Photosensitive composition and its uses

Abstract

The objective is to provide a photosensitive composition that can form a film with excellent contact hole formation properties and ITO crack suppression effects. [Solution] The above problem can be solved by a photosensitive composition comprising a colorant, a polymerization initiator, and a polymerizable compound, wherein the polymerizable compound comprises a polymerizable compound containing an ethyleneoxy group and a propyleneoxy group. The molar ratio of the ethyleneoxy group to the propyleneoxy group is preferably 95:5 to 5:95.

Description

[Technical Field]

[0001] The present invention relates to a photosensitive composition used for forming films such as color filters. [Background technology]

[0002] A liquid crystal display panel with a high transmittance structure employing a color-filter-on-array (COA) substrate, in which a color filter is formed on an array substrate, has been developed. The COA method significantly improves the aperture ratio, making it possible to achieve high image quality and low power consumption in color liquid crystal display devices. In the COA method, it is necessary to provide contact holes connecting the transparent electrode ITO and the TFT (Thin Film Transistor) within the colored layer, so the photosensitive composition used to form the colored layer must have excellent contact hole formation properties. Furthermore, in the case of the COA method, the colored layer needs to be formed thicker than in the non-COA method in order to reduce crosstalk between ITO and TFT. A problem with thick colored layers was that, in the step after ITO film formation, the colored layer located beneath the ITO film expanded due to the influence of NMP (N-methyl-2-pyrrolidone) contained in the coating solution applied to the ITO film, making the inorganic ITO film prone to cracking (hereinafter simply referred to as "ITO cracks").

[0003] Therefore, to improve contact hole formation, Patent Document 1 discloses a colored photosensitive resin composition for ultraviolet laser exposure, comprising an aliphatic polyfunctional thiol compound and a photopolymerization initiator of a specific structure. Furthermore, to suppress ITO cracking, Patent Document 2 discloses a colorant dispersion containing a colorant, a solvent, and an AB block copolymer of a specific structure. [Prior art documents] [Patent Documents]

[0004] [Patent Document 1] Japanese Patent Publication No. 2012-14052 [Patent Document 2] International Publication No. 2018 / 159458

Summary of the Invention

Problems to be Solved by the Invention

[0005] However, conventional compositions have had the problem that they cannot achieve both contact hole formation and ITO crack suppression.

[0006] An object of the present invention is to provide a photosensitive composition capable of forming a film with good contact hole formation properties and less likely to generate ITO cracks.

Means for Solving the Problems

[0007] The photosensitive composition of the present invention contains a colorant, a polymerization initiator, and a polymerizable compound, and the polymerizable compound contains a polymerizable compound containing an ethyleneoxy group and a propyleneoxy group, and is a photosensitive composition.

Effects of the Invention

[0008] According to the present invention described above, it is possible to provide a photosensitive composition capable of forming a film with good contact hole formation properties and less likely to generate ITO cracks. Further, the present invention can provide a film, an optical filter, a color filter, a solid-state imaging device, an image display device, and an infrared sensor.

Brief Description of the Drawings

[0009] [Figure 1] FIG. 1 shows a schematic cross-sectional view of an infrared sensor having an optical filter of the present invention.

Embodiments for Carrying Out the Invention

[0010] Hereinafter, embodiments for carrying out the photosensitive composition of the present invention will be described in detail. Note that the present invention is not limited to the following embodiments and can be implemented with modifications within the range capable of solving the problems.

[0011] In this specification, unless otherwise specified, "(meth)acryloyl," "(meth)acrylic," "(meth)acrylic acid," "(meth)acrylate," or "(meth)acrylamide" means "acryloyl and / or methacryloyl," "acrylic and / or methacrylic," "acrylic acid and / or methacrylic acid," "acrylate and / or methacrylate," or "acrylamide and / or methacrylamide," respectively. Also, "CI" means Color Index (CI; published by The Society of Dyers and Colourists). In this specification, a polymerizable unsaturated group is an ethylenically unsaturated double bond. Examples of ethylenically unsaturated double bonds include vinyl groups, (meth)allyl groups, (meth)acryloyl groups, (meth)acryloyloxy groups, (meth)acryloylamide groups, and the like. In this specification, a monomer is a compound that forms a resin by polymerization. A monomer is in an unreacted state, and a monomer unit is in a state where the monomer has formed a resin after polymerization. In this specification, low molecular weight compounds whose molecular weight can be identified are those whose molecular weight is calculated (formula weight) or measured by ESI-MS (electrospray ionization mass spectrometry), and compounds with a molecular weight distribution are those whose molecular weight is the weight-average molecular weight in polystyrene terms, measured by gel permeation chromatography using tetrahydrofuran as the solvent. In this specification, a numerical range represented by "~" means a range that includes the numbers written before and after "~" as the lower and upper limits, respectively.

[0012] <Photosensitive composition> A photosensitive composition according to one embodiment of the present invention comprises a colorant, a polymerization initiator, and a polymerizable compound, wherein the polymerizable compound includes a polymerizable compound containing an ethyleneoxy group and a propyleneoxy group. The photosensitive composition is preferably used as a film formed by coating.

[0013] The mechanism by which the above-described photosensitive composition can solve the problems of the present invention is not clear, but we speculate as follows. The polymerizable compound containing ethyleneoxy and propyleneoxy groups (hereinafter also referred to as the "specific polymerizable compound") contained in the photosensitive composition of the present invention has a flexible structure derived from the ethyleneoxy and propyleneoxy groups. This flexible structure is presumed to enhance the mobility of the polymerizable groups of the polymerizable compound and contribute to improved reactivity. Furthermore, the ethyleneoxy and propyleneoxy groups have different polarities and exhibit broad compatibility with multiple compounds contained in the photosensitive composition. This improved compatibility effect is presumed to reduce the intermolecular distance and the distance between polymerizable groups between the specific polymerizable compound and other compounds, thereby resulting in higher reactivity. In addition, because the ethyleneoxy and propyleneoxy groups are highly hydrophilic, they are also effective in suppressing defects such as pattern peeling, loss, and residue during the development process. Furthermore, contact hole formation typically involves proximity exposure, where an exposure gap is created between the photomask and the workpiece. This exposure weakens diffracted light due to interference, resulting in insufficient photocuring and a tendency for the hole shape to deteriorate. In addition, when forming fine hole patterns, the volume of the unexposed portion within the hole decreases, making it difficult for the developer to penetrate the hole. This leads to insufficient dissolution of the unexposed portion within the hole, and a tendency for development residue to form. However, as described above, specific polymerizable compounds with excellent photocurability and developability can form better hole patterns. Moreover, ITO cracks are thought to be caused by the swelling of the colored layer due to NMP. However, the specific polymerizable compound of this application suppresses the infiltration of NMP into the colored layer and inhibits deformation of the colored layer by improving the crosslinking density due to the improved reactivity during polymerization. Furthermore, the flexible structure derived from ethyleneoxy and propyleneoxy groups absorbs the stress caused by the swelling of the colored layer due to NMP infiltration, and is expected to further effectively suppress deformation of the colored layer, thus exhibiting an excellent ITO crack suppression effect.

[0014] [Polymerizable compound] The photosensitive composition of the present invention contains a polymerizable compound.

[0015] Polymerizable compounds are compounds that are polymerizable and do not have a vinyl polymerization chain. The polymerization chain is formed by polymerizing ethylenically unsaturated groups. Known compounds can be used as polymerizable compounds. Examples include monomers and oligomers having ethylenically unsaturated groups. Examples of ethylenically unsaturated groups include vinyl groups, (meth)allyl groups, (meth)acryloyl groups, (meth)acryloyloxy groups, and styryl groups. The weight-average molecular weight (or formula weight) of the polymerizable compound is 5,000 or less.

[0016] Polymerizable compounds can be used alone or in combination of two or more types.

[0017] From the viewpoint of suppressing foreign matter, the copper ion concentration in the polymerizable compound is preferably 50 ppm or less.

[0018] (Polymerizable compounds containing ethyleneoxy and propyleneoxy groups) Polymerizable compounds containing ethyleneoxy groups and propyleneoxy groups (hereinafter also referred to as "specific polymerizable compounds") can form films with excellent contact hole formation properties and ITO crack suppression effects due to the presence of ethyleneoxy and propyleneoxy groups. Furthermore, in order to form films with excellent contact hole formation properties and ITO crack suppression effects, it is preferable that the specific polymerizable compounds do not contain alkyleneoxy groups other than ethyleneoxy and propyleneoxy groups. Moreover, from the viewpoint of storage stability, it is preferable that the specific polymerizable compounds do not contain hydroxyl groups.

[0019] The number of ethylenically unsaturated groups in the specific polymerizable compound is preferably 2 to 10, more preferably 2 to 6, and even more preferably 2 to 4.

[0020] [Compounds represented by general formula (1) or general formula (2)] The aforementioned specific polymerizable compound is preferably a compound represented by the following general formula (1) or general formula (2) from the viewpoint of contact hole formation and ITO crack suppression effect. The compound represented by general formula (1) is a specific polymerizable compound with a diglycerin skeleton, and the compound represented by general formula (2) is a specific polymerizable compound with a glycerin skeleton.

[0021] General formula (1) [ka]

[0022] In general formula (1), the four Rs are each independently selected from the group consisting of an ethyleneoxy group, a propyleneoxy group, and an ethyleneoxypropyleneoxy group, and of the four Rs, at least one R contains an ethyleneoxy group and at least one R contains a propyleneoxy group. 1 Each of these independently represents a hydrogen atom or a methyl group. x, y, w, and z represent integers totaling 4 to 30. The sum of x, y, w, and z is preferably between 4 and 10, and more preferably between 4 and 6. Note that x, y, w, and z are at least 1. Furthermore, an ethyleneoxypropyleneoxy group is a group formed by the bonding of an ethyleneoxy group and a propyleneoxy group, and the order in which the ethyleneoxy group and the propyleneoxy group are bonded does not matter, and they may be bonded alternately.

[0023] The molar ratio of ethyleneoxy group to propyleneoxy group of the compound represented by general formula (1) is preferably 95:5 to 5:95, more preferably 95:5 to 50:50, and even more preferably 95:5 to 70:30, from the viewpoint of contact hole formation and ITO crack suppression effect.

[0024] Examples of compounds represented by general formula (1) include those represented by the following chemical formulas (M-8) and (M-9).

[0025] [ka]

[0026] [ka]

[0027] Of the compounds represented by general formula (1), the compound of chemical formula (M-8) is preferred from the viewpoint of contact hole formation and ITO crack suppression effect.

[0028] Examples of commercially available compounds represented by general formula (1) include PRO36335 manufactured by Arkema.

[0029] General formula (2) [ka]

[0030] In general formula (2), R and R 1 This is the same as in the general formula (1) above. The sum of x, y, and w represents 3 to 20. Preferably, the sum of x, y, and w is 3 to 10, and more preferably 3 to 4. Note that x, y, and w are at least 1.

[0031] The molar ratio of ethyleneoxy groups to propyleneoxy groups in the compound represented by general formula (2) is preferably 95:5 to 5:95, more preferably 95:5 to 30:70, and even more preferably 95:5 to 60:40, from the viewpoint of contact hole formation and ITO crack suppression effect.

[0032] Examples of compounds represented by general formula (2) include those represented by the following chemical formulas (M-10) and (M-11).

[0033] [ka]

[0034] [ka]

[0035] Of the compounds represented by general formula (2), the compound represented by chemical formula (M-10) is preferred from the viewpoint of contact hole formation and ITO crack suppression effect.

[0036] [Other specific polymerizable compounds] The specified polymerizable compound may be a compound other than the compound represented by general formula (1) or general formula (2) (hereinafter also referred to as "other specified polymerizable compounds"). From the viewpoint of contact hole formation and ITO crack suppression effect, the other specified polymerizable compound preferably contains at least one selected from the trimethylolpropane skeleton, ditrimethylolpropane skeleton, pentaerythritol skeleton, dipentaerythritol skeleton, glycerin skeleton, diglycerin skeleton, isocyanurate skeleton, alkylene glycol skeleton, bisphenol skeleton, and sorbitol skeleton, and more preferably the trimethylolpropane skeleton, ditrimethylolpropane skeleton, pentaerythritol skeleton, dipentaerythritol skeleton, glycerin skeleton, and diglycerin skeleton.

[0037] Other specific polymerizable compounds include, for example, the compounds represented by the following chemical formulas (M-1) to (M-7).

[0038] (Compounds having a trimethylolpropane skeleton) [ka] (Compounds containing a ditrimethylolpropane skeleton) [ka] (Compounds containing a pentaerythritol skeleton) [ka] (Compounds containing a dipentaerythritol skeleton) [ka] (Compounds having an isocyanurate skeleton) [ka] (Compounds having an alkylene glycol skeleton) [ka] (Compounds containing a bisphenol skeleton) [ka]

[0039] Specific polymerizable compounds can be used alone or in combination of two or more types.

[0040] The content of the specific polymerizable compound is preferably 1 to 80% by mass, more preferably 5 to 70% by mass, and even more preferably 5 to 30% by mass, based on 100% by mass of the nonvolatile content of the photosensitive composition.

[0041] (Polymerizable compounds other than specific polymerizable compounds) The polymerizable compounds of this application may contain polymerizable compounds other than the specified polymerizable compounds. Examples of polymerizable compounds other than the specified polymerizable compounds include polymerizable compounds having an amine structure, lactone-modified polymerizable compounds, polymerizable compounds having an acidic group, polymerizable compounds having a hydroxyl group, polymerizable compounds having a urethane bond, polymerizable compounds having a dendrimer structure or a hyperbranch structure, and other polymerizable compounds.

[0042] (Polymerizable compounds having an amine structure) Using polymerizable compounds with an amine structure can further suppress ITO cracking. In addition to normal radical polymerization, polymerizable compounds with an amine structure have a highly electronegative nitrogen atom in their molecule. Therefore, a polymerization initiator can extract a hydrogen atom from a carbon atom adjacent to the nitrogen atom, initiating a polymerization reaction using the resulting active radical. This makes them less susceptible to polymerization inhibition by oxygen, resulting in the formation of a coating with a high crosslink density on the film surface. This is presumed to suppress NMP penetration and improve the ITO crack suppression effect.

[0043] Polymerizable compounds having an amine structure may include primary amino groups, secondary amino groups, and tertiary amino groups. Among these, secondary and tertiary amino groups are preferred. Note that the amine structure does not include amide, imide, urethane, or cyclic amine structures in which the carbonyl group is directly bonded to a nitrogen atom.

[0044] Polymerizable compounds having an amine structure include, for example, tris(acryloyloxyethyl)amine, tris(methacryloyloxyethyl)amine, tris(2-hydroxy-3-methacryloyloxypropyl)amine, and Michael addition reaction products of (meth)acrylate compound (X) and amine compound (Y).

[0045] Polymerizable compounds having an amine structure may also have an acidic group and / or a hydroxyl group. Methods for introducing an acidic group and / or a hydroxyl group include, for example, using a compound having an acidic group and / or a hydroxyl group with a (meth)acrylate compound (X) or an amine compound (Y), or adding an acid anhydride after a Michael addition reaction.

[0046] Examples of commercially available polymerizable compounds having an amine structure include Arronix MT-3041 and 3042 from Toagosei Co., Ltd., EBECRYL80 and 7100 from Daicel Ornex Corporation, CN371NS, 372, 374, 383, and 386 from Arkema Corporation, and Photomer4250, 4771, 4775, 4967, and 5006 from IGM Resins.

[0047] Polymerizable compounds having an amine structure preferably also have urethane bonds. This allows for the formation of a crosslinked structure through polymerization, as well as chemical bonds through intermolecular hydrogen bonding between the urethane bonds. The molecular cohesive energy of the intermolecular hydrogen bonds in these urethane bond portions is greater than that of other organic structures such as ether bonds. Therefore, the film becomes flexible and strong due to the interaction between the urethane bonds, and it is presumed that this improves the ITO crack suppression effect by suppressing NMP penetration and the resulting film swelling.

[0048] A method for introducing urethane bonds can be used, for example, by a urethane reaction between a Michael addition reaction product (precursor) of the above-mentioned (meth)acrylate compound (X) and the above-mentioned hydroxyl group-containing amine compound (Y), and a polyisocyanate compound (Z).

[0049] A method for the urethane reaction between the precursor and the polyisocyanate compound (Z) can be described, for example, by the method described in Japanese Patent Publication No. 2018-517797.

[0050] Examples of commercially available polymerizable compounds having an amine structure and a urethane bond include CN9906NS manufactured by Arkema.

[0051] The content of the polymerizable compound having an amine structure is preferably 0.1 to 80% by mass, and more preferably 0.5 to 60% by mass, based on 100% by mass of the polymerizable compound.

[0052] From the viewpoint of suppressing ITO cracking, polymerizable compounds having an amine structure are preferably present in amounts of 1 to 10% by mass, and more preferably 1 to 3% by mass, of the nonvolatile content of the photosensitive composition.

