publication No. 2024-129724, metal compounds as described in Japanese Patent Publication No. 2024-128802, metal compounds as described in Japanese Patent Publication No. 2024-128809, and metal compounds as described in Japanese Patent Publication No. 2024-129723.

[0285] The curable composition of the present invention may contain a lightfastness modifier. Examples of lightfastness modifiers include the compounds described in paragraph 0183 of International Publication No. 2022 / 085485.

[0286] The curable composition of the present invention may contain compounds derived from biomass raw materials, compounds containing radioactive carbon atoms, and compounds having a percentage modern carbon content of 50% or more. The content of compounds derived from biomass raw materials relative to the total compounds contained in the curable composition of the present invention may be 20% by mass or more.

[0287] The curable composition of the present invention preferably contains substantially no terephthalate ester. Here, "substantially free" means that the terephthalate ester content is 1,000 ppb by mass or less of the total amount of the curable composition, more preferably 100 ppb by mass or less, and particularly preferably zero.

[0288] From the viewpoint of environmental regulations, the curable composition of the present invention preferably has a melamine content of 10,000 ppm by mass or less.

[0289] The curable composition of the present invention preferably has a free metal content of 100 ppm or less, and more preferably 50 ppm or less. Furthermore, the free halogen content is preferably 100 ppm or less, and more preferably 50 ppm or less. Methods for reducing free metals and halogens in the curable composition include washing with deionized water, filtration, ultrafiltration, and purification with ion exchange resin.

[0290] From an environmental perspective, the use of perfluoroalkyl sulfonic acid and its salts, and perfluoroalkyl carboxylic acid and its salts may be restricted. In the curable composition of the present invention, when the content of the above-mentioned compounds is reduced, the content of perfluoroalkyl sulfonic acid (particularly perfluoroalkyl sulfonic acid having 6 to 8 carbon atoms in the perfluoroalkyl group) and its salts, and perfluoroalkyl carboxylic acid (particularly perfluoroalkyl carboxylic acid having 6 to 8 carbon atoms in the perfluoroalkyl group) and its salts is preferably in the range of 0.01 ppb to 1000 ppb, more preferably in the range of 0.05 ppb to 500 ppb, and even more preferably in the range of 0.1 ppb to 300 ppb, relative to the total solid content of the curable composition. The curable composition of the present invention may substantially not contain perfluoroalkyl sulfonic acid and its salts, and perfluoroalkyl carboxylic acid and its salts. For example, a curable composition substantially free of perfluoroalkyl sulfonic acid and its salts, and perfluoroalkyl carboxylic acid and its salts, may be selected by using compounds that can substitute for perfluoroalkyl sulfonic acid and its salts, and compounds that can substitute for perfluoroalkyl carboxylic acid and its salts. Examples of compounds that can substitute for regulated compounds include compounds that have been excluded from regulation due to differences in the number of carbon atoms in the perfluoroalkyl group. However, the above does not preclude the use of perfluoroalkyl sulfonic acid and its salts, and perfluoroalkyl carboxylic acid and its salts. The curable composition of the present invention may contain perfluoroalkyl sulfonic acid and its salts, and perfluoroalkyl carboxylic acid and its salts, to the maximum permissible extent.

[0291] The curable composition of the present invention may contain water. The water content of the curable composition is preferably 0.01 to 2.0% by mass, more preferably 0.05 to 1.0% by mass. The water content can be measured by known methods, such as the Karl Fischer method. Furthermore, water may be removed from the pigment dispersion and the curable composition to adjust the water content. Methods for removing water include, for example, dehydration using azeotrope of the solvent by heating, reduced pressure, or bubbling with dry air, dehydration using a desiccant such as a water-absorbing polymer, and dehydration using a water permeable membrane.

[0292] The curable composition of the present invention can be used by adjusting its viscosity for purposes such as adjusting the film surface (flatness, etc.) and adjusting the film thickness. The viscosity value can be appropriately selected as needed, but for example, 0.3 mPa·s to 50 mPa·s is preferred at 25°C, and 0.5 mPa·s to 20 mPa·s is more preferred. As a method for measuring viscosity, for example, a cone-plate type viscometer can be used and the measurement can be taken while the temperature has been adjusted to 25°C.

[0293] <<Container>> There are no particular limitations on the container used to contain the curable composition, and any known container can be used. Alternatively, the container described in paragraph 0187 of International Publication No. 2022 / 085485 can be used as the container.

[0294] <Method for preparing the 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 dissolved and / or dispersed simultaneously in a solvent to prepare the curable composition, or, if necessary, each component may be prepared as two or more solutions or dispersions and mixed at the time of use (coating) to prepare the curable composition.

[0295] The preparation of the curable composition preferably includes a process for dispersing the pigment. Examples of mechanical forces used in the pigment dispersion process include compression, squeezing, impact, shearing, and cavitation. Specific examples of these processes include bead mills, sand mills, roll mills, ball mills, paint shakers, microfluidizers, high-speed impellers, sand grinders, flow jet mixers, high-pressure wet atomization, and ultrasonic dispersion. Furthermore, in the grinding of the pigment in a sand mill (bead mill), it is preferable to process the material under conditions that enhance grinding efficiency, such as by using small-diameter beads or increasing the bead packing density. It is also preferable to remove coarse particles after the grinding process by filtration or centrifugation. Furthermore, the processes and dispersers for dispersing the pigments can suitably be those described in "Complete Collection of Dispersion Technologies, published by Joho Kiko Co., Ltd., July 15, 2005," "Comprehensive Data Collection on Dispersion Technologies and Industrial Applications Focusing on Suspensions (Solid / Liquid Dispersion Systems), published by Keiei Kaihatsu Center Publishing Department, October 10, 1978," and paragraph 0022 of Japanese Patent Publication No. 2015-157893. In addition, in the process of dispersing the pigments, particle refinement treatment may be performed in a salt milling step. For materials, equipment, and processing conditions used in the salt milling step, for example, refer to the descriptions in Japanese Patent Publication No. 2015-194521 and Japanese Patent Publication No. 2012-046629. Examples of bead materials used for dispersion include zirconia, agate, quartz, titania, tungsten carbide, silicon nitride, alumina, stainless steel, and glass. Furthermore, inorganic compounds with a Mohs hardness of 2 or higher can be used as beads. The curable composition may contain 1 to 10,000 ppm of the above-mentioned beads.