[0053] (Polymerizable compound containing urethane bonds) Using polymerizable compounds containing urethane bonds can further suppress ITO cracking. Furthermore, polymerizable compounds having urethane bonds do not have an amino structure. Polymerizable compounds containing urethane bonds include, for example, urethane (meth)acrylates obtained by reacting a hydroxyl group-containing (meth)acrylate with a polyfunctional isocyanate, and urethane (meth)acrylates obtained by reacting a polyhydric alcohol with a polyfunctional isocyanate and then reacting it with a hydroxyl group-containing (meth)acrylate. Polymerizable compounds containing urethane bonds do not contain amine structures. It is hypothesized that polymerizable compounds containing urethane bonds can suppress NMP penetration and the resulting film swelling, thereby improving the ITO crack suppression effect, because they generate strong cohesive forces derived from the urethane bonds.

[0054] Polymerizable compounds having urethane bonds may also have acidic groups. Examples of acidic groups include sulfonic acid groups, carboxyl groups, and phosphate groups. Among these, carboxyl groups are preferred.

[0055] One method for introducing an acidic group into a polymerizable compound having a urethane bond is to first react the hydroxyl group-containing (meth)acrylate with the polyfunctional isocyanate, and then add a mercapto compound having a carboxyl group to the product.

[0056] Examples of commercially available polymerizable compounds containing urethane bonds include AH-600, UA-306H, UA-306T, UA-306I, UA-510H, and UF-8001G from Kyoeisha Chemical Co., Ltd., UA-1100H, U-6LPA, UA-33H, U-10HA, and U-15HA from Shin Nakamura Chemical Co., Ltd., and EBECRYL1290 and KRM8452 from Daicel Ornex Co., Ltd.

[0057] The polymerizable compound having a urethane bond is preferably present in an amount of 1 to 90% by mass, and more preferably 1 to 50% by mass, of 100% by mass of the polymerizable compound.

[0058] The polymerizable compound having a urethane bond is preferably present in an amount of 1 to 12% by mass, and more preferably 1 to 8% by mass, of the nonvolatile content of the photosensitive composition.

[0059] (Hydroxy group-containing polymerizable compound) Using a hydroxyl group-containing polymerizable compound can further suppress ITO cracking. Note that the hydroxyl group-containing polymerizable compound does not have an amino structure. Examples of hydroxyl group-containing polymerizable compounds include acrylic acid esters such as 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 2-hydroxybutyl (meth)acrylate, 3-hydroxybutyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, 2,3-hydroxypropyl (meth)acrylate, glycerol mono(meth)acrylate, glycerol di(meth)acrylate, cyclohexanedimethanol mono(meth)acrylate, 2-hydroxy-3-phenoxypropyl acrylate, pentaerythritol tri(meth)acrylate, dipentaerythritol penta(meth)acrylate, polypentaerythritol penta(meth)acrylate, and dipentaerythritol caprolactone-modified penta(meth)acrylate, as well as epoxy(meth)acrylates obtained by reacting the epoxy group of an epoxy compound with the carboxyl group of (meth)acrylic acid. Among these, glycerol di(meth)acrylate, pentaerythritol tri(meth)acrylate, and dipentaerythritol penta(meth)acrylate are preferred.

[0060] Examples of commercially available hydroxyl group-containing polymerizable compounds include KAYARAD R-128H and R-167 from Nippon Kayaku Co., Ltd., Aronix M-5700 and M-920 from Toagosei Co., Ltd., NK Ester 701A from Shin Nakamura Chemical Co., Ltd., Light Ester HOP(N), HOA(N), HOP-A(N), HOB(N), G-201P, Epoxy Ester M-600A, 40EM, 70PA, 200PA, 80MFA, 3002M(N), 3002A(N), and 3000A from Kyoeisha Chemical Co., Ltd., and OGSOL GA-5060P and GA-2800 from Osaka Gas Chemical Co., Ltd.

[0061] The content of the hydroxyl group-containing polymerizable compound is preferably 10 to 99% by mass, and more preferably 20 to 90% by mass, based on 100% by mass of the polymerizable compound.

[0062] (Acidic group-containing polymerizable compound) Using polymerizable compounds containing acidic groups can further suppress ITO cracking. Note that polymerizable compounds containing acidic groups do not have an amino structure. Examples of polymerizable compounds containing acidic groups include poly(meth)acrylates containing free hydroxyl groups of polyhydric alcohols and (meth)acrylic acid, esterified with dicarboxylic acids; and esterified polycarboxylic acids and monohydroxyalkyl (meth)acrylates.

[0063] Examples of the polyhydric alcohols mentioned above include ethylene glycol, propylene glycol, polyethylene glycol, polypropylene glycol, glycerin, trimethylolpropane, ditrimethylolpropane, pentaerythritol, and dipentaerythritol.

[0064] Examples of the dicarboxylic acids mentioned above include malonic acid, succinic acid, maleic acid, glutaric acid, phthalic acid, and itaconic acid.

[0065] Examples of the polycarboxylic acids mentioned above include trimellitic acid and pyromellitic acid. Examples of monohydroxyalkyl (meth)acrylates include 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 2-hydroxybutyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, pentaerythritol triacrylate, and 2-hydroxy-3-acryloyloxypropyl methacrylate.

[0066] Examples of commercially available polymerizable compounds containing acidic groups include Aronics M-5300, M-5400, M-510, M-520, and M-521 from Toagosei Co., Ltd., and Beta-CEA from Daicel Ornex Co., Ltd.

[0067] The content of the acidic group-containing polymerizable compound is preferably 1 to 90% by mass, and more preferably 1 to 50% by mass, based on 100% by mass of the polymerizable compound.

[0068] (Lactone-modified polymerizable compound) Lactone-modified polymerizable compounds are compounds that have a structure modified with lactone within their molecule. For example, lactone-modified polymerizable compounds can be synthesized by esterification reactions of polyhydric alcohols such as trimethylolethane, ditrimethylolethane, trimethylolpropane, ditrimethylolpropane, pentaerythritol, tripentaerythritol, glycerin, diglycerol, and trimethylolmelamine with (meth)acrylic acid and ε-caprolactone or other lactone compounds.

[0069] Examples of commercially available lactone-modified polymerizable compounds include KAYARAD DPCA-20, DPCA-30, DPCA-60, and DPCA-120 manufactured by Nippon Kayaku Co., Ltd.

[0070] (Polymerizable compounds having a dendrimer structure or hyperbranch structure) Compounds with a dendrimer structure have a chemical structure in which a core (hereinafter also referred to as the core portion) repeatedly branches outwards in a regular manner, with polymerizable unsaturated groups bonded to the ends of these branches. They have a highly controlled spherical chemical structure and molecular weight. Hyperbranched structures have a chemical structure similar to that of dendrimer structures.

[0071] Examples of commercially available polymerizable compounds having a dendrimer or hyperbranched structure include: Viscoat #1000LT (dendrimer structure, average acryloyl group count 14) and SIRUS-501 (dendrimer structure, average acryloyl group count 18) from Osaka Organic Chemical Industry Co., Ltd.; MIRAMER SP-1106 (dendrimer structure, average acryloyl group count 18) and SP-1108 (dendrimer structure, average acryloyl group count 13) from MIWON SPECIALTY CHEMICAL Co., Ltd.; CN2301 (hyperbranched structure, average acryloyl group count 9), CN2302 (hyperbranched structure, average acryloyl group count 16), CN2303 (hyperbranched structure, average acryloyl group count 6), and CN2304 (hyperbranched structure, average acryloyl group count 18) from SARTOMER Co., Ltd.; and ETERNAL Examples include ETERCURE 6361-100 (hyperbranch structure, average acryloyl group count 8), 6362-100 (hyperbranch structure, average acryloyl group count 12), 6363 (hyperbranch structure, average acryloyl group count 16), and DR-E522 (hyperbranch structure, average acryloyl group count 15), all manufactured by MATERIALS.

[0072] The polymerizable compound having a dendrimer structure or hyperbranch structure is preferably present in an amount of 1 to 90% by mass, and more preferably 1 to 50% by mass, of 100% by mass of the polymerizable compound.

[0073] (Other polymerizable compounds) Other polymerizable compounds include, for example, methyl (meth)acrylate, ethyl (meth)acrylate, cyclohexyl (meth)acrylate, polyethylene glycol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, triethylene glycol di(meth)acrylate, polypropylene glycol di(meth)acrylate, trimethylolpropane tri(meth)acrylate, phenoxytetraethylene glycol (meth)acrylate, phenoxyhexaethylene glycol (meth)acrylate, ditrimethylolpropane tetra(meth)acrylate, pentaerythritol tetra(meth)acrylate, dipentaerythritol hexa(meth)acrylate, tricyclodecanyl (meth)acrylate, (meth)acrylic acid esters such as (meth)acrylic acid esters of methylolated melamine, styrene, vinyl acetate, ethylene glycol divinyl ether, pentaerythritol trivinyl ether, (meth)acrylamide, N-vinylformamide, acrylonitrile, and the like.

[0074] Other commercially available polymerizable compounds include, for example, Aronics M-140, M-220, M-225, M-270, M-240, M-309, and M-408 from Toagosei Co., Ltd., and NK esters A-HD-N, A-NPG, A-200, A-400, APG-200, APG-400, A-DCP, A-TMPT, A-TMMT, and AD-TMP from Shin Nakamura Chemical Industry Co., Ltd.

[0075] Polymerizable compounds can be used alone or in combination of two or more types.

[0076] The polymerizable compound content is preferably 1 to 80% by mass, and more preferably 5 to 70% by mass, based on 100% by mass of the nonvolatile content of the photosensitive composition.

[0077] [Polymerization initiator] The photosensitive composition of the present invention contains a polymerization initiator. The polymerization initiator is preferably an oxime ester compound. Among oxime ester compounds, a polymerization initiator having an absorption peak at a wavelength of 367 nm or higher is preferred.

[0078] (Polymerization initiators having an absorption peak at a wavelength of 367 nm or higher) The photosensitive composition of the present invention may contain a polymerization initiator having an absorption peak at a wavelength of 367 nm or higher (hereinafter also simply referred to as "specific polymerization initiator") as a polymerization initiator. The specific polymerization initiator generates radical species with long-wavelength light that is effective for curing deep within the film. This allows photocuring to proceed from the surface to the depths of the film, suppressing the penetration of NMP and thus improving the ITO crack suppression effect. From the viewpoint of the ITO crack suppression effect, the absorption peak wavelength of the specific polymerization initiator is more preferably 370 nm or higher, and even more preferably 375 nm or higher. When used for color filter applications, for example, the absorption peak wavelength is preferably 420 nm or lower from the viewpoint of brightness.

[0079] (Specific oxime ester compounds) Examples of the specific oxime ester compounds that serve as the specific polymerization initiators are given below. Chemical formula (Ini-3) below represents a specific oxime ester compound with an absorption peak at 368 nm, and chemical formula (Ini-15) below represents a specific oxime ester compound with an absorption peak at 379 nm. [ka]

[0080] Examples of commercially available specific oxime ester compounds include NCI-831 manufactured by Adeka Corporation and PBG-345 manufactured by Changzhou Strong Co., Ltd.

[0081] From the viewpoint of contact hole formation and ITO crack suppression effect, the content of the specific oxime ester compound is preferably 10 to 95% by mass, and more preferably 50 to 95% by mass, of 100% by mass of the polymerization initiator.

[0082] (Polymerization initiators other than specific oxime ester compounds that have an absorption peak at a wavelength of 367 nm or higher) The photosensitive composition of the present invention may contain polymerization initiators other than specific oxime ester compounds that have an absorption peak at a wavelength of 367 nm or higher (hereinafter also simply referred to as "specific polymerization initiators other than specific oxime ester compounds").

[0083] The following are specific examples of specific polymerization initiators other than specific oxime ester compounds. However, the present invention is not limited to these examples. (Specific polymerization initiators having a phosphine oxide structure) The following are examples of specific polymerization initiators having a phosphine oxide structure. The chemical formula (Ini-16) below represents a compound with an absorption peak at 380 nm, and the chemical formula (Ini-17) below represents a compound with an absorption peak at 370 nm. [ka]

[0084] Among specific polymerization initiators other than specific oxime ester compounds, compounds having a phosphine oxide structure are preferred because they tend to yield absorption peaks in longer wavelength regions. From the viewpoint of ITO crack suppression effect, compounds represented by chemical formulas (Ini-16) and (Ini-17) are preferred among the specific polymerization initiators having a phosphine oxide structure.

[0085] Examples of commercially available specific polymerization initiators having a phosphine oxide structure include OMNIRAD 819, TPO-L, and TPO N from BASF.

[0086] From the viewpoint of contact hole formation and ITO crack suppression effect, the content of the specific polymerization initiator is preferably 10 to 95% by mass, and more preferably 50 to 95% by mass, of 100% by mass of the polymerization initiator.

[0087] (Oximeter compounds other than specified oximeter compounds) Other than the specified oxime ester compounds, at least one selected from the group consisting of compounds having an indole structure, compounds having a carbazole structure, and compounds having a benzofuran structure is preferred from the viewpoint of contact hole formation and ITO crack suppression effect, and compounds having an indole structure are more preferred.

[0088] (Compounds having a carbazole structure) The following are specific examples of compounds having a carbazole structure. However, the present invention is not limited to these examples.

[0089] [ka]

[0090] (Compounds having a benzofuran structure) The following are specific examples of compounds having a benzofuran structure. However, the present invention is not limited to these examples.

[0091] [ka]

[0092] (Compounds containing an indole structure) The compound having the above indole structure is preferably a compound represented by the following general formula (4).

[0093] General formula (4) [ka]

[0094] In general formula (4), R1 and R2 each independently represent a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 30 carbon atoms, an arylalkyl group having 7 to 30 carbon atoms, or a heterocyclic group having 2 to 20 carbon atoms. Alkyl groups having 1 to 20 carbon atoms can be linear, branched, cyclic, or a combination thereof. These alkyl groups can be substituted with halogen atoms, cyano groups, amino groups, alkoxy groups, etc. Examples of these alkyl groups include methyl, ethyl, propyl, isopropyl, butyl, isobutyl, tert-butyl, amyl, isoamyl, pentyl, hexyl, heptyl, octyl, isooctyl, 2-ethylhexyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, cyclopentyl, cyclopentylmethyl, cyclohexyl, and cyclohexylmethyl groups. Examples of aryl groups having 6 to 30 carbon atoms include phenyl, tolyl, xylyl, ethylphenyl, naphthyl, and anthuryl groups. The aryl group may also be substituted with a halogen atom, cyano, amino, or alkoxy group. Examples of arylalkyl groups having 7 to 30 carbon atoms include benzyl, α-methylbenzyl, α,α-dimethylbenzyl, and phenylethyl groups. The arylalkyl group may also be an aryl group substituted with a halogen atom, a cyano group, an amino group, an alkoxy group, or the like. Examples of heterocyclic groups having 2 to 20 carbon atoms include pyridyl, pyrimidyl, furyl, tetrahydrofuryl, dioxolanyl, imidazolidyl, oxazolidyl, piperidyl, and morpholinyl groups. The heterocyclic group may also be an aryl group substituted with a halogen atom, cyano, amino, or alkoxy group. Among these, R1 is preferably an alkyl group having 1 to 20 carbon atoms, and more preferably an alkyl group having 3 to 8 carbon atoms. R2 is preferably a methyl group, an ethyl group, or a phenyl group, and more preferably a methyl group or a phenyl group.

[0095] A method for producing the compound represented by general formula (4) is, for example, the method described in International Publication No. 2015 / 152153.

[0096] The following are specific examples of compounds represented by general formula (4). However, the present invention is not limited to these examples.

[0097] [ka]

[0098] [ka]

[0099] The following chemical formulas (Ini-9) to (Ini-13) can also be used as oxime ester compounds other than the specified oxime ester compounds mentioned above. However, the present invention is not limited to these. JPEG2026068945000022.jpg88133

[0100] The content of oxime ester compounds other than the specified oxime ester compounds is preferably 10 to 90% by mass, and more preferably 50 to 90% by mass, of 100% by mass of the polymerization initiator, from the viewpoint of contact hole formation and ITO crack suppression effect.

[0101] (Other polymerization initiators) From the viewpoint of contact hole formation, the polymerization initiator may contain the above-mentioned specific oxime ester compound, the specific polymerization initiator, and polymerization initiators other than the specific oxime ester compound (hereinafter also simply referred to as "other polymerization initiators").

[0102] Other polymerization initiators are not limited and any known compounds can be used. For example, acetophenone compounds such as 4-phenoxydichloroacetophenone, 4-t-butyl-dichloroacetophenone, diethoxyacetophenone, 1-(4-isopropylphenyl)-2-hydroxy-2-methylpropan-1-one, 1-hydroxycyclohexylphenyl ketone, 2-methyl-1-[4-(methylthio)phenyl]-2-morpholinopropan-1-one, 2-(dimethylamino)-1-[4-(4-morpholino)phenyl]-2-(phenylmethyl)-1-butanone, and 2-(dimethylamino)-2-[(4-methylphenyl)methyl]-1-[4-(4-morpholinyl)phenyl]-1-butanone; Examples of triazine compounds include 2,4,6-trichloro-s-triazine, 2-phenyl-4,6-bis(trichloromethyl)-s-triazine, 2-(p-methoxyphenyl)-4,6-bis(trichloromethyl)-s-triazine, 2-(p-tolyl)-4,6-bis(trichloromethyl)-s-triazine, 2-piperonyl-4,6-bis(trichloromethyl)-s-triazine, 2,4-bis(trichloromethyl)-6-styryl-s-triazine, 2-(naphtho-1-yl)-4,6-bis(trichloromethyl)-s-triazine, 2-(4-methoxy-naphtho-1-yl)-4,6-bis(trichloromethyl)-s-triazine, 2,4-trichloromethyl-(piperonyl)-6-triazine, and 2,4-trichloromethyl-(4'-methoxystyryl)-6-triazine.

[0103] The content of other polymerization initiators is preferably 1 to 20% by mass, and more preferably 2 to 10% by mass, based on 100% by mass of the nonvolatile content of the photosensitive composition.

[0104] Polymerization initiators can be used alone or in combination of two or more types.

[0105] The polymerization initiator content is preferably 0.5 to 15% by mass, and more preferably 1 to 5% by mass, based on 100% by mass of the nonvolatile content of the photosensitive composition.

[0106] [Compounds represented by general formula (5) or general formula (6)] The photosensitive composition of the present invention preferably contains a compound represented by general formula (5) or general formula (6). The compound represented by general formula (5) or general formula (6) acts as a polymerization inhibitor. The compound represented by general formula (5) or general formula (6) has a phenolic hydroxyl group and a relatively small molecular weight, and therefore has the advantage of being able to be incorporated in a larger number of moles per mass compared to other polymerization inhibitors. As a result, polymerization inhibition can be performed more broadly and uniformly, and the molecular weight of the polymer obtained in the exposure process is more uniform, resulting in uniform developability. This improves contact hole formation.

[0107] General formula (5) [ka] (In general formula (5), R 1 (This represents a hydrocarbon group with 1 to 4 carbon atoms.)

[0108] R 1 Examples of hydrocarbon groups having 1 to 4 carbon atoms include the methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, and isobutyl group.

[0109] Compounds represented by general formula (5) include methylhydroquinone, ethylhydroquinone, propylhydroquinone, and tert-butylhydroquinone. Among these, methylhydroquinone is preferred from the viewpoint of contact hole formation. It is expected that a remarkable effect will be obtained due to its high compatibility with the specific polymerizable compound of this application.

[0110] General formula (6) [ka] (In general formula (6), R 1 R represents a hydrocarbon group having 1 to 4 carbon atoms, or an alkoxy group having 1 to 4 carbon atoms. 2 Each of these independently represents either a hydrogen atom or a hydrocarbon group having 1 to 4 carbon atoms.

[0111] R1 and R 2 The hydrocarbon group having 1 to 4 carbon atoms is the same as that in general formula (5). Examples of alkoxy groups having 1 to 4 carbon atoms include the methoxy group, ethoxy group, propoxy group, and butoxy group.

[0112] The compounds represented by general formula (6) are preferably p-methoxyphenol and 2,6-di-tert-butyl-4-methylphenol. Of these, 2,6-di-tert-butyl-4-methylphenol is preferred from the viewpoint of contact hole formation. It is presumed that a remarkable effect can be obtained because of its high compatibility with the specific polymerizable compound of this application.

[0113] Compounds represented by general formula (5) or general formula (6) may be used in combination of two or more types.

[0114] From the viewpoint of contact hole formation, the content of the compound represented by general formula (5) or general formula (6) is preferably 0.005 to 0.4% by mass of 100% by mass of the nonvolatile content of the photosensitive composition.

[0115] Compounds represented by general formula (5) or general formula (6) may be used in combination with other polymerization inhibitors. Other polymerization inhibitors are not limited to known compounds and can be used. Examples include phenol compounds, hydroquinone compounds, benzoquinone compounds, phenothiazine compounds, catechol compounds, nitrobenzene compounds, nitroso compounds, amine compounds, hindered amine compounds, phosphorus compounds, etc.

[0116] [Alkali-soluble resin] The photosensitive composition of the present invention may contain an alkali-soluble resin. The alkali-soluble resin is a resin that can be dissolved in an alkaline developer used in photolithography.

[0117] Alkali-soluble resins are not limited to and are known resins. Examples of alkali-soluble resins include (meth)acrylic resins, styrene resins, styrene / (meth)acrylic resins, epoxy resins, urethane resins, polycarbonate resins, polyester resins, polyether resins, polyimide resins, polyamide-imide resins, and cyclic olefin resins.

[0118] Examples of alkali-soluble groups in alkali-soluble resins include acidic groups such as carboxyl groups, phosphate groups, and sulfonic acid groups. Among these, carboxyl groups are more preferred from the viewpoint of contact hole formation.

[0119] The molecular structures of alkali-soluble resins include, for example, chain-like random structures, chain-like block structures, graft structures, comb-like structures, and star-like structures. Among these, chain-like random structures (random polymers) are preferred from the viewpoint of contact hole formation and ITO crack suppression effect.

[0120] The weight-average molecular weight (Mw) of the alkali-soluble resin is preferably 3,000 to 50,000, and more preferably 4,000 to 40,000.

[0121] The acid value of the alkali-soluble resin is preferably 30 to 200 mg KOH / g, and more preferably 40 to 180 mg KOH / g.

[0122] Alkali-soluble resins can be used alone or in combination of two or more types.

[0123] The alkali-soluble resin is preferably present in an amount of 1 to 95% by mass, and more preferably 5 to 80% by mass, of 100% by mass of the nonvolatile content of the photosensitive composition.

[0124] The alkali-soluble resin preferably contains (a) polymerizable unsaturated group-containing monomer units, or (b) thermally crosslinkable group-containing monomer units. This improves contact hole formation and ITO crack suppression. Examples of alkali-soluble resins include copolymers of (a) polymerizable unsaturated group-containing monomer units, or (b) thermally crosslinkable group-containing monomer units, and other monomers that can be optionally copolymerized. The alkali-soluble resin may also contain (a) polymerizable unsaturated group-containing monomer units and (b) thermally crosslinkable group-containing monomer units.

[0125] [(a) Polymerizable unsaturated group-containing monomer units] Methods for incorporating polymerizable unsaturated group-containing monomer units into an alkali-soluble resin include, for example, the methods (I) to (III) shown below. From the viewpoint of contact hole formation and ITO crack suppression effect, the structure of the polymerizable unsaturated group-containing monomer unit obtained by method (I) is preferred. By combining it with the specific polymerizable compound of this application, a cured film with a higher degree of crosslinking can be obtained, and the ITO crack suppression effect is improved. Hereinafter, the resin containing (a) polymerizable unsaturated group-containing monomer units will also be referred to as "alkali-soluble resin 1".

[0126] <Method (I)> Method (I) involves, for example, first synthesizing polymers (precursors) of epoxy group-containing monomers and other monomers. Then, a carboxyl group-containing monomer (modified compound) is added to the epoxy group of the precursor.

[0127] Examples of epoxy group-containing monomers include glycidyl (meth)acrylate, methylglycidyl (meth)acrylate, 2-glycidoxyethyl (meth)acrylate, 3,4-epoxybutyl (meth)acrylate, and 3,4-epoxycyclohexyl (meth)acrylate. Among these, glycidyl (meth)acrylate is preferred from the viewpoint of reactivity.

[0128] Examples of the carboxyl group-containing monomer include acrylic acid, methacrylic acid, crotonic acid, itaconic acid, maleic acid, fumaric acid, etc. Among these, acrylic acid and methacrylic acid are preferred.

[0129] From the viewpoint of developability, an acid anhydride can be reacted with a site where a carboxyl group of a carboxyl group-containing monomer is added to an epoxy group of an epoxy group-containing monomer unit to coexist a polymerizable unsaturated group and a carboxyl group.

[0130] Examples of the acid anhydride include tetrahydrophthalic anhydride, phthalic anhydride, hexahydrophthalic anhydride, succinic anhydride, maleic anhydride, etc.

[0131] The resin obtained by the method (I) is preferably an alkali-soluble resin having a repeating unit represented by the following general formula (7) from the viewpoints of pattern forming property and ITO crack suppressing effect.

[0132] General formula (7)

Chemical formula

[0133] In the general formula (7), R represents a hydrogen atom or a methyl group. L 1represents a divalent hydrocarbon group. Examples of the divalent hydrocarbon group include a divalent aliphatic hydrocarbon group, a divalent aromatic hydrocarbon ring group, etc. The divalent aliphatic hydrocarbon group may be linear, branched, cyclic, or a combination thereof. Further, a part of the divalent aliphatic hydrocarbon group can be substituted with an alkoxy group, a carboxy group, a halogen atom, etc. The number of carbon atoms of the divalent aliphatic hydrocarbon group is preferably 1 to 15, more preferably 3 to 10. Examples of the divalent aliphatic hydrocarbon group include an ethylene group, a propylene group, an ethenylene group, a cyclohex-4-en-1,2-diyl group, a cyclohex-1,2-diyl group, etc. The divalent aromatic hydrocarbon ring group is a monocyclic or condensed ring. A part of the divalent aromatic hydrocarbon ring group can be substituted with an alkoxy group, a carboxy group, a halogen atom, etc. Examples of the divalent aromatic hydrocarbon ring group include a benzene ring, a naphthalene ring, an anthracene ring, a phenanthrene ring, a perylene ring, a pyrene ring, a fluorene ring, etc. The divalent aliphatic hydrocarbon group is preferably an ethylene group or a cyclohex-4-en-1,2-diyl group.

[0134] <Method (II)> Method (II) is, for example, first, a polymer (precursor) of a carboxyl group-containing monomer and other monomers is synthesized. Next, an epoxy group-containing monomer (modifying compound) is added to the carboxyl group of the precursor.

[0135] <Method (III)> Method (III) is, for example, first, a polymer (precursor) of a hydroxyl group-containing monomer and other monomers is synthesized. Next, the hydroxyl group of the precursor is reacted with the isocyanate group of an isocyanate group-containing monomer (modifying compound).

[0136] Examples of the hydroxyl group-containing monomer include hydroxyalkyl (meth) acrylates such as 2-hydroxyethyl (meth) acrylate, 2- or 3-hydroxypropyl (meth) acrylate, 2- or 3- or 4-hydroxybutyl (meth) acrylate, glycerol mono (meth) acrylate, or cyclohexanedimethanol mono (meth) acrylate.

[0137] The isocyanate group-containing monomer includes, for example, 2-(meth)acryloylethyl isocyanate, 2-(meth)acryloyloxyethyl isocyanate, 1,1-bis[methacryloyloxy]ethyl isocyanate, and the like.

[0138] From the viewpoints of contact hole forming property and ITO crack suppressing effect, the content of the polymerizable unsaturated group-containing monomer unit is preferably 5 to 80 mol%, more preferably 30 to 80 mol%, based on all the monomer units of the alkali-soluble resin 1.

[0139] [[(b) Monomer unit containing a thermally crosslinkable group]] The thermally crosslinkable group is a group that undergoes a crosslinking reaction and crosslinks upon heating. Examples thereof include a cyclic ether group, a methylol group, an isocyanate group, a blocked isocyanate group, an acetoacetoxy group, an alkoxysilyl group, a tertiary alkyl group, and the like. Among these, from the viewpoints of contact hole forming property and ITO crack suppressing effect, at least one selected from the group consisting of a blocked isocyanate group, an acetoacetoxy group, an alkoxysilyl group, and a tertiary alkyl group is preferable. Hereinafter, the resin containing the (b) monomer unit containing a thermally crosslinkable group is also referred to as "alkali-soluble resin 2". From the viewpoints of contact hole forming property and ITO crack suppressing effect, the thermally crosslinkable group-containing monomer unit is preferably formed from monomers represented by the following general formulas (8) to (12), more preferably general formulas (8) to (9), and even more preferably general formula (8). Also, when the (b) thermally crosslinkable group-containing monomer unit is 1 mol% or less in all the monomer units, it is not included in the (b) thermally crosslinkable group-containing monomer unit. Furthermore, the (a) polymerizable unsaturated group-containing monomer unit and the (b) thermally crosslinkable group-containing monomer unit may be used in combination.

[0140] The monomer of general formula (8) is a blocked isocyanate group-containing compound. A blocked isocyanate group-containing compound is a compound in which the isocyanate group of an isocyanate group-containing compound is protected with a blocking agent. The reaction of the blocked isocyanate group can be (a) by thermal elimination of the blocking agent to regenerate the isocyanate, and the regenerated isocyanate group undergoes a crosslinking reaction, or (b) by a transesterification reaction. From the viewpoint of suppressing ITO cracking, the elimination temperature of the blocking agent or the temperature at which the transesterification reaction proceeds is preferably 60 to 160°C, more preferably 70 to 130°C, and particularly preferably 80 to 110°C.

[0141] General formula (8) [ka]

[0142] In general formula (8), R 1 represents a hydrogen atom or a methyl group. R 2 and R 3 Each of these independently represents an alkyl group having 1 to 10 carbon atoms. C1 to 10 alkyl groups can be linear or branched. Examples include methyl group, ethyl group, n-propyl group, n-butyl group, n-pentyl group, n-hexyl group, isopropyl group, isobutyl group, amyl group, isoamyl group, pentyl group, hexyl group, heptyl group, octyl group, isooctyl group, 2-ethylhexyl group, nonyl group, decyl group, etc. Among these, methyl group, ethyl group, and n-propyl group are preferred. L 1represents a single bond or a divalent organic group. Examples of the divalent organic group include an alkylene group having 1 to 20 carbon atoms or a group having -O- between carbon-carbon bonds of an alkylene group having 1 to 20 carbon atoms. The alkylene group having 1 to 20 carbon atoms is linear or branched. For example, methylene group, ethylene group, n-propylene group, n-butylene group, n-pentylene group, n-hexylene group, n-heptylene group, n-octylene group, isopropylene group, 2-methylpropylene group, 2-methylhexylene group, tetramethylethylene group, etc. are included. Among these, methylene group, ethylene group, and n-propylene group are preferred. L 2 represents a single bond or an oxygen atom. L 3 and L 4 each independently represents a single bond or a divalent organic group. Examples of the divalent organic group include an alkylene group having 1 to 20 carbon atoms. The alkylene group having 1 to 20 carbon atoms is the same as described above.

[0143] The method for producing the monomer represented by the general formula (8) is not limited, and known methods can be used. For example, the methods described in JP-A-10-316643, International Publication No. 2022 / 145298, etc. are included.

[0144] Hereinafter, examples of the monomer represented by the general formula (8) include compounds represented by chemical formulas (1-1) to (1-14). Note that the present invention is not limited to these.

[0145]

Chemical formula

[0146] From the viewpoint of the ITO crack suppression effect, the monomer represented by the general formula (8) is preferably one or more selected from the compounds of the above chemical formulas (1-1), chemical formula (1-2), chemical formula (1-3), chemical formula (1-4), chemical formula (1-9), chemical formula (1-10), chemical formula (1-11), chemical formula (1-12), chemical formula (1-13), and chemical formula (1-14).

[0147] The monomer represented by the general formula (9) is a compound containing an ethylenically unsaturated double bond. It is described in International Publication No. 2022 / 145298 etc. that the ethylenically unsaturated double bond has reactivity at 90°C.

[0148] General formula (9)

Chemical formula

[0149] In the general formula (9), R 1 represents a hydrogen atom or a methyl group. R 4 ~R 6 each independently represents a hydrogen atom or an alkyl group having 1 to 10 carbon atoms. The alkyl group having 1 to 10 carbon atoms is the same as above. Among these, R 4 and R 5 are preferably hydrogen atoms, and R 6 is preferably a methyl group, an ethyl group, or an n-propyl group.

[0150] L 1 represents a single bond or a divalent organic group. Examples of the divalent organic group include an alkylene group having 1 to 20 carbon atoms or a group having -O- between carbon-carbon bonds of an alkylene group having 1 to 20 carbon atoms. The alkylene group having 1 to 20 carbon atoms is the same as above.

[0151] The method for producing the monomer represented by the general formula (9) is not limited, and known methods can be used. For example, the methods described in International Publication No. 2022 / 145298 etc. can be mentioned.

[0152] Hereinafter, compounds represented by chemical formulas (2-1) to (2-6), which are specific examples of the monomer represented by the general formula (9), are mentioned. Note that the present invention is not limited to these.

[0153]

Chemical formula

[0154] The monomer represented by the general formula (10) is a monomer containing an acetoacetyl group. It is known that the acetoacetyl group reacts with an acetoacetyl group or a hydroxyl group by heating to form a crosslinked structure (e.g., Japanese Patent Laid-Open No. 2007-138114, etc.).

[0155] General formula (10)

Chemical formula

[0156] In the general formula (10), R 1 represents a hydrogen atom or a methyl group. R 7 represents an alkyl group having 1 to 10 carbon atoms. The alkyl group having 1 to 10 carbon atoms is the same as described above. L 1 represents a single bond or a divalent organic group. Examples of the divalent organic group include an alkylene group having 1 to 20 carbon atoms or a group having -O- between carbon-carbon bonds of an alkylene group having 1 to 20 carbon atoms. The alkylene group having 1 to 20 carbon atoms is the same as described above.