[0296] In preparing a curable composition, it is preferable to filter the composition with a filter for purposes such as removing foreign matter and reducing defects. Examples of filters and filtration methods used for filtration include those described in paragraphs 0196 to 0199 of International Publication No. 2022 / 085485.

[0297] <Membrane> The membrane of the present invention is a membrane obtained by curing the curable composition of the present invention described above. The membrane of the present invention can be used in optical filters such as color filters, infrared transmission filters and infrared cut filters.

[0298] The film thickness of the film of the present invention can be appropriately adjusted depending on the purpose. For example, the film thickness is preferably 20 μm or less, more preferably 10 μm or less, and even more preferably 5 μm or less. The lower limit of the film thickness is preferably 0.1 μm or more, more preferably 0.2 μm or more, and even more preferably 0.3 μm or more.

[0299] When the film of the present invention is used as a color filter, it is preferable that the film has a hue of green, red, blue, cyan, magenta, or yellow. Furthermore, the film of the present invention can be preferably used as a colored pixel of a color filter. Examples of colored pixels include red pixels, green pixels, blue pixels, magenta pixels, cyan pixels, and yellow pixels.

[0300] <Method for Manufacturing Pixels> A method for manufacturing pixels using the curable composition of the present invention will now be described. The method for manufacturing pixels includes the steps of forming a composition layer on a support using the curable composition of the present invention, exposing the composition layer in a pattern, and developing and removing the unexposed parts of the composition layer. If necessary, a step of drying the composition layer (pre-bake step) and a step of heat-treating the developed pattern (pixel) (post-bake step) may be provided.

[0301] In the step of forming the composition layer, the curable composition of the present invention is used to form the composition layer on a support. The support is not particularly limited and can be appropriately selected depending on the application. Examples include glass substrates and silicon substrates, with silicon substrates being preferred. A charge-coupled device (CCD), complementary metal-oxide-semiconductor (CMOS), transparent conductive film, etc., may be formed on the silicon substrate. A black matrix that isolates each pixel may also be formed on the silicon substrate. Furthermore, a base layer may be provided on the silicon substrate to improve adhesion with the upper layer, prevent diffusion of substances, or flatten the substrate surface. The surface contact angle of the base layer is preferably 20 to 70° when measured with diiodomethane. It is also preferably 30 to 80° when measured with water.

[0302] Known methods can be used for coating the curable composition. For example, drop casting; slit coating; spray coating; roll coating; spin coating; casting; slit and spin coating; pre-wetting (for example, the method described in Japanese Patent Application Publication No. 2009-145395); various printing methods such as inkjet (for example, on-demand, piezo, and thermal), nozzle jet printing, flexographic printing, screen printing, gravure printing, reverse offset printing, and metal mask printing; transfer methods using molds, etc.; and nanoimprint methods. In addition, the coating method described in paragraph 0207 of International Publication No. 2022 / 085485 can also be used.

[0303] The composition layer formed on the support may be dried (pre-baked). Pre-baking is not necessary when manufacturing the film by a low-temperature process. If pre-baking is performed, the pre-baking 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, and also 80°C or higher. The pre-baking time is preferably 10 to 300 seconds, more preferably 40 to 250 seconds, and even more preferably 80 to 220 seconds. Pre-baking can be performed using a hot plate, oven, etc.

[0304] Next, the composition layer is exposed in a pattern (exposure step). For example, the composition layer can be exposed in a pattern by exposing it through a mask having a predetermined mask pattern using a stepper exposure machine, a scanner exposure machine, or the like. Thereby, the exposed portion can be cured.

[0305] Examples of the radiation (light) that can be used for exposure include g-line, i-line, etc. Also, light with a wavelength of 150 to 300 nm can be used. Examples of light with a wavelength of 150 to 300 nm include KrF line (wavelength 248 nm), ArF line (wavelength 193 nm), etc., and KrF line (wavelength 248 nm) is preferable. The light with a wavelength of 150 to 300 nm is preferably excimer laser light with a wavelength of 150 to 300 nm. Also, a light source with a long wavelength of 300 nm or more can be used for exposure.

[0306] During exposure, the light may be continuously irradiated for exposure, or may be irradiated pulsedly for exposure (pulse exposure). Note that pulse exposure is an exposure method in which light irradiation and pause are repeated in a cycle of a short time (for example, below the millisecond level) for exposure.

[0307] The irradiation amount (exposure amount) is, for example, preferably 0.03 to 2.5 J / cm ２ and more preferably 0.05 to 1.0 J / cm ２ The oxygen concentration during exposure can be appropriately selected. In addition to performing it under the atmosphere, for example, it may be exposed in a low oxygen atmosphere with an oxygen concentration of 19% by volume or less (for example, 15% by volume, 5% by volume, or substantially oxygen-free), or in a high oxygen atmosphere with an oxygen concentration exceeding 21% by volume (for example, 22% by volume, 30% by volume, or 50% by volume). Also, the exposure illuminance can be appropriately set and is usually 1000 W / m ２ to 100000 W / m ２ (for example, 5000 W / m ２ 、15000 W / m ２ 、or 35000 W / m ２ ) and can be selected from the range. The oxygen concentration and the exposure illuminance may be combined with appropriate conditions. For example, at an oxygen concentration of 10% by volume and an illuminance of 10000 W / m ２At an oxygen concentration of 35% by volume, the illuminance is 20,000 W / m². ２ This can be done as follows.