[0157] The method for producing the monomer represented by the general formula (10) is not particularly limited, and known methods can be used. For example, the methods described in Coatings Technology, Vol. 62 by Witzeman, J.S. and Dell Rector, F.J. can be mentioned.

[0158] Hereinafter, examples of the monomer represented by the general formula (10) include compounds represented by chemical formulas (3-1) to (3-4). However, the present invention is not limited thereto.

[0159]

Chemical formula

[0160] The monomer represented by the general formula (11) is an alkoxysilyl group-containing monomer. The alkoxysilyl group readily generates a silanol group upon hydrolysis, and the silanol group dehydrates and condenses with the hydroxyl group in the photosensitive composition upon heating, forming a covalent bond.

[0161] General formula (11) [ka]

[0162] In general formula (11), R 1 represents a hydrogen atom or a methyl group. R 8 ~R 10 Each of these independently represents a hydrogen atom, a C1-C6 alkyl group, or a C1-C6 alkoxy group. However, R 8 ~R 10 At least one of these is an alkoxy group having 1 to 6 carbon atoms. Examples of alkyl groups having 1 to 6 carbon atoms include methyl, ethyl, butyl, n-propyl, n-butyl, n-pentyl, n-hexyl, isopropyl, and isobutyl groups. Examples of alkoxy groups having 1 to 6 carbon atoms include methoxy, ethoxy, propoxy, butoxy, and isopropoxy groups. Among these, methoxy and ethoxy groups are preferred from the viewpoint of ITO crack suppression effect. Furthermore, from the viewpoint of ITO crack suppression effect, in general formula (11), R 8 ~R 10 At least two of these are preferably alkoxy groups having 1 to 6 carbon atoms.

[0163] In general formula (11), L 1 This represents a single bond or a divalent organic group. Divalent organic groups include alkylene groups having 1 to 20 carbon atoms, or groups of alkylene groups having 1 to 20 carbon atoms that have -O- between the carbon-carbon bonds. Alkylene groups having 1 to 20 carbon atoms are as described above.

[0164] The following are examples of monomers represented by general formula (11), shown by chemical formulas (4-1) to (4-6). However, the present invention is not limited to these.

[0165] [ka]

[0166] Examples of commercially available monomers represented by general formula (11) include KBM-502, 503, 5103, 5803, KBE-502, and 503 from Shin-Etsu Chemical Co., Ltd.

[0167] The monomer represented by the general formula (12) is a compound having a branched alkyl group with 4 to 6 carbon atoms and a tertiary carbon. The monomer represented by the general formula (12) readily detaches the tertiary alkyl ester group upon heating, generating a carboxyl group. The carboxyl group, for example, undergoes dehydration condensation with a hydroxyl group in the photosensitive composition upon heating, forming a covalent bond.

[0168] General formula (12) [ka]

[0169] In general formula (12), R 1 represents a hydrogen atom or a methyl group. R 11 ~R 13 Each of these independently represents an alkyl group having 1 to 10 carbon atoms. The alkyl groups having 1 to 10 carbon atoms are as described above. Among these, the methyl group is preferred. L 1 This represents a single bond or a divalent organic group. Divalent organic groups include alkylene groups with 1 to 20 carbon atoms, groups containing -NH-, or combinations thereof. Alkylene groups with 1 to 20 carbon atoms are as described above.

[0170] The following are examples of monomers represented by general formula (12), as shown by the compounds represented by chemical formulas (5-1) to (5-6). However, the present invention is not limited to these. [ka]

[0171] From the viewpoint of suppressing ITO cracks, monomer units containing thermally crosslinkable groups are more preferably those represented by general formula (8) and those represented by general formula (9).

[0172] Thermocrosslinkable group-containing monomer units can be formed by using monomers represented by general formulas (8) to (12) individually or in combination of two or more types.

[0173] The thermo-crosslinkable group-containing monomer unit can be formed from monomers represented by general formulas (8) to (12) and from monomers other than those represented by general formulas (8) to (12).

[0174] Monomers other than those represented by general formulas (8) to (12) include, for example, glycidyl (meth)acrylate, methylglycidyl (meth)acrylate, 2-glycidoxyethyl (meth)acrylate, 3,4-epoxybutyl (meth)acrylate, 3,4-epoxycyclohexyl (meth)acrylate, and 3,4-epoxytricyclo[5.2.1.0 2,6 ] Decane-8-yl(meth)acrylate, 3,4-epoxytricyclo[5.2.1.0 2,6 Examples include decane-9-yl(meth)acrylate, 2-[(3,5-dimethylpyrazolyl)carbonylamino]ethyl(meth)acrylate, and 2-[O-(1'-methylpropyleneamino)carboxyamino]ethyl(meth)acrylate.

[0175] From the viewpoint of suppressing ITO cracking, the content of thermocrosslinkable group-containing monomers is preferably 1 to 80 mol%, and more preferably 5 to 70 mol%, of the total monomer units of the alkali-soluble resin.

[0176] The alkali-soluble resin of this application may contain monomer units other than (a) polymerizable unsaturated group-containing monomer units or (b) thermocrossable group-containing monomer units. Examples include acidic group-containing monomer units, aliphatic condensed ring-containing monomer units, hydroxyl group-containing monomer units, and epoxy group-containing monomer units.

[0177] [Acidic group-containing monomer unit] Examples of monomers containing acidic groups include (meth)acrylic acid, crotonic acid, propiolic acid, cinnamic acid, itaconic acid, itaconic anhydride, maleic acid, monomethyl maleate, monoethyl maleate, monoisopropyl maleate, maleic anhydride, fumaric acid, 2-methacryloyloxyethyl succinic acid, 2-acryloyloxyethyl phthalic acid, 2-acryloyloxyethylhexyl hydrophthalic acid, p-styrene sulfonic acid, vinyl sulfonic acid, 2-acrylamido-2-methylpropanesulfonic acid, tert-butylacrylamidosulfonic acid, and 2-(meth)acryloyloxyethyl acid phosphate. Note that the acidic group includes acid anhydride groups.

[0178] [Aliphatic condensed ring-containing monomer units] Alkali-soluble resin 1 is more preferably composed of aliphatic condensed ring-containing monomer units from the viewpoint of contact hole formation and ITO crack suppression effect.

[0179] Examples of aliphatic condensed ring-containing monomers include isobolonyl (meth)acrylate, dicyclopentanyl (meth)acrylate, dicyclopentenyl (meth)acrylate, dicyclopentanyloxyethyl (meth)acrylate, dicyclopentenyloxyethyl (meth)acrylate, and adamantyl (meth)acrylate. Among these, dicyclopentanyl (meth)acrylate, dicyclopentenyl (meth)acrylate, and dicyclopentanyloxyethyl (meth)acrylate are preferred.

[0180] From the viewpoint of contact hole formation and ITO crack suppression effect, the content of aliphatic condensed ring-containing monomer units is preferably 1 to 40 mol% of the total monomer units of alkali-soluble resin 1.

[0181] [Hydroxyl group-containing monomer unit] Examples of hydroxyl group-containing monomers include 2-hydroxyethyl methacrylate, 2-hydroxypropyl methacrylate, 2-hydroxybutyl methacrylate, 3-hydroxybutyl methacrylate, 4-hydroxybutyl methacrylate, 2,3-dihydroxypropyl (meth)acrylate, glycerol mono(meth)acrylate, cyclohexanedimethanol mono(meth)acrylate, 2-hydroxy-3-phenoxypropyl acrylate, and 2-acryloyloxyethyl-2-hydroxyethyl phthalic acid.

[0182] [Epoxy group-containing monomer unit] Examples of epoxy group-containing monomers include oxyranyl (meth)acrylate, glycidyl (meth)acrylate, 2-methylglycidyl (meth)acrylate, 2-ethylglycidyl (meth)acrylate, 2-oxyranyl ethyl (meth)acrylate, 2-glycidyloxyethyl (meth)acrylate, 3,4-epoxycyclohexyl (meth)acrylate, 3,4-epoxycyclohexylmethyl (meth)acrylate, 2-(3,4-epoxycyclohexyl)ethyl (meth)acrylate, 2-(3,4-epoxycyclohexylmethyloxy)ethyl (meth)acrylate, and 3-(3,4-epoxycyclohexylmethyloxy)propyl (meth)acrylate.

[0183] Alkali-soluble resin 2 may contain, in addition to thermocrosslinkable group-containing monomer units, other monomer units such as acidic group-containing monomer units, hydroxyl group-containing monomer units, aliphatic condensed ring structure-containing monomer units, polymerizable unsaturated group-containing monomer units, and other monomer units.

[0184] (Other alkali-soluble resins) The photosensitive composition of the present invention may contain an alkali-soluble resin that does not contain (a) polymerizable unsaturated group-containing monomer units, or (b) thermocrossable group-containing monomer units.

[0185] [Coloring agent] Colorants are not limited to pigments and dyes. Pigments and dyes can be used in combination. Pigments include inorganic pigments and organic pigments. Inorganic and organic pigments can be used in combination. Organic-inorganic composites are also considered pigments.

[0186] (Pigment) Pigments are not limited to those listed above, and include, for example, compounds classified as pigments in the color index.

[0187] Red pigments include, for example, CI Pigment Red 1, 2, 3, 4, 5, 6, 7, 8, 9, 12, 14, 15, 16, 17, 21, 22, 23, 31, 32, 37, 38, 41, 47, 48, 48:1, 48:2, 48:3, 48:4, 49, 49:1, 49:2, 50:1, 52:1, 52:2, 53, 53:1, 53:2, 53:3, 57, 57:1, 57:2, 58:4, 60, 63, 63:1,63:2,64,64:1,68,69,81,81:1,81:2,81:3,81:4,83,88,90:1,101,101:1,104,108,108:1,109,112,113,114,122,123,144,146,147,149,151,166,168,169,170,172,173,174,175,176,177,178,179 ,181,184,185,187,188,190,193,194,200,202,206,207,208,209,210,214,216,220,221,224,230,231,232,233,235,236,237,238,239,242,243,245,247,249,250,251,253,254,255,256,257,258,259, Examples include pigments 260, 262, 263, 264, 265, 266, 267, 268, 269, 270, 271, 272, 273, 274, 275, 276, 277, 278, 279, 280, 281, 282, 283, 284, 285, 286, 287, 291, 295, 296, pigments described in Japanese Patent Publication No. 2014-134712, pigments described in Japanese Patent Publication No. 6368844, and the like.

[0188] Examples of orange pigments include CI Pigment Orange 36, 38, 43, 64, 71, and 73.

[0189] Examples of the yellow pigment include C.I. Pigment Yellow 1, 2, 3, 4, 5, 6, 10, 12, 13, 14, 15, 16, 17, 18, 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, 93, 94, 95, 97, 98, 100, 101, 104, 106, 108, 109, 110, 113, 114, 115, 116, 117, 118, 119, 120, 123, 126, 127, 128, 129, 138, 139, 147, 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, 192, 193, 194, 196, 198, 199, 213, 214, 231, 233, and the pigments described in JP-A-2012-226110.

[0190] The yellow pigment also includes at least one anion selected from the group consisting of mono, di, tri, and tetra anions of an azo compound represented by the following general formula (13) and its azo compound of the tautomeric structure, at least two metal ions selected from Cd, Co, Al, Cr, Sn, Pb, Zn, Fe, Ni, Cu, and Mn, and a pigment containing a compound represented by the following general formula (14).

[0191] General formula (13)

Chemical formula

[0192] In the general formula (13), two R1s each independently represent -OH, -NH2, -NH-CN, an acylamino group, an alkylamino group, or an arylamino group. Two R2s each independently represent -OH or -NH2.

[0193] General formula (14) [Chemical]

[0194] In general formula (14), the three R3s each independently represent a hydrogen atom or an alkyl group.

[0195] Examples of the green pigment include C.I. Pigment Green 1, 2, 4, 7, 8, 10, 13, 14, 15, 17, 18, 19, 26, 36, 37, 45, 48, 50, 51, 54, 55, 58, 59, 62, 63, etc. Examples of the blue pigment include C.I. Pigment Blue 1, 1:2, 9, 14, 15, 15:1, 15:2, 15:3, 15:4, 15:6, 16, 17, 19, 25, 27, 28, 29, 33, 35, 36, 56, 56:1, 60, 61, 61:1, 62, 63, 66, 67, 68, 71, 72, 73, 74, 75, 76, 78, 79, etc. Examples of the purple pigment include C.I. Pigment Violet 1, 1:1, 2, 2:2, 3, 3:1, 3:3, 5, 5:1, 14, 15, 16, 19, 23, 25, 27, 29, 31, 32, 37, 39, 42, 44, 47, 49, 50, etc. Examples of the black pigment include C.I. Pigment Black 1, 6, 7, 12, 20, 31, etc.

[0196] In addition, inorganic pigments such as silica, talc, titanium oxide, zinc oxide, barium sulfate, zinc white, lead sulfate, yellow lead, zinc yellow, red iron oxide (III), cadmium red, ultramarine, cobalt blue, chromium oxide green, cobalt green, amber, synthetic iron black, etc. can be mentioned.

[0197] In addition, fluorescent pigments, near-infrared absorbing pigments, etc. can also be mentioned.

[0198] It is preferable to use the pigment after it has been finely milled. The milling method is not particularly limited, and for example, wet milling, dry milling, or dissolution milling can all be used. Among these, salt milling by the kneader method, which is a type of wet milling, is preferred. The average primary particle size of the finely milled pigment, as determined by TEM (transmission electron microscopy), is preferably 5 to 90 nm. However, from the viewpoint of dispersibility and contrast ratio, an average primary particle size of 10 to 70 nm is more preferable.

[0199] Resin may be added to the salt milling process as needed. By adding resin, the pigment is coated with resin, improving stability, lightfastness, etc. The type of resin is not particularly limited and includes natural resins, modified natural resins, synthetic resins, and synthetic resins modified with natural resins. Among these, it is preferable that the resin is solid at room temperature, insoluble in water, and partially soluble in organic solvents. The amount of resin added is preferably 2 to 200 parts by mass per 100 parts by mass of pigment.

[0200] (dye) The dyes are not limited and may contain known compounds. Examples include acid dyes, direct dyes, basic dyes, salt-forming dyes, oil-soluble dyes, disperse dyes, reactive dyes, mordant dyes, vat dyes, sulfur dyes, fluorescent dyes, and near-infrared absorbing dyes. Derivatives of these dyes, lakes, salt-forming compounds, and polymers are also examples.

[0201] Acid dyes preferably have acidic groups such as sulfonic acid or carboxylic acid. Direct dyes preferably form salt compounds with an inorganic salt of the acid dye, or with an acid dye and a nitrogen-containing compound such as a quaternary ammonium salt compound, tertiary amine compound, secondary amine compound, or primary amine compound. Salt compounds that are salts of a resin component having these functional groups and an acid dye are also preferred. Furthermore, by sulfonamidating the salt compound to a sulfonic acid amide compound, it is easy to obtain a photosensitive composition with excellent resistance (lightfastness, solvent resistance). Furthermore, salt-forming compounds of acid dyes and compounds containing an onium base are also preferred due to their excellent resistance (light resistance and solvent resistance). The compound containing the onium base is preferably a resin having a cationic group.

[0202] Basic dyes can be used as is, but salt compounds formed by chlorinating them with organic acids, perchloric acid, or their metal salts are preferred. Salt compounds of basic dyes are preferred because they have excellent resistance (lightfastness, solvent resistance) and affinity with pigments. Furthermore, in salt compounds of basic dyes, preferred anionic components that act as counterions are those formed by chlorinating organic sulfonic acids, organic sulfuric acids, fluorine-containing phosphorus anionic compounds, fluorine-containing boron anionic compounds, cyano-containing nitrogen anionic compounds, anionic compounds having a conjugate base of an organic acid with a halogenated hydrocarbon group, and acid dyes. Note that the resistance of the salt compound is further improved if it contains polymerizable unsaturated groups in its molecule.

[0203] From the viewpoint of color characteristics such as hue, color separation, and color unevenness, the chemical structure of the dye is preferably derived from pigments selected from, for example, azo dyes, xanthene dyes, cyanine dyes, triphenylmethane dyes, anthraquinone dyes, dipyromethene dyes, squarylium dyes, quinophthalone dyes, phthalocyanine dyes, and subphthalocyanine dyes, and more preferably derived from pigments selected from xanthene dyes, cyanine dyes, triphenylmethane dyes, anthraquinone dyes, dipyromethene dyes, and phthalocyanine dyes.

[0204] From the viewpoint of contact hole formation, dyes and salt-forming compounds of dyes and resins that form salts are preferred. It is presumed that the dyes moderately reduce the curability of the photocurable component and suppress the increase in molecular weight of polymers in the cured film, thereby contributing to the reduction of residue in the contact holes.

[0205] From the viewpoint of contact hole formation, dyes with a xanthene skeleton are preferred. This is presumed to be because the compatibility between specific polymerizable compounds and the xanthene skeleton is good, suppressing elution during development and thus contributing to the reduction of residue in contact holes.