[0308] Next, the unexposed areas of the composition layer are developed and removed to form a pattern (pixels). The unexposed areas of the composition layer can be developed and removed using a developer. This causes the unexposed areas of the composition layer in the exposure process to dissolve in the developer, leaving only the photocured parts. The temperature of the developer is preferably, for example, 20 to 30°C. The development time is preferably 20 to 180 seconds. In addition, to improve the ability to remove residue, the developer may be emptied every 60 seconds, and the process of supplying fresh developer may be repeated several times.

[0309] Examples of developing solutions include organic solvents and alkaline developers, with alkaline developers being preferred. For the developing solution and the rinsing method after development, the developing solution and rinsing method described in paragraph 0214 of International Publication No. 2022 / 085485 may be used.

[0310] After development and drying, it is preferable to perform additional exposure or heat treatment (post-bake). Additional exposure and post-bake are curing treatments after development to ensure complete hardening. The heating temperature in post-bake is preferably 100 to 300°C, and more preferably 200 to 270°C. Post-bake can be performed continuously or in batches using heating means such as a hot plate, convection oven (hot air circulation dryer), or high-frequency heater to achieve the above conditions. When performing additional exposure, it is preferable that the light used for exposure has a wavelength of 400 nm or less. The additional exposure may also be performed by the method described in Korean Published Patent No. 10-2017-0122130.

[0311] <Optical Filter> The optical filter of the present invention includes the film of the present invention described above. Examples of types of optical filters include color filters, infrared cut filters, and infrared transmission filters, with color filters being preferred. The color filter preferably has the film of the present invention as its pixels, and more preferably has the film of the present invention as its colored pixels.

[0312] The optical filter may have a protective layer on the surface of the film of the present invention. By providing a protective layer, various functions such as oxygen barrier, low reflectivity, hydrophilicity, and shielding of light of specific wavelengths (ultraviolet rays, infrared rays, etc.) can be imparted. The thickness of the protective layer is preferably 0.01 to 10 μm, and more preferably 0.1 to 5 μm. Methods for forming the protective layer include applying a resin composition for forming the protective layer, chemical vapor deposition, and attaching molded resin with an adhesive. The components that make up the protective layer include (meth)acrylic resin, ene-thiol resin, polycarbonate resin, polyether resin, polyarylate resin, polysulfone resin, polyethersulfone resin, polyphenylene resin, polyarylene etherphosphine oxide resin, polyimide resin, polyamide-imide resin, polyolefin resin, cyclic olefin resin, polyester resin, styrene resin, polyol resin, polyvinylidene chloride resin, melamine resin, urethane resin, aramid resin, polyamide resin, alkyd resin, epoxy resin, modified silicone resin, fluororesin, polyacrylonitrile resin, cellulose resin, Si, C, W, Al ２ O ３ Mo, SiO ２ Si ２ N ４ Examples include, and two or more of these components may be included. For example, in the case of a protective layer intended for oxygen barrier, the protective layer may be made of polyol resin and SiO ２ And, Si ２ N ４ It is preferable that it contains [a specific component]. Furthermore, in the case of a protective layer intended for low reflectivity, it is preferable that the protective layer contains (meth)acrylic resin and fluororesin.

[0313] When forming a protective layer by coating a resin composition, known methods such as spin coating, casting, screen printing, and inkjet printing can be used as the coating method for the resin composition. The organic solvent contained in the resin composition can be a known organic solvent (for example, propylene glycol 1-monomethyl ether 2-acetate, cyclopentanone, ethyl lactate, etc.). When forming the protective layer by chemical vapor deposition, known chemical vapor deposition methods (thermochemical vapor deposition, plasma chemical vapor deposition, photochemical vapor deposition) can be used.

[0314] The protective layer may contain additives such as organic and inorganic fine particles, light absorbers of specific wavelengths (e.g., ultraviolet, infrared, etc.), refractive index adjusters, antioxidants, adhesives, and surfactants, as needed. Examples of organic and inorganic fine particles include polymer fine particles (e.g., silicone resin fine particles, polystyrene fine particles, melamine resin fine particles), titanium dioxide, zinc oxide, zirconium oxide, indium oxide, aluminum oxide, titanium nitride, titanium oxynitride, magnesium fluoride, hollow silica, silica, calcium carbonate, and barium sulfate. Known light absorbers can be used for light absorbers of specific wavelengths. The content of these additives can be adjusted as appropriate, but is preferably 0.1 to 70% by mass and more preferably 1 to 60% by mass relative to the total mass of the protective layer.

[0315] As a protective layer, the protective layer described in paragraphs 0073 to 0092 of Japanese Patent Publication No. 2017-151176 can also be used.

[0316] The optical filter may have a structure in which each pixel is embedded in a space partitioned, for example, in a grid pattern by a partition wall.

[0317] <Optical Sensor> The film of the present invention can be used in optical sensors. Examples of optical sensors include solid-state image sensors. The configuration of the solid-state image sensor is not particularly limited as long as it is equipped with the film of the present invention and functions as a solid-state image sensor, but examples include the following configuration.

[0318] The device has a substrate on which multiple photodiodes and transfer electrodes made of polysilicon or the like constitute the light-receiving area of ​​a solid-state image sensor (such as a CCD (charge-coupled device) image sensor or a CMOS (complementary metal-oxide-semiconductor) image sensor), a light-shielding film with an opening only for the light-receiving portion of the photodiode is placed on the photodiode and transfer electrodes, a device protection film made of silicon nitride or the like is formed on the light-shielding film to cover the entire surface of the light-shielding film and the light-receiving portion of the photodiode, and a color filter is placed on the device protection film. Furthermore, the device may have a configuration in which a light-gathering means (for example, a microlens; the same applies hereinafter) is placed on the device protection film and below the color filter (on the side closer to the substrate), or a configuration in which the light-gathering means is placed on the color filter. The color filter may also have a structure in which each colored pixel is embedded in a space partitioned by partitions, for example in a grid pattern. In this case, it is preferable that the partitions have a lower refractive index than each colored pixel. Examples of imaging devices having such a structure include those described in Japanese Patent Publication No. 2012-227478, Japanese Patent Publication No. 2014-179577, and International Publication No. 2018 / 043654. Furthermore, as shown in Japanese Patent Publication No. 2019-211559, the light resistance may be improved by providing an ultraviolet absorption layer within the structure of the solid-state image sensor. The imaging device equipped with the solid-state image sensor of the present invention can be used not only in digital cameras and electronic devices with imaging functions (such as mobile phones), but also in in-vehicle cameras and surveillance cameras.

[0319] <Image Display Devices> The film of the present invention can be used in image display devices. Examples of image display devices include liquid crystal displays and organic electroluminescent displays. For definitions of image display devices and details of each image display device, see, for example, "Electronic Display Devices" (by Akio Sasaki, Kogyo Chosakai Co., Ltd., published in 1990) and "Display Devices" (by Yoshiaki Ibuki, Sangyo Tosho Co., Ltd., published in 1989). Liquid crystal displays are described, for example, in "Next-Generation Liquid Crystal Display Technology" (edited by Tatsuo Uchida, Kogyo Chosakai Co., Ltd., published in 1994). There are no particular restrictions on the liquid crystal display devices to which the present invention can be applied; for example, it can be applied to various types of liquid crystal display devices described in the above-mentioned "Next-Generation Liquid Crystal Display Technology".

[0320] The present invention will be described in more detail below with reference to examples. The materials, amounts used, proportions, processing content, and processing procedures shown in the following examples can be modified as appropriate, as long as they do not depart from the spirit of the present invention. Therefore, the scope of the present invention is not limited to the specific examples shown below. In the structural formulas shown below, Me represents a methyl group, Et represents an ethyl group, iPr represents an isopropyl group, Bu represents a butyl group, and Ph represents a phenyl group.

[0321] <Production of Dispersion> The materials listed in the table below are mixed to obtain a mixture. The resulting mixture is then dispersed using an Ultra Apex Mill manufactured by Kotobuki Kogyo Co., Ltd. as a circulating dispersion device (bead mill) to produce dispersions 1-43, 101-113, and comparative dispersion 1.

[0322]

[0323] The details of the materials listed in the abbreviations in the table above are as follows: (Colorants) P-1: C.I. Pigment Red 254 (red pigment) P-2: C.I. Pigment Red 272 (red pigment) P-3: C.I. Pigment Green 36 (green pigment) P-4: C.I. Pigment Blue 15:6 (blue pigment) P-5: C.I. Pigment Yellow 139 (yellow pigment) P-6: C.I. Pigment Yellow 129 (yellow pigment) P-7: C.I. Pigment Yellow 150 (yellow pigment) P-8: C.I. Pigment Violet 23 (purple pigment) P-9: Silica particles (Aerosil 50, manufactured by Evonik) P-10: Titanium oxide particles (manufactured by Ishihara Sangyo Co., Ltd., TTO-51(C), white pigment) P-11: Titanium oxynitride particles (titanium black, black pigment) P-12: Compound with the following structure (infrared absorbing pigment) P-13: Compound (dye) with the following structure

[0324] P-101 to P-117: Fine pigments P-101 to P-117 manufactured by the following method: 100 parts by mass of the raw material colorant listed in the table below, 10 parts by mass of the raw material dispersion aid listed in the table below, 1000 parts by mass of crushed salt, and 120 parts by mass of diethylene glycol are placed in a stainless steel 1-gallon kneader (manufactured by Inoue Seisakusho) and kneaded at 60°C for 10 hours. This mixture is added to 2000 parts of warm water and stirred in a high-speed mixer for about 1 hour while heating to about 80°C to form a slurry. After removing the salt and solvent by repeated filtration and washing, it is dried at 80°C for 24 hours to obtain 105 parts by mass of fine pigments P-101 to P-117. The raw material colorants P-1, P-3, P-4, P-5, P-6, P-7, P-8, and P-12 in the table below are the same colorants P-1, P-3, P-4, P-5, P-6, P-7, P-8, and P-12 mentioned above. The raw material dispersing aids Syn-1, Syn-3, Syn-4, Syn-5, Syn-6, Syn-7, Syn-8, Syn-9, and Syn-12 in the table below are the same dispersing aids Syn-1, Syn-3, Syn-4, Syn-5, Syn-6, Syn-7, Syn-8, Syn-9, and Syn-12 described later.

[0325]

[0326] P-201: C.I. Pigment Green 58 (green pigment) P-201: C.I. Pigment Yellow 185 (yellow pigment)

[0327] (Dispersing agent) Syn-1 to Syn-12, Syn-101 to Syn-107: Compounds with the following structures. Syn-1, Syn-3, Syn-9, Syn-10, Syn-11, and Syn-101 are compounds that have a dye structure and an acid group, and have a molecular weight of 100 or more and less than 2000. Syn-2, Syn-4, Syn-5, Syn-6, Syn-7, Syn-8, Syn-12, and Syn-102 to Syn-107 are compounds that have a dye structure and a basic group, and have a molecular weight of 100 or more and less than 2000.