[0206] Compounds having a xanthene skeleton include those described in CI Acid Violet 9, 30, 102, CI Basic Violet 10, 11, 25, CI Acid Red 51, 52, 87, 92, 94, 289, 388, 463, JP 2012-013758, JP 2012-208452, JP 2013-033194, International Publication No. 2016 / 031442, International Publication No. 2016 / 121194, JP 2019-109490, International Publication No. 2019 / 031292, etc. Among these, CI Acid Red 52, 289, 463 is preferred.

[0207] (Dyes, and salt-forming compounds of the dye and a resin that forms a salt) The resin that forms salts with dyes (hereinafter also simply referred to as "salt-forming resin") is not limited to any resin that can form salts with dyes. In this specification, the salt-forming resin is preferably a resin having repeating units represented by the following general formula (15).

[0208] [ka]

[0209] In general formula (15), R1 represents a hydrogen atom or a methyl group. R2 to R4 each independently represent a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, or an aralkyl group having 7 to 20 carbon atoms. Furthermore, two or more of R2 to R4 may bond to each other to form a cyclic structure. The alkyl group having 1 to 20 carbon atoms can be linear, branched, cyclic, or a combination thereof. The alkyl group is the same as the example above. Among these, methyl, ethyl, propyl, and butyl groups are preferred. Aryl groups having 6 to 20 carbon atoms include, for example, a phenyl group, a naphthyl group, a biphenyl group, an anthracenyl group and the like. Among these, a phenyl group is preferred. Aralkyl groups having 7 to 20 carbon atoms include, for example, a benzyl group, a phenethyl group, a phenylpropyl group, a phenylbutyl group, a phenylisopropyl group and the like. Among these, a benzyl group and a phenethyl group are preferred. The alkyl group, aryl group, or aralkyl group of R2 to R4 may have a substituent, and examples of the substituent include a halogen atom, an alkoxy group, a benzoyl group and the like.

[0210] The cyclic structure formed by bonding two or more of R2 to R4 to each other includes a nitrogen-containing heterocyclic ring having 5 to 7 members. Examples of the nitrogen-containing heterocyclic ring include the following cyclic structures. R in the following formula is any group of R2 to R4.

[0211]

Chemical formula

[0212] These cyclic structures may have a substituent. Examples of the substituent include a halogen atom, an alkoxy group, a hydroxyl group and the like.

[0213] In general formula (15), L1 represents a divalent linking group. Examples of the divalent linking group include an alkylene group having 1 to 10 carbon atoms, an arylene group having 6 to 12 carbon atoms, -CONH-R5-, or -COO-R6- (where R5 and R6 are each independently a single bond, an alkylene group having 1 to 10 carbon atoms, or an ether group having 2 to 10 carbon atoms (alkyloxyalkyl group)). Among these, -COO-R6- in which R6 is an alkylene group having 1 to 3 carbon atoms is preferred. Y1 - represents a counter anion. Y1 - is, for example, Cl - 、Br - 、I - 、ClO4 - 、BF4 -CH3COO - PF6 - , SO3 - Examples include aromatic dicarboxylate imide anions, aromatic sulfonate anions, aromatic phosphonate anions, and aromatic carboxylate anions.

[0214] Repeating units represented by general formula (15) include, for example, alkyl (meth)acrylate quaternary ammonium salts such as (meth)acryloyloxyethyltrimethylammonium chloride, (meth)acryloyloxyethyltriethylammonium chloride, (meth)acryloyloxyethyldimethylbenzylammonium chloride, and (meth)acryloyloxyethylmethylmorpholinoammonium chloride; alkyl (meth)acryloylamide quaternary ammonium salts such as (meth)acryloylaminopropyltrimethylammonium chloride, (meth)acryloylaminoethyltriethylammonium chloride, and (meth)acryloylaminoethyldimethylbenzylammonium chloride; dimethyldiallylammonium methyl sulfate, trimethylvinylphenylammonium chloride, and the like. These can be used individually or in combination of two or more.

[0215] The repeating units represented by general formula (15) are preferably present in an amount of 1 to 70 mol%, and more preferably 1 to 60 mol%, of the total repeating units of the salt-forming resin.

[0216] The salt-forming resin may contain repeating units other than the repeating unit represented by general formula (15) (hereinafter also referred to as other repeating units). Examples of other repeating units include the aforementioned acidic group-containing monomer units, aliphatic condensed ring-containing monomer units, hydroxyl group-containing monomer units, epoxy group-containing monomer units, and so on.

[0217] Furthermore, the salt-forming resin may contain the polymerizable unsaturated group-containing monomer units.

[0218] Examples of structures for salt-forming resins include random structures, block structures, graft structures, comb-like structures, and star-shaped structures.

[0219] The weight-average molecular weight of the salt-forming resin is preferably 3,000 to 50,000, and more preferably 4,000 to 40,000.

[0220] Salt-forming resins can be used alone or in combination of two or more types.

[0221] The method for producing the salt-forming compound from the dye and salt-forming resin is not limited and known methods can be used. For example, it is described in paragraphs 0360 to 0371 of Japanese Patent Publication No. 2015-28587 and paragraph 0135 of Japanese Patent Publication No. 2018-172542.

[0222] The salt-forming compound content of the dye and salt-forming resin is preferably 0.5 to 100% by mass, and more preferably 1 to 80% by mass, based on 100% by mass of the coloring agent.

[0223] (A dye polymer having a dye monomer with a dye residue and an ethylenically unsaturated group as its structural unit.) The photosensitive composition of the present invention may contain a dye polymer (hereinafter also simply referred to as "specific dye polymer") having a dye monomer unit having a dye residue and an ethylenically unsaturated group. Examples of dye residues include the dye structure described above. Examples of the specific dye monomer include the monomer represented by the following general formula (16).

[0224] General formula (16) [ka]

[0225] In general formula (16), R 1 X represents a hydrogen atom or a methyl group. 1 D represents a single bond, substituted or unsubstituted divalent hydrocarbon group, or a "divalent group formed by combining a divalent hydrocarbon group with a divalent linking group containing a heteroatom" (hereinafter also referred to as a "specific linking group"), 1This represents a dye residue.

[0226] The aforementioned X 1 Examples of divalent hydrocarbon groups include divalent aliphatic hydrocarbon groups, divalent alicyclic hydrocarbon groups, and divalent aromatic hydrocarbon groups.

[0227] Examples of divalent aliphatic hydrocarbon groups include alkanediyl groups and alkenediyl groups. The number of carbon atoms in the divalent aliphatic hydrocarbon group is preferably 1 to 20, more preferably 2 to 12, and even more preferably 2 to 6. Examples of the alkanediyl group are linear alkanediyl groups such as methylene group, ethylene group, propane-1,3-diyl group, propane-1,2-diyl group, butane-1,4-diyl group, pentane-1,5-diyl group, and hexane-1,6-diyl group; Examples of branched alkanediyl groups include 1-methylpropane-1,3-diyl group, 2-methylpropane-1,3-diyl group, 2-methylpropane-1,2-diyl group, 1-methylbutane-1,4-diyl group, and 2-methylbutane-1,4-diyl group. Examples of the alkanediyl group include ethene-1,1-diyl group, ethene-1,2-diyl group, propene-1,2-diyl group, propene-1,3-diyl group, propene-2,3-diyl group, 1-butene-1,2-diyl group, 1-butene-1,3-diyl group, 1-butene-1,4-diyl group, 2-pentene-1,5-diyl group, and 3-hexene-1,6-diyl group. Examples of divalent alicyclic hydrocarbon groups include cycloalkylene groups and cycloalkenylene groups. The number of carbon atoms in the divalent alicyclic hydrocarbon group is preferably 3 to 20, and more preferably 3 to 12. Examples of the cycloalkylene group include monocyclic hydrocarbon groups such as cyclopropylene, cyclobutylene, cyclopentylene, and cyclohexylene; norbornylene groups such as 1,4-norbornylene and 2,5-norbornylene; and bridged hydrocarbon groups such as 1,5-adamantilene and 2,6-adamantilene. Examples of the cycloalkenylene group include monocyclic hydrocarbon groups such as cyclobutenylene, cyclopentenylene, and cyclohexenylene. Examples of divalent aromatic hydrocarbon groups include arylene groups. The number of carbon atoms in the divalent aromatic hydrocarbon group is preferably 6 to 14. Examples of arylene groups include phenylene groups, biphenylene groups, and naphthylene groups.

[0228] Furthermore, examples of divalent linking groups containing heteroatoms included in the specified linking group include -O-, -S-, -SO2-, -CO-, -COO-, -OCO-, -CONRa- (Ra represents a hydrogen atom or an alkylene group having 1 to 6 carbon atoms), and -NRa- (Ra has the same meaning as above). One or more divalent linking groups containing heteroatoms may be present in the specified linking group. The bonding position of the linking group is arbitrary and can be, for example, at the end of a divalent hydrocarbon group or between CC bonds, but it is preferable to have it at one end or between CC bonds. In addition, a divalent hydrocarbon group and a divalent linking group containing a heteroatom may bond to form a ring structure.

[0229] Furthermore, groups having a ring structure formed by the bonding of a divalent hydrocarbon group and a divalent linking group containing a heteroatom include, but are not limited to, the following chemical structures.

[0230] [ka]

[0231] Substituents of a divalent hydrocarbon group include halogen atoms, nitro groups, hydroxyl groups, substituted or unsubstituted alkoxyl groups, and substituted or unsubstituted aryloxy groups. Examples of halogen atoms include fluorine atoms, chlorine atoms, bromine atoms, and iodine atoms. Examples of alkoxyl groups include linear and branched chains. The number of carbon atoms is preferably 1 to 6. Examples of alkoxyl groups include methoxy groups, ethoxy groups, propoxy groups, and butoxy groups. The number of carbon atoms of an aryloxy group is preferably 6 to 14. Examples of aryloxy groups include phenoxy groups and benzyloxy groups. Furthermore, substituents of alkoxyl groups and aryloxy groups include halogen atoms, nitro groups, hydroxyl groups, amino groups, carboxyl groups, and sulfanyl groups. In addition, divalent alicyclic hydrocarbon groups and divalent aromatic hydrocarbon groups may have substituted or unsubstituted alkyl groups and substituted or unsubstituted alkenyl groups as substituents. The number of carbon atoms of alkyl groups and alkenyl groups is preferably 1 to 6. Examples of alkyl groups include methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, tert-butyl, and hexyl groups, while examples of alkenyl groups include ethenyl, 1-propenyl, 1-butenyl, 1-pentenyl, 1-hexenyl, and 2-ethyl-2-butenyl groups.

[0232] D 1 The ∫ represents a dye residue. Examples of dyes that form the dye residue include xanthene dyes, triarylmethane dyes, cyanine dyes, anthraquinone dyes, azo dyes, dipyromethene dyes, quinophthalone dyes, coumarin dyes, pyrazolone dyes, quinoline dyes, nitro dyes, quinoneimine dyes, and phthalocyanine dyes. Among these, the dye residues are preferably triarylmethane dyes, xanthene dyes, azo dyes, dipyromethene dyes, methine dyes, and cyanine dyes, more preferably triarylmethane dyes, xanthene dyes, dipyromethene dyes, and cyanine dyes, and even more preferably triarylmethane dyes. Acid dyes and basic dyes are preferred.

[0233] Colorants can be used alone or in combination of two or more types.

[0234] The colorant content is preferably 1 to 70% by mass, and more preferably 5 to 60% by mass, based on 100% by mass of the nonvolatile content of the photosensitive composition.

[0235] From the viewpoint of brightness, the coloring agent preferably contains a dye.

[0236] [Thermal crosslinkable compound] The photosensitive composition of the present invention may contain a thermally crosslinkable compound. The thermally crosslinkable compound crosslinks with other components upon heating, forming a tough film, thus further improving the ITO crack suppression effect. The thermally crosslinkable compound is a compound that does not possess polymerizable unsaturated groups or alkali solubility. Therefore, it is a different compound from alkali-soluble resins and polymerizable compounds. The weight-average molecular weight (or formula weight) of the thermally crosslinkable compound is 5,000 or less.

[0237] The thermally crosslinkable compound is not limited and any known compound can be used. Examples of thermally crosslinkable compounds include oxetanyl group-containing compounds, methylol group-containing compounds, phenol group-containing compounds, alkoxyalkyl group-containing compounds, blocked isocyanate group-containing compounds, epoxy compounds, and the like. Among these, blocked isocyanate group-containing compounds and epoxy compounds are preferred, with blocked isocyanate group-containing compounds being more preferred.

[0238] [Compounds containing blocked isocyanate groups] A blocked isocyanate group-containing compound is a compound having a blocked isocyanate group. A blocked isocyanate group-containing compound is a compound in which the isocyanate group of a compound having an isocyanate group is protected with a blocking agent. From the viewpoint of the ITO crack suppression effect, the desorption temperature of the blocking agent is preferably 60 to 160°C, more preferably 70 to 130°C, and particularly preferably 80 to 110°C.

[0239] Methods for synthesizing blocked isocyanate group-containing compounds are described, for example, in Japanese Patent Publication No. 52-116420, Japanese Patent Publication No. 60-149572, Japanese Patent Publication No. 7-31953, Japanese Patent Publication No. 10-306136, and Japanese Patent Publication No. 2012-012567.

[0240] The blocking agent is preferably one or more selected from the group consisting of oxime compounds, lactam compounds, phenol compounds, alcohol compounds, amine compounds, activated methylene compounds, pyrazole compounds, mercaptan compounds, imidazole compounds, and imide compounds, with oxime compounds, phenol compounds, activated methylene compounds, and pyrazole compounds being more preferred, and activated methylene compounds being particularly preferred from the viewpoint of solvent resistance after low-temperature heating. The desorption temperature of activated methylene compounds, or the temperature of the transesterification reaction, is low, at 80 to 110°C, and the reaction proceeds sufficiently even at low temperatures, improving resistance.

[0241] Compounds having an isocyanate group include, for example, aliphatic compounds such as butane-1,4-diisocyanate, hexamethylene diisocyanate, isopropyl diisocyanate, methylene diisocyanate, and 2,2,4-trimethylhexamethylene diisocyanate; Compounds having an alicyclic structure, such as cyclohexane-1,4-diisocyanate, isophorone diisocyanate, dimethylcyclohexyl diisocyanate, methylcyclohexyl diisocyanate, dicyclohexylmethane-4,4'-diisocyanate, 1,3-bis(isocyanate-methyl)cyclohexane, methylcyclohexane diisocyanate, norbornane diisocyanate, and bis(isocyanate-methyl)cyclohexane; Examples of aromatic compounds include 1,5-naphthylene diisocyanate, 4,4'-diphenylmethane diisocyanate, 4,4'-diphenyldimethylmethane diisocyanate, 4,4'-dibenzyli isocyanate, dialkyldiphenylmethane diisocyanate, tetraalkyldiphenylmethane diisocyanate, 1,3-phenylenedi isocyanate, 1,4-phenylenedi isocyanate, 2,4-toluene diisocyanate, 2,6-toluene diisocyanate, xylylene diisocyanate, M-tetramethylxylylene diisocyanate, 4,4-diphenylmethane diisocyanate, tolylene diisocyanate, bischloromethyldiphenylmethane diisocyanate, 2,6-diisocyanate-benzyl chloride, and bis(isocyanatemethyl)benzene. Other examples include the biuret, isocyanurate, adduct, and allophanate forms of these compounds, as well as reaction products of these compounds with polyols.

[0242] The compounds having an isocyanate group are preferably in the form of bilets, isocyanurates, adducts, and allophanates of compounds having an aliphatic structure or an alicyclic structure, and more preferably in the form of bilets and isocyanurates of compounds having an aliphatic structure.

[0243] Examples of compounds containing blocked isocyanate groups include the following compounds. In the compounds represented by the following chemical formulas (N-1) to (N-7), X represents a blocked isocyanate group. However, the present invention is not limited to these.

[0244] [ka]

[0245] Among the above, from the viewpoint of ITO crack suppression effect, compounds represented by chemical formulas (N-1), (N-2), (N-4), and (N-7) are preferred, compounds represented by chemical formulas (N-1) and (N-2) are more preferred, and the compound represented by chemical formula (N-1) is even more preferred.

[0246] The aforementioned X (blocked isocyanate group) can be exemplified by the structures shown in the following chemical formulas (X-1) to (X-8). In the following structures, * represents a bond. However, the present invention is not limited to these structures.

[0247] [ka]

[0248] Among the above structures, from the viewpoint of ITO crack suppression effect, chemical formulas (X-1), (X-4), (X-6), (X-7), and (X-8) are preferred, chemical formulas (X-1) and (X-8) are more preferred, and chemical formula (X-1) is even more preferred.

[0249] Among the blocked isocyanate group-containing compounds, compounds combining chemical formula (N-1) or chemical formula (N-2) with chemical formula (X-1), chemical formula (X-4), or chemical formula (X-8) are preferred from the viewpoint of ITO crack suppression effect.

[0250] By using chemical formulas (X-1) and (X-8) in combination, a high level of ITO crack suppression effect can be achieved simultaneously. The molar ratio of chemical formulas (X-1) and (X-8) used together is preferably 90:10 to 10:90, more preferably 90:10 to 30:70, and even more preferably 90:10 to 70:30.

[0251] Examples of commercially available compounds containing blocked isocyanate groups that have an aliphatic structure include, for example, Asahi Kasei's Duranate SBN-70D, SBB-70P, SBF-70E, TPA-B80E, 17B-60P, E402-B80B, WM44-L70G; Mitsui Chemicals' Takenate B-882; and Baxenden Chemical's BI7960, BI7961, BI7982, BI7991, BI7992, etc. Examples of compounds having an alicyclic structure include Takenate B-846N from Mitsui Chemicals, Coronate BI-301, 2507, 2554 from Tosoh Corporation, and BI7950, BI7951, BI7990 from Baxenden Chemical. Examples of compounds having an aromatic structure include Takenate B-830 and B-815N, manufactured by Mitsui Chemicals, Inc.

[0252] The number of blocked isocyanate groups in the blocked isocyanate group-containing compound is preferably 1 to 20, and more preferably 2 to 15.

[0253] The weight-average molecular weight of the blocked isocyanate group-containing compound is preferably 300 to 5,000, and more preferably 500 to 3,000.

[0254] The acid value of the blocked isocyanate group-containing compound is preferably less than 10 mg KOH / g.

[0255] Blocked isocyanate group-containing compounds can be used alone or in combination of two or more types.

[0256] From the viewpoint of inhibiting ITO cracking, the content of the blocked isocyanate group-containing compound is preferably 1 to 20% by mass, more preferably 3 to 15% by mass, and particularly preferably 5 to 10% by mass, based on 100% by mass of the nonvolatile content of the photosensitive composition.

[0257] [Epoxy compounds] Epoxy compounds are compounds that contain epoxy groups. These epoxy groups include alicyclic epoxy groups. Note that epoxy compounds do not contain alkoxysilyl groups and do not contain (meth)acrylic polymers.

[0258] Epoxy compounds include polyglycidyl ether compounds of bisphenols, such as bisphenol A diglycidyl ether, bisphenol F diglycidyl ether, bisphenol S diglycidyl ether, hydrogenated bisphenol A diglycidyl ether, and hydrogenated bisphenol F diglycidyl ether; Polyglycidyl ether compounds of polyhydric alcohols such as 1,4-butanediol diglycidyl ether, 1,6-hexanediol diglycidyl ether, glycerin triglycidyl ether, trimethylolpropane triglycidyl ether, polyethylene glycol diglycidyl ether, and polypropylene glycol diglycidyl ether; Polyglycidyl ether compounds of polyether polyols obtained by adding alkylene oxides to polyhydric alcohols such as ethylene glycol, propylene glycol, and glycerin; 3,4-Epoxycyclohexylmethyl-3,4-Epoxycyclohexanecarboxylate, 3,4-Epoxy-1-methylcyclohexyl-3,4-Epoxy-1-methylhexanecarboxylate, 6-methyl-3,4-Epoxycyclohexylmethyl-6-methyl-3,4-Epoxycyclohexanecarboxylate, 3,4-Epoxy-3-methylcyclohexylmethyl-3,4-Epoxy-3-methylcyclohexanecarboxylate, 3,4-Epoxy-5-methylcyclohexylmethyl-3,4-Epoxy-5-methylcyclohexanecarboxylate, 2-(3,4-Epoxycyclohexyl Compounds having two or more 3,4-epoxycyclohexyl groups in their molecule, such as ru-5,5-spiro-3,4-epoxy)cyclohexane-methadioxane, bis(3,4-epoxycyclohexylmethyl)adipate, 3,4-epoxy-6-methylcyclohexylcarboxylate, methylenebis(3,4-epoxycyclohexane), ethylenebis(3,4-epoxycyclohexanecarboxylate), dioctyl epoxyhexahydrophthalate, 1-epoxyethyl-3,4-epoxycyclohexane, and tetra(3,4-epoxycyclohexylmethyl)-modified E-caprolactone of butanetetracarboxylic acid; Examples include the 1,2-epoxy-4-(2-oxyranyl)cyclohexane adduct of 2,2-bis(hydroxymethyl)-1-butanol.

[0259] Commercially available epoxy compounds include, for example, JER807, 815, 825, 827, 828, 190P, 191P, 1004, 1256, 1032H60, 157S65, 157S70, 152, 154 from Mitsubishi Chemical Corporation, and TECHMORE from Mitsui Chemicals Corporation. VG3101L, EPPN-201, 501H, 502H, EOCN-102S, 103S, 104S, 1020 from Nippon Kayaku Co., Ltd., Celoxide 2021, EHPE-3150, Epolid GT401 from Daicel Corporation, Denacol EX-211, 212, 252, 313, 314, 321, 411, 421, 512, 521, 611, 612, 614, 614B, 622, 711, 721 from Nagase ChemteX Corporation, TEPIC-L, H, S from Nissan Chemical Industries, Ltd., and EPICLON from DIC Corporation. Examples include 830, 840, 850, 860, 1050, 3050, 4050, N-660, N-670, N-740, N-770, N865, HP-7200, HP-4700, HP-4770, HP-5000, HP-6000, HP-9500, etc.

[0260] Epoxy compounds are preferably those having 2 to 50 epoxy groups in their molecule.

[0261] From the viewpoint of suppressing ITO cracking, the epoxy equivalent of the epoxy compound is preferably 50 to 400 G / eq, and more preferably 90 to 220 G / eq. Note that epoxy equivalent is defined as the mass of the epoxy compound containing one equivalent of epoxy groups.

[0262] From the viewpoint of suppressing ITO cracking, the epoxy compound more preferably contains a compound represented by the following general formula (50).

[0263] General formula (50) [ka]

[0264] In general formula (50), R represents a group obtained by removing m hydroxyl groups from an m-valent alcohol, m is an integer from 1 to 6, and n is an integer from 1 to 30.

[0265] R is preferably an alkyl group having 2 to 20 carbon atoms, and may be linear, branched, cyclic, or a group in which these are bonded. The alkyl groups having 2 to 20 carbon atoms are the same as those exemplified above. Among these, branched alkyl groups having 3 to 12 carbon atoms are more preferred. Furthermore, when m is 2 or greater, the n in each of the bases in parentheses in general formula (50) may be the same or different.

[0266] Compounds represented by general formula (50) include, for example, the 1,2-epoxy-4-(2-oxyranyl)cyclohexane adduct of 2,2-bis(hydroxymethyl)-1-butanol. Commercially available products include EHPE-3150 and EHPE-3150CE manufactured by Daicel Corporation.

[0267] The acid value of the epoxy compound is preferably 10 mg KOH / g or less.

[0268] Epoxy compounds can be used alone or in combination of two or more types.

[0269] The epoxy compound content is preferably 0.5 to 20% by mass, more preferably 2 to 7% by mass, and particularly preferably 3 to 5% by mass, based on 100% by mass of the nonvolatile content of the photosensitive composition, from the viewpoint of resolubility and development stains.

[0270] From the viewpoint of suppressing ITO cracking, it is preferable to use a combination of a thermally crosslinkable compound containing a blocked isocyanate group and an epoxy compound.

[0271] From the viewpoint of ITO crack suppression effect, the mass ratio of the blocked isocyanate group-containing compound to the epoxy compound is preferably 5:95 to 95:5, more preferably 37:63 to 91:9, and particularly preferably 55:45 to 77:23.

[0272] Thermally crosslinkable compounds can be used alone or in combination of two or more types.

[0273] From the viewpoint of suppressing ITO cracking, the content of the thermally crosslinkable compound is preferably 0.5 to 40% by mass, more preferably 1 to 30% by mass, and particularly preferably 5 to 20% by mass, based on 100% by mass of the nonvolatile content of the photosensitive composition.

[0274] [Pigment derivatives] The photosensitive composition of the present invention may contain a pigment derivative.

[0275] Pigment derivatives are not limited and any known compounds can be used. Examples of pigment derivatives include compounds having a structure in which part of the pigment is substituted with an acidic group, a basic group, a neutral group, etc. Pigment derivatives include compounds having acidic substituents such as sulfo groups, carboxyl groups, and phosphate groups, as well as amine salts thereof, compounds having basic substituents such as sulfonamide groups or tertiary amino groups at the terminal, and compounds having neutral substituents such as phenyl groups or phthalimidoalkyl groups. Examples of pigments include diketopyrrolopyrrole compounds, phthalocyanine compounds, anthraquinone compounds, quinacridone compounds, dioxazine compounds, perinone compounds, perylene compounds, thiaidine indigo compounds, triazine compounds, benzimidazolon compounds, benzoisoindole compounds, isoindoline compounds, isoindolinone compounds, quinophthalone compounds, naphthol compounds, squarylium compounds, surene compounds, naphthalocyanine compounds, and the like.

[0276] The pigment derivative is preferably added during the fine-graining of the pigment as described above, or during the dispersion treatment of the pigment. The average primary particle size of the pigment derivative is preferably 5 to 200 nm.

[0277] Pigment derivatives can be used alone or in combination of two or more types.

[0278] The pigment derivative content is preferably 1 to 50 parts by mass, and more preferably 2 to 40 parts by mass, per 100 parts by mass of colorant.

[0279] [Dispersion resin] The photosensitive composition of the present invention may contain a dispersion resin. The dispersion resin is a resin other than an alkali-soluble resin.

[0280] The dispersion resin is preferably a resin having adsorption groups that have a high affinity for the colorant. The adsorption groups contain one or more basic groups and acidic groups.

[0281] Basic groups include, for example, primary amino groups, secondary amino groups, tertiary amino groups, quaternary ammonium bases, and nitrogen-containing heterocycles and other groups containing nitrogen atoms.

[0282] Examples of acidic groups include carboxyl groups, phosphate groups, and sulfonic acid groups.

[0283] Examples of the resin types used in the dispersion resin include urethane resins, polycarboxylic acid esters such as polyacrylates, unsaturated polyamides, polycarboxylic acids, polycarboxylic acid (partial)amine salts, polycarboxylic acid ammonium salts, polycarboxylic acid alkylamine salts, polysiloxanes, long-chain polyaminoamide phosphates, and hydroxyl group-containing polycarboxylic acid esters, as well as modified products thereof; amides and their salts formed by the reaction of poly(lower alkyleneimines) with polyesters having free carboxyl groups; water-soluble resins and water-soluble polymer compounds such as (meth)acrylic acid-styrene copolymers, (meth)acrylic acid-(meth)acrylic acid ester copolymers, styrene-maleic acid copolymers, polyvinyl alcohol, and polyvinylpyrrolidone; polyester systems, modified polyacrylate systems, ethylene oxide / propylene oxide adduct compounds, and phosphate ester systems.

[0284] Examples of dispersion resin structures include random structures, block structures, graft structures, comb structures, and star structures. Among these, block structures, graft structures, and comb structures are preferred from the viewpoint of dispersion stability.

[0285] Commercially available dispersion resins include, for example, Disperbyk-101, 103, 107, 108, 110, 111, 116, 130, 140, 154, 161, 162, 163, 164, 165, 166, 167, 168, 170, 171, 174, 180, 181, 182, 183, 184, 185, 190, 2000, 2001, 2009, 2010, 2020, 2025, 2050, 2070, 2095, 2 from BIC Chemie Japan. SOLSPERSE-3000, 9000, 13000, 13240, 13650, 13940, 16000, 17000, 18000, 20000, 21000, 24000, 260, etc. manufactured by Lubrizol Japan, including 150, 2155, 2163, 2164, or Anti-Terra-U203, 204, or BYK-P104, P104S, 220S, or Lactimon, Lactimon-WS, or Bykumen. 00,27000,28000,31845,32000,32500,32550,33500,32600,34750,35100,36600,38500,41000,41090,53095,55000,56000,76500 etc., BASF Japan EFKA-46,47,48,452,4008,4009,4010,4015,4020,4047,4050,4055,4060,4080,4400, Examples include 4401, 4402, 4403, 4406, 4408, 4300, 4310, 4320, 4330, 4340, 450, 451, 453, 4540, 4550, 4560, 4800, 5010, 5065, 5066, 5070, 7500, 7554, 1101, 120, 150, 1501, 1502, 1503, etc., as well as Ajisper PA111, PB711, PB821, PB822, PB824 manufactured by Ajinomoto Fine Techno Co., Ltd. Furthermore, the resins described in Japanese Patent Publication No. 2008-029901, Japanese Patent Publication No. 2009-155406, Japanese Patent Publication No. 2010-185934, Japanese Patent Publication No. 2011-157416, International Publication No. 2013175978, paragraphs 0122-0155, the resins described in Japanese Patent Publication No. 2019-78878, paragraphs 0317-0321, and International Publication No. 2018 / 139534, paragraph 00 Examples include the resins described in 83, the resins described in paragraphs 0167 to 0191 of International Publication No. 2019 / 163505, the resins described in paragraphs 0299 ​​to 0310 of International Publication No. 2021 / 131927, the resins described in paragraphs 0080 to 0085 of International Publication No. 2022 / 102367, and the resins described in paragraphs 0099 to 0109 of International Publication No. 2022 / 172607.

[0286] The dispersion resin can be used alone or in combination of two or more types.

[0287] From the viewpoint of suppressing ITO cracking, a dispersion resin having basic properties is preferred.

[0288] The content of the dispersion resin is preferably 3 to 200 parts by mass, and more preferably 5 to 100 parts by mass, per 100 parts by mass of the colorant.

[0289] [Thiol-based chain transfer agents] The photosensitive composition of the present invention may contain a thiol-based chain transfer agent.

[0290] Examples of thiol chain transfer agents include monofunctional thiol compounds such as thiophenol, 2-mercaptobenzothiazole, 2-mercaptobenzimidazole, 2-mercaptobenzoxazole, 2-mercapto-5-methoxybenzothiazole, 2-mercapto-5-benzimidazole, butanethiol, octanthiol, 1-dodecanethiol, methyl 3-mercaptopropionate, ethyl 3-mercaptopropionate, octyl 3-mercaptopropionate, and 2-ethylhexyl 3-mercaptopropionate; Monofunctional thiol compounds containing hydroxyl groups or acidic groups, such as 2-mercaptoethanol, 1-thioglycerol, thioglycolic acid, 2-mercaptobenzoic acid, 3-mercaptobenzoic acid, 4-mercaptonicotinic acid, 2-mercaptopropionic acid, 3-mercaptopropionic acid, 4-mercaptobutanoic acid, octyl thioglycolate, mercaptosuccinic acid, 11-mercaptoundecanoic acid, and 2-mercaptoethanesulfonic acid; Examples of polyfunctional thiol compounds include hexanedithiol, decanedithiol, 1,4-butanediol bisthiopropionate, 1,4-butanediol bisthioglycolate, ethylene glycol bisthioglycolate, ethylene glycol bisthiopropionate, trimethylolpropane tristhioglycolate, trimethylolpropane tristhiopropionate, trimethylolpropane tris(3-mercaptobutyrate), pentaerythritol tetrakisthioglycolate, pentaerythritol tetrakis(3-mercaptopropionate), tris(2-hydroxyethyl) isocyanurate trimercaptopropionate, 1,4-dimethylmercaptobenzene, 2,4,6-trimercapto-S-triazine, and 2-(N,N-dibutylamino)-4,6-dimercapto-S-triazine.

[0291] Thiol-based chain transfer agents can be used alone or in combination of two or more types.

[0292] The content of the thiol-based chain transfer agent is preferably 1 to 10% by mass of 100% by mass of the non-volatile content of the photosensitive composition. [Silane coupling agent] The photosensitive composition of the present invention may contain a silane coupling agent.

[0293] Silane coupling agents are compounds having an alkoxysilyl group and other reactive functional groups. The alkoxysilyl group is a group in which an alkoxy group is bonded to a silicon atom, and which produces a silanol group through hydrolysis. Examples of alkoxy groups include methoxy groups, ethoxy groups, and butoxy groups. Examples of the aforementioned other functional groups include epoxy groups, amino groups, vinyl groups, (meth)acryloyl groups, isocyanate groups, isocyanurate groups, mercapto groups, oxetanyl groups, styryl groups, and ureido groups.

[0294] (Silane coupling agents having alkoxysilyl groups, (meth)acryloyl groups, and urethane bonds) Silane coupling agents may contain silane coupling agents having an alkoxysilyl group, a (meth)acryloyl group, and a urethane bond (hereinafter also referred to as "specific SC agents"). Specific SC agents are not included in polymerizable compounds having a urethane bond.

[0295] Specific SC agents can be synthesized, for example, by a urethane reaction between a compound containing an alkoxysilyl group and an isocyanate group and a hydroxyl group-containing (meth)acrylate.