[0328] (Dispersed resin) D-1: Resin with the following structure (the values ​​attached to the main chain are molar ratios, and the values ​​attached to the side chains are the number of repeating units. Weight-average molecular weight 25,000, acid value 61.7 mgKOH / g.)

[0329] D-2: Resin with the following structure (the values ​​attached to the main chain are molar ratios, and the values ​​attached to the side chains are the number of repeating units. Weight-average molecular weight 20,000, acid value 66.6 mgKOH / g)

[0330] D-3: Resin with the following structure (weight-average molecular weight 18000, acid value 82.1 mgKOH / g)

[0331] D-4: Resin with the following structure (a compound having a basic group and a graft chain, with a weight-average molecular weight of 2000 to 30000. The values ​​attached to the main chain are molar ratios, and the values ​​attached to the side chains are the number of repeating units. Weight-average molecular weight 15000, acid value 99.6 mgKOH / g, amine value 108.9 mgKOH / g)

[0332] D-5: Resin with the following structure (a compound having a basic group and a graft chain, with a weight-average molecular weight of 2000 to 30000. The values ​​attached to the main chain are molar ratios, and the values ​​attached to the side chains are the number of repeating units. Weight-average molecular weight 22000, acid value 36 mgKOH / g, amine value 47 mgKOH / g)

[0333] D-6: Acrylic block copolymer obtained by the following method. In a reactor equipped with a gas inlet tube, condenser, stirring blade, and thermometer, 50 parts by mass of methyl methacrylate, 20 parts by mass of n-butyl methacrylate, and 13.2 parts by mass of tetramethylethylenediamine as a catalyst are charged, and the mixture is stirred at 50°C for 1 hour while flowing nitrogen to purge the system with nitrogen. Next, 9.3 parts by mass of ethyl bromoisobutyrate as an initiator, 5.6 parts by mass of cuprous chloride as a catalyst, and 133 parts by mass of methoxypropyl acetate are charged, and the temperature is raised to 110°C under a nitrogen atmosphere to start polymerization of the first block (block B). After polymerization for 4 hours, 61 parts by mass of methoxypropyl acetate, 20 parts by mass of dimethylaminoethyl methacrylate as the monomer for the second block (block A), and 10 parts by mass of benzyl chloride salt of dimethylaminoethyl methacrylate are added to the reactor, and the reaction is continued by stirring while maintaining 110°C and a nitrogen atmosphere. Two hours after adding dimethylaminoethyl methacrylate, the reaction solution is cooled to room temperature to stop polymerization and synthesize an acrylic block copolymer. The weight-average molecular weight of the obtained acrylic block copolymer is 12,000, and the amine value is 71.4 mg KOH / g.

[0334] A-11: Polyethyleneimine (weight-average molecular weight 3000)

[0335] D-1 to D-3 are materials corresponding to compounds having an acidic group and a graft chain, with a weight-average molecular weight of 2,000 to 30,000 (compound B1 mentioned above). D-4 and D-5 are materials corresponding to compounds having a basic group and a graft chain, with a weight-average molecular weight of 2,000 to 30,000 (compound A1 mentioned above). D-6 is a material corresponding to a block copolymer having a basic group and a weight-average molecular weight of 2,000 to 30,000 (compound A1 mentioned above).

[0336] (Solvents) S-1: Propylene glycol monomethyl ether acetate S-2: Propylene glycol monomethyl ether S-3: Cyclopentanone

[0337] <Manufacturing of Curable Composition> The curable composition is manufactured by mixing the materials listed in the table below.

[0338] The details of the materials listed in the table above are as follows:

[0339] (Dispersion) Dispersion 1-43, 101-113, comparative dispersion 1: Dispersion 1-43, 101-113, comparative dispersion 1

[0340] (Resin) B-1: Copolymer of methacrylic acid (MAA) and benzyl methacrylate (BnMA) (MAA:BnMA = 70:30 (molar ratio), acid value 112.8 mg KOH / g, weight-average molecular weight 30000) B-2: Resin with the following structure (the values ​​attached to the main chain are molar ratios. Weight-average molecular weight 12000, acid value 31.8 mg KOH / g) B-3: Prysurf A212C (manufactured by Daiichi Kogyo Yakuhin Co., Ltd., acid value 100-120 mg KOH / g)

[0341] (Polymerizable compounds) M-1 to M-5, M-7: Compounds with the following structure M-6: EBECRYL 80 (manufactured by Daicel Ornex, a polymerizable compound having an amino group and an ethylenically unsaturated bond-containing group)

[0342] (Photopolymerization initiators) I-1 to I-3: Compounds with the following structure (glyoxylate compounds) CI-1 to CI-3: Compounds with the following structure (oxime compounds) CI-4: TR-PBG-301 (manufactured by Tronly, oxime compound) CI-5: TR-PBG-314 (manufactured by Tronly, oxime compound) CI-6: TR-PBG-358 (manufactured by Tronly, oxime compound) CI-7: TR-PBG-365 (manufactured by Tronly, oxime compound)

[0343] (Other components 1) Su-1: KF-6001 (manufactured by Shin-Etsu Chemical Co., Ltd., silicone-based surfactant) Su-2: KF-6000 (manufactured by Shin-Etsu Chemical Co., Ltd., silicone-based surfactant) Su-3: SH8400 (manufactured by Dow Toray Industries, Inc., silicone-based surfactant) In-1: p-methoxyphenol (polymerization inhibitor)