[0296] Examples of compounds containing the alkoxysilyl group and isocyanate group include isocyanatetopropyltriethoxysilane, isocyanatetopropylmethyldiethoxysilane, isocyanatetopropyldimethylethoxysilane, isocyanatetopropyltrimethoxysilane, isocyanatetopropylmethyldimethoxysilane, isocyanatetopropyldimethylmethoxysilane, isocyanatetopropyltripropoxysilane, isocyanatetopropylmethyldipropoxysilane, isocyanatetopropyldimethylpropoxysilane, isocyanatetopropyltributoxysilane, isocyanatetopropylmethyldibutoxysilane, and isocyanatetopropyldimethylbutoxysilane.

[0297] Examples of the hydroxyl group-containing (meth)acrylates include 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 2-hydroxybutyl (meth)acrylate, 3-hydroxybutyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, 2,3-dihydroxypropyl (meth)acrylate, glycerol mono(meth)acrylate, cyclohexanedimethanol mono(meth)acrylate, 2-hydroxy-3-phenoxypropyl acrylate, 2-acryloyloxyethyl-2-hydroxyethyl phthalic acid, 4-hydroxyphenyl (meth)acrylate, pentaerythritol tri(meth)acrylate, dipentaerythritol penta(meth)acrylate, polypentaerythritol penta(meth)acrylate, and dipentaerythritol caprolactone-modified penta(meth)acrylate.

[0298] The urethane reaction can use a solvent and reaction catalyst as needed. Suitable solvents include hydrocarbon solvents. Among these, chain hydrocarbons, cyclic hydrocarbons, and aromatic hydrocarbons are preferred. Suitable reaction catalysts include urethane catalysts such as tertiary amines and tin compounds.

[0299] From the viewpoint of ITO crack suppression effect, the specific SC agent preferably has 1 to 5 (meth)acryloyl groups per alkoxysilyl group, and more preferably 1 to 3.

[0300] From the viewpoint of ITO crack suppression effect, the specific SC agent is preferably a methoxysilyl group or an ethoxysilyl group.

[0301] The preferred SC agent is a compound represented by the following general formula (17). The compound represented by general formula (17) forms a crosslinked structure near the film interface due to the hydrolysis of alkoxysilyl groups, and the ethylenically unsaturated groups react with polymerizable compounds by photocuring or other means to form a film formation network. Furthermore, it generates strong cohesive force derived from urethane bonds, which can suppress penetration of the film by NMP and film swelling. This is presumed to improve the ITO crack suppression effect.

[0302] General formula (17) [ka]

[0303] In general formula (17), the three R1s each independently represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, R2 represents an alkylene group having 1 to 8 carbon atoms, X is a group represented by the following general formulas (X-1) to (X-4), and n is an integer from 1 to 10.

[0304] [ka]

[0305] In general formula (X-1), R3 represents an alkylene group having 1 to 8 carbon atoms. In general formulas (X-1) to (X-4), R4 represents a hydrogen atom or a methyl group. * indicates a bond with an oxygen atom. From a reactivity standpoint, methyl groups are preferred for the three R1 groups. From the viewpoint of ITO crack suppression effect, X is preferably a group represented by the general formulas (X-1) to (X-3).

[0306] Specific SC agents can be used alone or in combination of two or more types.

[0307] From the viewpoint of ITO crack suppression effect, the content of the specific SC agent is preferably 0.1 to 15% by mass, and more preferably 0.5 to 10% by mass, of 100% by mass of the nonvolatile content of the photosensitive composition.

[0308] (Other silane coupling agents) Silane coupling agents may contain other silane coupling agents (other SC agents) in addition to specific SC agents.

[0309] Other SC agents include, for example, hydrochloric acid of 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, N-2-(aminoethyl)-3-aminopropylmethyldimethoxysilane, N-2-(aminoethyl)-3-aminopropyltrimethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, N-phenyl-3-aminopropyltrimethoxysilane, and N-(vinylbenzyl)-2-aminoethyl-3-aminopropyltrimethoxysilane. Examples include salts, vinyltrimethoxysilane, vinyltriethoxysilane, 3-methacryloxypropylmethyldimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropylmethyldiethoxysilane, 3-methacryloxypropyltriethoxysilane, 3-acryloxypropyltrimethoxysilane, 3-isocyanatetopropyltriethoxysilane, tris-(trimethoxysilylpropyl)isocyanurate, 3-mercaptopropylmethyldimethoxysilane, 3-mercaptopropyltrimethoxysilane, p-styryltrimethoxysilane, 3-ureidopropyltrialkoxysilane, etc.

[0310] Other commercially available SC agents include, for example, KBM-302, KBM-402, KBM-403, KBE-402, KBE-403, KBM-4803, KBM-602, KBM-603, KBM-903, KBE-9103P, KBM-573, KBM-6803, KBM-1003, KBE-1003, KBM-502, KBM-503, KBE-502, KBE-503, KBM-5803, X-12-1048, X-12-1050, KBE-9007N, KBM-9659, KBM-802, KBM-803, KBM-1043, KBE-585A, etc., all manufactured by Shin-Etsu Silicone Co., Ltd.

[0311] Furthermore, other SC agents may be of polymer type. Examples of polymer types include polysiloxane type and organic polymer type.

[0312] Polysiloxane-type silane coupling agents are polymers having a polysiloxane skeleton in their main chain, to which the alkoxysilyl groups and other functional groups are bonded. Commercially available polysiloxane-type products include KR-513, KR-516, KR-517, X-41-1805, and X-41-1810, manufactured by Shin-Etsu Silicone Co., Ltd.

[0313] The organic polymer type is a silane coupling agent in which the alkoxysilyl group and other functional groups are bonded to an organic polymer whose main chain has an organic structure. Commercially available organic polymer type products include X-12-9815, X-12-9845, X-12-1154, X-12-972F, X-12-1159L, etc., manufactured by Shin-Etsu Silicone Co., Ltd.

[0314] Other SC agents can be used alone or in combination of two or more types.

[0315] From the viewpoint of contact hole formation, the content of other SC agents is preferably 0.1 to 15% by mass, and more preferably 0.5 to 10% by mass, of 100% by mass of the nonvolatile content of the photosensitive composition.

[0316] [UV absorber] The photosensitive composition of the present invention may contain an ultraviolet absorber. Among these, a hydroxyphenyl group-containing triazine compound is preferred from the viewpoint of contact hole formation. A hydroxyphenyl group-containing triazine compound is a compound in which a hydroxyphenyl group is bonded to a triazine ring, and is an ultraviolet absorber.

[0317] (Hydroxyphenyl group-containing triazine compound) The hydroxyphenyl group-containing triazine compound may contain at least one compound selected from the compounds represented by the following general formulas (15) and (16) (hereinafter also simply referred to as the "specific triazine compound"). Using the specific triazine compound provides appropriate photocurability to the polymerizable compound, thereby further improving contact hole formation.

[0318] (A hydroxyphenyl group-containing triazine compound represented by general formula (15))

[0319] General formula (15) [ka]

[0320] In general formula (15), R1 represents a hydrocarbon group having 1 to 12 carbon atoms. R2 represents a hydrogen atom or a hydrocarbon group having 1 to 6 carbon atoms.

[0321] The hydrocarbon group having 1 to 12 carbon atoms can be linear, branched, cyclic, or a combination thereof. Furthermore, the hydrocarbon group can be substituted with halogen atoms, cyano groups, amino groups, alkoxy groups, etc. The aforementioned hydrocarbon groups are as already exemplified. Octyl groups and isooctyl groups are preferred for the hydrocarbon group having 1 to 12 carbon atoms.

[0322] The hydrocarbon group having 1 to 6 carbon atoms can be linear, branched, cyclic, or a combination thereof. Furthermore, the hydrocarbon group can be substituted with halogen atoms, cyano groups, amino groups, alkoxy groups, etc. The hydrocarbon group is as already exemplified. Methyl groups and ethyl groups are preferred for the hydrocarbon group having 1 to 6 carbon atoms.

[0323] The following are specific examples of compounds with chemical formulas (UVA-1) to (UVA-4) that represent general formula (15). However, the present invention is not limited to these.

[0324] [ka] JPEG2026068945000050.jpg53118

[0325] A commercially available product of general formula (15) is, for example, the TINUVIN 479 manufactured by BASF Japan.

[0326] (A hydroxyphenyl group-containing triazine compound represented by general formula (16))

[0327] General formula (16) [ka]

[0328] In general formula (16), R1 and R2 are the same as in general formula (15).

[0329] The following are specific examples of compounds with chemical formulas (UVA-5) to (UVA-8) that represent general formula (16). However, the present invention is not limited to these. JPEG2026068945000052.jpg71151JPEG2026068945000053.jpg75151

[0330] A commercially available product of general formula (16) is, for example, the TINUVIN 477 manufactured by BASF Japan.

[0331] Specific triazine compounds can be used alone or in combination of two or more.

[0332] From the viewpoint of contact hole formation, the content of the specific triazine compound is preferably 0.1 to 10% by mass, and more preferably 0.4 to 4% by mass, in the nonvolatile content of the photosensitive composition.

[0333] (Other triazine compounds containing hydroxyphenyl groups) Hydroxyphenyl group-containing triazine compounds may contain other hydroxyphenyl group-containing triazine compounds besides the specified triazine compounds. Examples of commercially available products include TINUVIN 400, 405, and 1600 from BASF Japan, and ADEKA LA-46 and LA-F70 from ADEKA.

[0334] The following are specific examples of other triazine compounds containing hydroxyphenyl groups.

[0335] JPEG2026068945000054.jpg108117

[0336] Other hydroxyphenyl group-containing triazine compounds can be used alone or in combination of two or more.

[0337] The content of other hydroxyphenyl group-containing triazine compounds is preferably 0.1 to 10% by mass, and more preferably 0.4 to 4% by mass, based on 100% by mass of the nonvolatile content of the photosensitive composition.

[0338] (Other UV absorbers) The photosensitive composition of the present invention may contain other ultraviolet absorbers other than hydroxyphenyl group-containing triazine compounds. Examples of other ultraviolet absorbers include benzotriazole compounds, triazine compounds without hydroxyphenyl groups, benzophenone compounds, salicylate ester compounds, cyanoacrylate compounds, and salicylate compounds.

[0339] Examples of commercially available benzotriazole compounds include Chinuvin PS, 99-2, 326, 384-2, 900, 928, 970, 1130, and UVA-903KT from BASF Japan, and Adeka Stab LA-31RG and LA-31G from ADEKA.

[0340] Examples of commercially available benzophenone compounds include Ubinal A, 3049, 3050, and UVA-935LH from BASF Japan, Adeka Stab 1413 from ADEKA, and Omnirad EMK from IGM Resins.

[0341] Other UV absorbers can be used alone or in combination of two or more types.

[0342] From the viewpoint of lightfastness, the content of other ultraviolet absorbers is preferably 0.1 to 5% by mass, and more preferably 0.1 to 1% by mass, based on 100% by mass of the nonvolatile content of the photosensitive composition.

[0343] [Storage stabilizer] The photosensitive composition of the present invention may contain a storage stabilizer.

[0344] Storage stabilizers are not limited and any known compounds can be used. Examples include benzyl trimethyl chloride, quaternary ammonium chlorides such as diethylhydroxyamine, organic acids such as lactic acid and oxalic acid and their methyl ethers, organophosphines such as tert-butylpyrocatechol, tetraethylphosphine, and tetraphenyl, and phosphates.

[0345] The storage stabilizer content is preferably 0.05 to 5% by mass of 100% by mass of the nonvolatile content of the photosensitive composition.

[0346] [Antioxidant] The photosensitive composition of the present invention may contain an antioxidant. Examples of antioxidants include hindered phenol antioxidants, hindered amine antioxidants, phosphorus antioxidants, sulfur antioxidants, and the like.

[0347] Examples of commercially available hindered phenol antioxidants include ADEKA's ADEKA Stab AO-20, AO-30, AO-40, AO-50, AO-60, AO-80, and AO-330; Chemipro's KEMINOX 101, 179, 76, and 9425; BASF Japan's IRGANOX 1010, 1035, 1076, 1098, 1135, 1330, 1726, 1425WL, 1520L, 245, 259, 3114, 5057, and 565; and Sun Chemical's Cyanox CY-1790 and CY-2777.

[0348] Examples of commercially available hindered amine antioxidants include ADEKA's ADEKA Stab LA-52, LA-57, LA-63P, LA-68, LA-72, LA-77Y, LA-77G, LA-81, LA-82, LA-87, LA-402F, LA-502XP; KAMISTAB29, 62, 77, 94 from Chemipro Chemical; Tinuvin111FDL, 123, 144, 249, 292, 5100 from BASF Japan; and Siasorb UV-3346, UV-3529, UV-3853 from Sun Chemical.

[0349] Examples of commercially available phosphorus-based antioxidants include ADEKA's ADEKA Stab PEP-36, PEP-8, HP-10, 2112, 1178, 1500, C, 135A, 3010, and TPP; BASF Japan's IRGAFOS168; and Clariant Chemicals' Hostanox P-EPQ.

[0350] Examples of commercially available sulfur-based antioxidants include ADEKA's ADEKA Stab AO-412S and AO-503, and KEMINOXPLS from Chemipro Chemical Co., Ltd.

[0351] Antioxidants can be used alone or in combination of two or more types.

[0352] The antioxidant content is preferably 0.5 to 5.0% by mass of 100% by mass of the nonvolatile content of the photosensitive composition.

[0353] [Sensitizer] The photosensitive composition of the present invention may contain a sensitizer.

[0354] Examples of sensitizers include thioxanthone compounds and anthracene compounds. Of these, thioxanthone compounds are more preferred.

[0355] Examples of thioxanthone compounds include 2-isopropylthioxanthone and 2,4-diethylthioxanthone. Commercially available products include Kayacure DETX-S from Nippon Kayaku Co., Ltd., Omnirad ITX from IGM Resins, Ltd., and SpeedCure 7010 from Arkema, Inc. An example of anthracene compound is UVS-1331 from Kawasaki Chemical Industries, Ltd.

[0356] Sensitizers can be used alone or in combination of two or more types.

[0357] [Leveling agent] The photosensitive composition of the present invention may contain a leveling agent.

[0358] The leveling agent is not limited and any known compound can be used. Examples include silicone-based leveling agents, fluorine-based leveling agents, acrylic-based leveling agents, and acetylenediol-based leveling agents.

[0359] Commercially available silicone leveling agents include, for example, BYK-300, 306, 310, 313, 315N, 320, 322, 323, 330, 331, 333, 342, 345, 346, 347, 348, 349, 370, 377, 378, 3455, UV3510, 3570 from Bic Chemie, and FZ-7002, 2110, 2122, 2123, 2191, 5609 from Toray Dow Corning. Examples include X-22-4952, X-22-4272, X-22-6266, KF-351A, KF-354L, KF-355A, KF-945, KF-640, KF-642, KF-643, X-22-4515, KF-6004, KP-341 from Shin-Etsu Silicone Co., Ltd., and TegoGlide 432, 440, 450, TegoWet 250, 260, 265, 270, 280 from Evonik Corporation.

[0360] Examples of commercially available fluorine-based leveling agents include Surflon S-242, 243, 420, 611, 651, and 386 from AGC Seimi Chemical Co., Ltd., Megafac F-253, 477, 551, 552, 555, 558, 560, 570, 575, and 576, as well as R-40-LM, R-41, RS-72-K, and DS-21 from DIC Corporation, FC-4430 and 4432 from Sumitomo 3M Corporation, EF-PP31N09, EF-PP33G1, and EF-PP32C1 from Mitsubishi Materials Electronic Chemicals Co., Ltd., and Futergent 602A from Neos Corporation.

[0361] Examples of commercially available acrylic leveling agents include BYK-350, 352, 354, 355, 358, 380, 381, 392, and 394 from BIC Chemie, and Polyflow 57, 77, and 95 from Kyoeisha Chemical.

[0362] Examples of commercially available acetylenediol-based leveling agents include Surfinol 420, 440, 465, 485, SE, DF110D, DE85, and Orfin E1004, 1010, all manufactured by Nisshin Chemical Industry Co., Ltd.

[0363] Leveling agents can be used alone or in combination of two or more types.

[0364] The leveling agent content is preferably 0.001 to 2.0% by mass, and more preferably 0.005 to 1.0% by mass, based on 100% by mass of the nonvolatile content of the photosensitive composition.

[0365] The photosensitive composition of the present invention may contain components other than those listed above. Examples of other components include acid generators, salt generators, and curing catalysts. The content of these other components can be appropriately set within a range that solves the problems of the present invention.

[0366] [Content of specific metallic elements] The photosensitive composition of the present invention preferably contains a total content of Li, Na, K, Mg, Ca, Fe, and Cr (hereinafter also referred to as specific metal elements) of 500 ppm by mass or less.

[0367] Photosensitive compositions containing a total amount of specific metal elements within the above range exhibit excellent dispersion stability and sensitivity even after storage over time. The content of specific metal elements can be measured by inductively coupled plasma atomic emission spectrometry (ICP).