[0344] (Other components 2) A-1, A-2: Compounds with the following structure (ultraviolet absorbers) A-3: Adeka Stab AO-80 (manufactured by ADEKA Corporation, antioxidant) A-4: Adeka Stab LA-82 (manufactured by ADEKA Corporation, antioxidant) A-5: EHPE3150 (manufactured by Daicel Corporation, epoxy resin) A-6: Denacol EX-614 (manufactured by Nagase ChemteX Corporation, epoxy compound) A-7: Compound with the following structure (silane coupling agent) A-8: KBM-602 (Shin-Etsu Chemical Co., Ltd., silane coupling agent) A-9: Polyethylene glycol 400 A-10: Compound with the following structure (Solvents) S-1: Propylene glycol monomethyl ether acetate S-2: Propylene glycol monomethyl ether S-3: Cyclopentanone

[0345] <Evaluation> (Pigment Depletion) An 8-inch (20.32 cm) glass wafer is coated with a primer (CT-4000L, manufactured by Fujifilm Electronic Materials Co., Ltd.) using a spin coater to a thickness of 0.1 μm after post-baking. The wafer is then heated on a hot plate at 220°C for 300 seconds to form a base coat layer, obtaining a glass wafer with a base coat layer. Next, each curable composition is applied to the glass wafer with the base coat layer using a spin coater (manufactured by Mikasa Corporation) to a film thickness of 0.5 μm after post-baking to form a coating film. Next, the wafer is heated on a hot plate at 100°C for 2 minutes. Then, an i-line stepper exposure system FPA-3000i5+ (manufactured by Canon Corporation) is used to expose the wafer at 50 to 2500 mJ / cm². ２ Within the range of 25 mJ / cm ２Exposure is performed through a 1.7 μm square Island pattern mask at intervals of exposure. Next, paddle development is performed at 23°C for 60 seconds using a 0.3 mass% aqueous solution of tetramethylammonium hydroxide (TMAH). After that, rinsing is performed with a spin shower and then with pure water. Next, the pattern (pixels) is formed by heating (post-bake) at 220°C for 5 minutes using a hot plate. The glass wafer on which the above pixels have been formed is divided, platinum deposition is performed, and then cross-sectional scanning electron microscope (SEM) images of the pixels at each exposure are obtained using a scanning electron microscope (manufactured by Hitachi High-Tech Corporation). From each SEM image, the exposure amount (E_be) at which the line width of each pixel is 1.7 μm is derived.

[0346] Next, each curable composition is applied to a glass wafer with a base layer using a spin coater (Mikasa Corporation) to form a coating film so that the film thickness after post-baking is 0.5 μm. Then, it is heated at 100°C for 2 minutes using a hot plate. Next, it is exposed using an i-line stepper exposure apparatus FPA-3000i5+ (Canon Corporation) with an exposure amount = E_be through a 1 cm square Island pattern mask. Then, paddle development is performed at 23°C for 60 seconds using a 0.3 mass% aqueous solution of tetramethylammonium hydroxide (TMAH). After that, it is rinsed with a spin shower and then washed with pure water. Next, it is heated at 220°C for 5 minutes (post-baking) using a hot plate to form a pattern (pixels). The absorbance of light with wavelengths of 400 to 1300 nm is measured for the obtained pixels, and the maximum absorbance A_dev in the wavelength range of 400 to 600 nm is obtained.

[0347] Next, each curable composition is applied to a glass wafer with a base layer using a spin coater (Mikasa Corporation) so that the film thickness after post-baking is 0.5 μm, forming a coating film. Then, it is heated at 100°C for 2 minutes using a hot plate. Next, using an i-line stepper exposure system FPA-3000i5+ (Canon Corporation), exposure is performed through a 1 cm square Island pattern mask with an exposure amount of E_be. Then, the film is formed by heating at 220°C for 5 minutes (post-baking) using a hot plate. The absorbance of the obtained film with light at wavelengths of 400 to 1300 nm is measured, and the maximum absorbance A_nondev in the wavelength range of 400 to 600 nm is obtained. Based on these, "ΔA = A_dev / A_nondev" is calculated to evaluate pigment loss. The closer ΔA is to 1, the more suppressed the pigment loss is. 4:ΔA≧0.99 3:0.99>ΔA≧0.95 2:0.95>ΔA≧0.90 1:0.90>ΔA

[0348] (Sensitivity stability over time) An undercoat material (CT-4000L, manufactured by Fujifilm Electronic Materials Co., Ltd.) is applied to an 8-inch (20.32 cm) silicon wafer using a spin coater to a thickness of 0.1 μm after post-baking. The wafer is then heated on a hot plate at 220°C for 300 seconds to form an undercoat layer, obtaining a silicon wafer with an undercoat layer. A curable composition immediately after manufacturing is applied to the silicon wafer with the undercoat layer using a spin coater (manufactured by Mikasa Corporation) to a film thickness of 0.5 μm after post-baking to form a coating film. Next, the wafer is heated on a hot plate at 100°C for 2 minutes. Then, an i-line stepper exposure system FPA-3000i5+ (manufactured by Canon Corporation) is used to expose the wafer at 50 to 2500 mJ / cm². ２ Within the range of 25 mJ / cm ２Exposure is performed at intervals through a 1.7 μm square Island pattern mask. Next, paddle development is performed at 23°C for 60 seconds using a 0.3 mass% aqueous solution of tetramethylammonium hydroxide (TMAH). After that, rinsing is performed with a spin shower and then with pure water. Next, the wafer is heated on a hot plate at 220°C for 5 minutes (post-bake) to form the pattern (pixels). The silicon wafer on which the above pixels have been formed is divided, platinum deposition is performed, and then a scanning electron microscope (Hitachi High-Tech Corporation) is used to obtain cross-sectional scanning electron microscope (SEM) images of the pixels at each exposure level. For each exposure level, the average line width of the pixels is derived with N=45, and the exposure level (E_be) at which the average line width of each pixel is closest to 1.7 μm is derived. Subsequently, the same process is performed on each curable composition after storage at 25°C for 12 months, and the exposure level (E_af) at which the line width of each pixel is closest to 1.7 μm is derived. Based on these, we calculate "ΔE = |E_af - E_be|" to evaluate the temporal stability of the sensitivity. ΔE = 0 mJ / cm ２ The closer the value is to this, the better the sensitivity's stability over time. 4: ΔE < 50 mJ / cm ２ 3:200mJ / cm ２ >ΔE≧50mJ / cm ２ 2:ΔE≧200mJ / cm ２ 1: Unable to obtain E_af

[0349]

[0350]

[0351] As shown in the table above, the examples can form a film that exhibits excellent sensitivity stability over time and suppresses pigment loss during development.

[0352] Similar results can be obtained even if the glass wafer with a base layer used in each evaluation is changed to a glass wafer with a 3 nm thick base layer formed using the base material compositions 1 to 13 shown below.

[0353]

[0354] The details of the materials listed in the table above are as follows:

[0355] (Resin) B-U1: Resin with the following structure (weight-average molecular weight 30,000, the values ​​attached to the main chain are mass ratios, and the values ​​attached to the side chains are the number of repeating units.) B-U2: Cyclomer P (ACA) 230AA (manufactured by Daicel Corporation) B-U3: Resin with the following structure (weight-average molecular weight 30,000, the values ​​attached to the main chain are mass ratios, and the values ​​attached to the side chains are the number of repeating units.) B-U4: Acrycure-RD-F8 (manufactured by Nippon Shokubai Co., Ltd.)

[0356] (Additive) A-5: EHPE3150 (manufactured by Daicel Corporation, epoxy resin)

[0357] (Surfactants) Su-1: KF-6001 (manufactured by Shin-Etsu Chemical Co., Ltd., silicone-based surfactant) Su-2: KF-6000 (manufactured by Shin-Etsu Chemical Co., Ltd., silicone-based surfactant)

[0358] (Solvents) S-1: Propylene glycol monomethyl ether acetate S-U1: Propylene glycol diacetate S-U2: n-butyl acetate S-U3: 2-heptanone S-U4: 3-methoxybutanol

[0359] Red pixels can be formed using the curable composition of Example 1, green pixels using the curable composition of Example 2, and blue pixels using the curable composition of Example 3. These can then be combined with an infrared cut filter to produce an optical filter according to a known method. The infrared cut filter can be prepared using compositions in which the surfactants of compositions 4 to 5 described in International Publication No. 2016 / 178346 are replaced with surfactants 3 to 5 shown below. Similar effects can also be obtained by changing the amount of surfactant added to the above compositions to 5 parts by mass, 1 part by mass, or 0.1 parts by mass. Surfactant 3: X-22-4741 (manufactured by Shin-Etsu Chemical Co., Ltd., a silicone-based surfactant containing epoxy and polyether groups) Surfactant 4: BYK-UV3505 (manufactured by BYK) Surfactant 5: Compound described in Example 1 of Japanese Patent Application Publication No. 2023-169574

[0360] <Preparation of Dispersions 201-203> The pigments, dispersion resins, and solvents listed in the table below are mixed in the parts by mass listed in the table below. The mixture is then mixed and dispersed for 3 hours using a bead mill (zirconia beads, 0.1 mm diameter). Next, a high-pressure disperser with a vacuum mechanism, NANO-3000-10 (manufactured by Nippon BEE Co., Ltd.), is used to produce a mixture at a pressure of 2000 kg / cm². ２ The dispersion treatment is then carried out under the condition of a flow rate of 500 g / min. This dispersion treatment is repeated up to 10 times to obtain dispersions 201 to 203. The water content of each dispersion is recorded together. The water content of the dispersions is measured by the Karl Fischer method.

[0361]

[0362] The details of the materials listed in the table above are as follows:

[0363] (Pigments) W-1: Titanium dioxide particles (white pigment, manufactured by Ishihara Sangyo, Tipaque CR90-2, average primary particle size 250 nm) W-2: Titanium dioxide particles (white pigment, manufactured by Ishihara Sangyo, MPT-141, average primary particle size 90 nm, rutile type, calcination method, contains approximately 10% by mass of aluminum hydroxide as a surface treatment agent for the particles)

[0364] (Dispersed resins) D-101: Resin with the following structure (weight-average molecular weight 12100, acid value 156 mgKOH / g) D-102: Resin with the following structure (weight-average molecular weight 25500, acid value 148 mgKOH / g)

[0365] (Solvent) S-1: Propylene glycol monomethyl ether acetate (PGMEA) S-2: Propylene glycol monomethyl ether (PGME)

[0366] <Preparation of White Resin Compositions 1-15> The materials listed in the table below are mixed in the parts by mass listed in the table below and stirred for 1 hour at 25°C and 50% relative humidity. Then, the mixture is filtered through a PP (polypropylene) filter with a pore size of 6 μm to obtain white resin compositions 1-13. The water content of each white resin composition is listed together. The water content of the white resin compositions is measured by the Karl Fischer method.

[0367]

[0368] <Preparation of White Resin Compositions 16-18> The materials listed in the table below are mixed in the parts by mass listed in the table below and stirred for 1 hour at 25°C and 50% relative humidity. 20 parts by mass of propylene glycol monomethyl ether are added to the resulting composition to make a total of 120 parts by mass, and then the mixture is stirred and depressurized in an evaporator until the total volume is 100 parts by mass to evaporate the solvent. Another 20 parts by mass of propylene glycol monomethyl ether are added to make a total of 120 parts by mass, and the solvent is evaporated in an evaporator until the total volume is 100 parts by mass to obtain white resin compositions 16-18. The water content of each white resin composition is listed together. The water content of the white resin composition is measured by the Karl Fischer method.

[0369]

[0370] The materials listed in the table above are as follows:

[0371] (Dispersion) Dispersion 201-203: Dispersion 201-203 as described above

[0372] (Resin) B-101: Resin with the following structure (the values ​​appended to the main chain are mass ratios. Weight-average molecular weight 31500, acid value 70 mgKOH / g, Mw / Mn = 2.2) D-101, D-102: Resins indicated as the dispersion resins D-101 and D-102 mentioned above (Polymerizable compounds) M-1, M-6: Polymerizable compounds M-1, M-6 as described above M-101: Compound with the following structure

[0373] (Photopolymerization initiators) I-2, CI-1: Photopolymerization initiators I-2 and CI-1 as described above CI-101: Irgacure OXE01 (manufactured by BASF) CI-102: omnirad1314 (manufactured by IGM) CI-103: TR-PBG-301 (manufactured by TRONLY) CI-104: Irgacure OXE03-NP (manufactured by BASF) CI-105: (2,4,6-trimethylbenzoyl)bis(p-tolyl)phosphine oxide

[0374] (Surfactant) Su-1: The surfactant Su-1 mentioned above.

[0375] (Other components) In-1: Polymerization inhibitor In-1 as described above A-3: Antioxidant A-3 as described above A-7: Silane coupling agent A-7 as described above

[0376] (Solvent) S-1: Propylene glycol monomethyl ether acetate (PGMEA) S-2: Propylene glycol monomethyl ether (PGME)

[0377] An optical filter can be manufactured by combining a first filter layer (colored layer or infrared cut filter layer) formed from a curable composition selected from Examples 1-10 and 14-52, and a second filter layer (white layer) formed from a composition selected from white resin compositions 1-18, according to a known method. The first and second filter layers can be formed by the following method. A curable composition selected from Examples 1-10 and 14-52 is applied to a glass substrate using a spin coater (manufactured by Mikasa Corporation) to form a coating film with a film thickness of 0.5 μm after pre-baking. Then, after heating (pre-baking) at 100°C for 120 seconds using a hot plate, exposure is performed at 1000 mJ / cm using an i-line stepper exposure apparatus FPA-3000i5+ (manufactured by Canon Corporation). ２ After full-surface exposure with the specified exposure dose, the first filter layer is formed by heating again using a hot plate at 200°C for 300 seconds (post-bake). A white resin composition is then applied to the resulting first filter layer using a spin coater (manufactured by Mikasa Corporation) so that the film thickness after pre-baking is 5 μm. Next, the sample is heated using a hot plate at 120°C for 120 seconds (pre-bake), and then exposed at 50-2000 mJ / cm using an i-line stepper exposure apparatus FPA-3000i5+ (manufactured by Canon Corporation). ２ The material is exposed to light at the specified exposure level. Then, an optical filter is fabricated in which a second filter layer is formed on top of the first filter layer by heating it at 220°C for 5 minutes (post-bake) using a hot plate.

Claims

1. A curable composition comprising: a colorant containing a pigment; a photopolymerization initiator; a polymerizable compound; at least one selected from compound A1, compound A2, and compound A3; and a solvent, wherein the photopolymerization initiator contains a glyoxylate compound; compound A1 is at least one selected from compound A1-1, which has a basic group and a graft chain and a weight-average molecular weight of 2000 to 30000, and block copolymer A1-2, which has a basic group and a weight-average molecular weight of 2000 to 30000; compound A2 is a compound having at least one structure selected from a dye structure, an aromatic ring, and a heteroaromatic ring, and a basic group, and a molecular weight of 100 to less than 2000; and compound A3 is a polyalkylene imine.

2. The curable composition according to claim 1, wherein the curable composition comprises compound A1, and further comprises compound B1 having at least one structure selected from a dye structure, an aromatic ring, and a heteroaromatic ring, and an acid group, and having a molecular weight of 100 or more and less than 2000.

3. The curable composition according to claim 2, wherein the basic group of compound A1 is an amino group, and the amine value of compound A1 is 15 mg KOH / g or more.

4. The curable composition according to claim 1 or 2, wherein compound A1 is further a compound having an acid group.

5. The curable composition according to claim 1, wherein the curable composition comprises at least one selected from compound A2 and compound A3, and further comprises compound B2 having an acid group and a graft chain, and having a weight-average molecular weight of 2,000 or more and 30,000 or less.

6. The curable composition according to claim 1 or 2, wherein the polymerizable compound comprises a polymerizable compound having an amino group and an ethylenically unsaturated bond-containing group.

7. The curable composition according to claim 1 or 2, wherein the photopolymerization initiator comprises a compound different from the glyoxylate compound.

8. The curable composition according to claim 1 or 2, wherein the glyoxylate compound comprises a compound represented by formula (1) or formula (2); In formula (1), Ar １ R represents an m1+n1 valent group containing at least one selected from the group consisting of aromatic rings and heteroaromatic rings, １ R represents an alkyl group. ２ represents a halogen atom, nitro group, cyano group, or acyl group, n1 represents an integer from 1 to 4, and m1 represents an integer from 0 to 2; in formula (2), Ar １１ R represents an m²+1 valent group containing at least one selected from the group consisting of aromatic rings and heteroaromatic rings, １１ This represents an n-divalent organic group, and R １２ n² represents a halogen atom, nitro group, cyano group, or acyl group, n² represents an integer from 2 to 6, and m² represents an integer from 0 to 2.

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

10. An optical filter having the film described in claim 9.

11. An image display device having the film described in claim 9.

12. An optical sensor having the film described in claim 9.

Images