[0368] [Method for producing a photosensitive composition] The photosensitive composition of the present invention can be manufactured by mixing the above-mentioned components. During manufacturing, the components may be combined all at once, or they may be dissolved or dispersed in a polymerizable compound or solvent and then combined sequentially. When a pigment is used as a coloring agent, it is preferable to disperse the pigment. For example, a dispersion can be produced by adding a colorant, a dispersion resin, and a solvent and performing a dispersion treatment. Then, the dispersion can be mixed with a hydroxyphenyl group-containing triazine compound, an alkali-soluble resin, a polymerizable compound, a polymerization initiator, a surfactant, a blocked isocyanate group-containing compound, a silane coupling agent, etc. The timing of adding each material is arbitrary. The materials to be added can be selected arbitrarily. Furthermore, the dispersion process can be performed multiple times.

[0369] Examples of distributed processing machines include two-roll mills, three-roll mills, ball mills, horizontal sand mills, vertical sand mills, annular bead mills, or attritors.

[0370] The average dispersed particle size (secondary particle size) of the colorant particles in the dispersion is preferably 30 to 200 nm, and more preferably 40 to 200 nm. Having an appropriate particle size makes it easier to obtain a photosensitive composition with high dispersion stability.

[0371] The average dispersed particle diameter (secondary particle diameter) is measured using, for example, Nikkiso's Microtrac UPA-EX150, which employs dynamic light scattering (FFT power-spectrum method). The conditions are set to absorption mode for particle permeability, non-spherical particle shape, and D50 particle diameter as the average diameter. The diluent solvent used for dispersion is the same as the one used for measurement, and measuring immediately after sample preparation of ultrasonically treated samples yields results with less variation.

[0372] The photosensitive composition is preferably subjected to centrifugation, sintering filter filtration or membrane filter filtration to remove coarse particles of 5 μm or larger, preferably 1 μm or larger, more preferably 0.5 μm or larger, and any mixed dust. The photosensitive composition of the present invention preferably contains substantially no particles of 0.5 μm or larger, and more preferably contains no particles of 0.3 μm or smaller.

[0373] The photosensitive composition of the present invention is preferably used for pattern formation applications in photolithography. However, the present invention is not limited thereto.

[0374] <Membrane> The film of the present invention is a film formed from the photosensitive composition described above. While a patterned film is preferred, it can also be used as a flat film without a pattern.

[0375] [Membrane manufacturing method] The method for manufacturing the film is not limited, and known methods can be used. For example, it can be manufactured by coating the photosensitive composition of the present invention onto a substrate and drying it.

[0376] [Coating process] Examples of substrates include those made of materials such as glass, resin, and silicone. The glass can be colorless and transparent, or colored glass such as blue glass may be used depending on the application. Examples of resins include polyester resins such as polyester terephthalate, polyolefin resins such as polypropylene and polyethylene, polycarbonate resins, and epoxy resins. The thickness of the substrate is preferably 0.01 to 10 mm. An organic light-emitting layer may be formed on these substrates. Furthermore, an image sensor such as a CCD or CMOS may be formed on the substrate. Additionally, a primer layer may be provided on the substrate as needed to improve adhesion with the upper layer, prevent diffusion of materials, and flatten the surface.

[0377] A known coating method can be used. Examples include the drop method, slit coating method, spray method, roll coating method, rotary coating method, casting coating method, inkjet method, flexographic printing, screen printing, gravure printing, and offset printing.

[0378] The film thickness is preferably about 0.05 to 20.0 μm, and more preferably about 0.3 to 10.0 μm.

[0379] [Drying process] The film coated on the substrate can be dried as appropriate. Drying methods include, for example, vacuum drying, as well as heat drying using a hot plate, IR oven, and convection oven.

[0380] The drying temperature is preferably around 50-130°C. The drying time is preferably around 5 seconds to 5 minutes.

[0381] Next, the film is patterned. Methods for pattern formation include photolithography and dry etching. Of these, photolithography is preferred. Note that if the film is to be used as a flat film, the pattern formation step is not necessary.

[0382] The aforementioned photolithography method involves coating a substrate with a photosensitive composition, drying it to form a layer, exposing the resulting layer to a pattern through a mask (exposure step), and removing the unexposed areas by alkaline development (development step). The pattern is then heat-treated (post-bake step).

[0383] [Exposure process] The exposure process involves exposing the layer formed by coating and drying to a specific pattern via a mask using an exposure device such as a stepper. This allows the exposed area to harden. Examples of active energy rays used for exposure include ultraviolet rays such as g-rays (wavelength 436 nm), h-rays (wavelength 405 nm), and i-rays (wavelength 365 nm). Light with a wavelength of 300 nm or less can also be used. Examples of light with a wavelength of 300 nm or less include KrF-rays (wavelength 248 nm) and ArF-rays (wavelength 193 nm). When using light of a specific wavelength, optical filters can be used. Furthermore, exposure may be performed by continuously irradiating with light, or by repeatedly irradiating and pausing with light in short cycles (e.g., at the millisecond level or less) (pulsed exposure). Furthermore, multiple active energy rays can be used in combination, and exposure can be performed in multiple stages.

[0384] [Development process] Next, by performing an alkaline development treatment, the unexposed layers dissolve in the alkaline developer, leaving only the hardened parts and resulting in a patterned film. Examples of alkaline developers include aqueous solutions containing alkaline compounds such as sodium hydroxide, potassium hydroxide, sodium carbonate, sodium silicate, sodium metasilicate, aqueous ammonia, ethylamine, diethylamine, dimethylethanolamine, tetramethylammonium hydroxide, tetraethylammonium hydroxide, choline, pyrrole, piperidine, and 1,8-diazabicyclo-[5.4.0]-7-undecene. Two or more of these alkaline compounds can be used in combination. Alkaline developers may contain surfactants and organic solvents in addition to alkaline compounds and water. The concentration of the alkaline developer is preferably 0.001 to 10% by mass, and more preferably 0.01 to 1% by mass. The pH of the alkaline developer is preferably 11 to 13, and more preferably 11.5 to 12.5. Using an appropriate pH suppresses pattern roughness and peeling, and improves the residual film rate after development. Development methods include, for example, the dip method, spray method, and paddle method. The development temperature is preferably 15 to 40°C. After alkaline development, it is preferable to wash with pure water.

[0385] [Post-baking process] After development, a heat treatment (post-bake) is performed. Post-bake improves the durability of the film. The temperature is preferably 80 to 300°C, and more preferably 100 to 260°C. The duration is preferably 2 minutes to 2 hours. If a material with low heat resistance is used as the substrate, if a substrate having an organic electroluminescent element as the light-emitting layer is used, or from an environmental standpoint, a temperature of 180°C or lower is preferable.

[0386] <Optical filters> The optical filter of the present invention has the above-described film. Optical filters are used, for example, as clear filters, color filters, black matrices, light-shielding filters, anti-reflective filters, infrared cut filters, infrared transmission filters, etc. The optical filter of the present invention can be manufactured in the same manner as the above-described film.

[0387] <Solid-state image sensor> The solid-state image sensor of the present invention has the above-mentioned optical filter. The solid-state image sensor is not particularly limited as long as it is equipped with the optical filter of the present invention and functions as a solid-state image sensor, but for example, the following configuration is possible.

[0388] The present invention has a configuration in which a substrate has a plurality of photodiodes that constitute the light-receiving area of ​​a solid-state image sensor (CCD image sensor, CMOS image sensor, etc.) and transfer electrodes made of polysilicon or the like, a light-shielding film with an opening only for the light-receiving portion of the photodiode on the photodiode and transfer electrodes, a device protective film made of silicon nitride or the like formed on the light-shielding film so as to cover the entire surface of the light-shielding film and the light-receiving portion of the photodiode, and the optical filter (color filter) of the present invention is on the device protective film. Furthermore, the device protective film may have a configuration in which a light-gathering means (for example, a microlens, etc.; the same applies hereinafter) is provided on the device protective film and below the optical filter (on the side closer to the substrate), or a configuration in which the light-gathering means is provided on the optical filter. The filter may also have a structure in which a hardened film forming each colored pixel is embedded in a space partitioned, for example, in a grid pattern by partition walls. In this case, the partition walls are preferably low refractive index relative to each colored pixel. The imaging device equipped with the solid-state image sensor of the present invention can be used in a variety of applications, such as digital cameras, electronic devices with imaging functions (mobile phones, smartphones, etc.), in-vehicle cameras, and surveillance cameras.

[0389] <Image display device> The image display device of the present invention has the above-mentioned optical filter. Examples of image display devices include liquid crystal displays and organic EL displays. The form used in an image display device is not particularly limited, as long as it functions as an image display device. For example, the following configuration of a liquid crystal display can be considered.

[0390] A liquid crystal display (LCD) comprises a color filter, a counter substrate having a TFT array substrate or the like, and a liquid crystal layer formed between the color filter and the counter substrate. Examples of driving methods for the LCD include the TN method, IPS method, OCB method, and MVA method. The counter substrate can be appropriately selected according to the driving method. Depending on the driving method, the liquid crystal layer can use various liquid crystals with different dielectric anisotropy, or mixtures thereof.

[0391] <Infrared sensor> The infrared sensor of the present invention has the above-mentioned optical filter. The form used in the infrared sensor is not particularly limited as long as it incorporates the optical filter of the present invention and functions as an infrared sensor, but for example, the following configurations can be given.

[0392] The substrate has multiple photodiodes that constitute the light-receiving area of ​​a solid-state image sensor (CCD image sensor, CMOS image sensor, etc.) and transfer electrodes made of polysilicon or the like. A light-shielding film is provided on these photodiodes and transfer electrodes, with openings only in the light-receiving portions of the photodiodes. A device protective film is provided on this light-shielding film, and the optical filter of the present invention is provided on this device protective film. Furthermore, the configuration may include a light-gathering means (for example, a microlens, etc.; the same applies hereinafter) on the device protective film and below the optical filter (closer to the substrate), or a configuration in which the light-gathering means is provided on the optical filter.

[0393] Figure 1 is a schematic cross-sectional view showing an example configuration of an infrared sensor equipped with the optical filter of the present invention. It comprises the infrared sensor 100 and a solid-state image sensor 110 shown in Figure 1.

[0394] The imaging area on the solid-state image sensor 110 is formed by combining an infrared cut filter 111 and a color filter 112.

[0395] The infrared cut filter 111 transmits light in the visible light region (for example, light with a wavelength of 400 to 700 nm) and blocks light in the infrared region (for example, light with a wavelength of 800 to 1,300 nm).

[0396] The color filter 112 is a color filter in which pixels that transmit and absorb light of specific wavelengths in the visible light region are formed. For example, a color filter in which red (R), green (G), and blue (B) pixels are formed is used.

[0397] Between the infrared transmission filter 113 and the solid-state image sensor 110, a resin film 114 is placed that can transmit light of wavelengths that have passed through the infrared transmission filter 113.

[0398] The infrared transmission filter 113 is a filter that has visible light shielding properties and transmits infrared rays of a specific wavelength. Preferably, the infrared transmission filter 113 shields light with wavelengths of 400 to 830 nm and transmits light with wavelengths of 900 to 1,300 nm.

[0399] A microlens 115 is positioned on the incident light h side of the color filter 112 and the infrared transmission filter 113. A planarization film 116 is formed to cover the microlens 115.

[0400] In the configuration shown in Figure 1, a resin film 114 is arranged, but an infrared transmission filter 113 may be formed instead of the resin film 114.

[0401] This infrared sensor can simultaneously capture image information, enabling motion sensing and other applications that recognize moving objects. Furthermore, because it can acquire distance information, it can capture images containing 3D data. In addition, this infrared sensor can be used as a biometric authentication sensor.

[0402] [Example of an embodiment] Examples of embodiments of the present invention are given below. The present invention is not limited to the following.

[0403] <1> The present invention relates to a photosensitive composition comprising a colorant, a polymerization initiator, and a polymerizable compound, wherein the polymerizable compound comprises a polymerizable compound containing an ethyleneoxy group and a propyleneoxy group. <2> The molar ratio of the ethyleneoxy group to the propyleneoxy group is 95:5 to 5:95. <1> A photosensitive composition. <3> The polymerizable compound containing the ethyleneoxy group and the propyleneoxy group includes one selected from the group consisting of a trimethylolpropane skeleton, a ditrimethylolpropane skeleton, a pentaerythritol skeleton, a dipentaerythritol skeleton, a glycerin skeleton, a diglycerin skeleton, an isocyanurate skeleton, an alkylene glycol skeleton, a bisphenol skeleton, and a sorbitol skeleton. <1> or <2> A photosensitive composition. <4> Furthermore, the present invention comprises an alkali-soluble resin, wherein the alkali-soluble resin comprises at least one monomer unit selected from (a) or (b) below. <1> ~ <3> Any photosensitive composition. (a) Polymerizable unsaturated group-containing monomer units (b) Monomer units containing thermocrosslinkable groups <5> The polymerization initiator comprises an oxime ester compound. <1> ~ <4> Any photosensitive composition. <6> The polymerization initiator includes a polymerization initiator having an absorption peak at a wavelength of 367 nm or higher. <1> ~ <5> Any photosensitive composition. <7> Furthermore, the compound includes a compound represented by general formula (5) or general formula (6), <1> ~ <6> Any photosensitive composition. [ka] (In general formula (5), R 1 This represents a hydrocarbon group with 1 to 4 carbon atoms. In general formula (6), R 1 R represents a hydrocarbon group having 1 to 4 carbon atoms, or an alkoxy group having 1 to 4 carbon atoms. 2 Each of these independently represents either a hydrogen atom or a hydrocarbon group having 1 to 4 carbon atoms. <8> The polymerizable compound further comprises at least one selected from the group consisting of polymerizable compounds having an amine structure, polymerizable compounds having a hydroxyl group, polymerizable compounds having an acidic group, and polymerizable compounds having a urethane bond. <1> ~ <7> Any photosensitive composition. <9> The coloring agent comprises at least one selected from (A) or (B) below. <1> ~ <8> Any photosensitive composition. (A) Dyes and salt-forming compounds of the dye and a resin that forms salts (B) Dye polymer having a dye monomer having a dye residue and an ethylenically unsaturated group as a structural unit. <10> <1> ~ <9> A film formed from any of the following photosensitive compositions. <11> <10> An optical filter having a film. <12> <10> A color filter having a film. <13> <10> A solid-state image sensor having an optical filter. <14> <10> An image display device having an optical filter. <15> <10> An infrared sensor having an optical filter. [Examples]

[0404] The present invention will be described in more detail below with reference to examples. However, the present invention is not limited to these examples. Note that "parts" refers to "parts by mass" and "%" refers to "mass percent". In the present invention, non-volatile content or non-volatile content concentration refers to the mass residue after standing in an oven at 120°C for 60 minutes.

[0405] Prior to the examples, each measurement method will be described.

[0406] The weight-average molecular weight (Mw), number-average molecular weight (Mn), acid value (mgKOH / g), amine value (mgKOH / g), and extinction coefficient (L / mol·cm) of the resin are measured as follows.

[0407] (Molecular Weight) The number-average molecular weight (Mn) and weight-average molecular weight (Mw) were measured using gel permeation chromatography (GPC) equipped with an RI detector. An HLC-8220GPC (Tosoh Corporation) was used as the instrument, with two separation columns connected in series and two TSK-GEL SUPER HZM-N packing materials connected in series on both columns. The oven temperature was 40°C, tetrahydrofuran (THF) was used as the eluent, and measurements were taken at a flow rate of 0.35 ml / min. A 1% by mass THF solution was prepared for the sample, and 20 microliters were injected. Molecular weight is expressed as polystyrene equivalent.

[0408] (Acid value) 0.5 to 1 g of the sample solution was mixed with 80 ml of acetone and 10 ml of water and stirred to dissolve uniformly. The solution was then titrated using an automatic titrator ("COM-555," manufactured by Hiranuma Sangyo Co., Ltd.) with a 0.1 mol / L aqueous KOH solution as the titrant, and the acid value (mg KOH / g) was measured. The acid value per unit of non-volatile matter was then calculated from the acid value of the solution and the concentration of non-volatile matter in the solution.

[0409] (Amine value) The amine value is calculated by converting the total amine value (mgKOH / g), measured according to the ASTM D 2074 method, into non-volatile content.

[0410] <Manufacturing of specific polymerizable compounds> (Specific polymerizable compound (1)) 166.2 parts (1 mole) of diglycerin and 2.0 parts of KOH were charged into an autoclave, and dehydration was carried out at 110°C and 1.3 kPa for 30 minutes. After dehydration, the air in the autoclave was replaced with nitrogen, and the temperature inside the autoclave was raised to 130°C, after which 127.7 parts (2.9 moles) of ethylene oxide were charged. After addition reaction and maturation at 130°C, it was cooled to 80°C, and unreacted ethylene oxide in the autoclave was removed at 4.0 kPa for 30 minutes. Next, 75.5 parts (1.3 moles) of propylene oxide were charged. After addition reaction and maturation at 130°C, it was cooled to 80°C, and unreacted propylene oxide in the autoclave was removed at 4.0 kPa for 30 minutes. Next, 3.0 parts of acetic acid were added to the autoclave and held at 80°C for 30 minutes, after which it was removed to obtain precursor 1 of a specific polymerizable compound (1) to which 2.8 moles of ethylene oxy groups and 1.2 moles of propylene oxy groups were added. The obtained precursor 1 was reacted with 317.1 parts (4.4 moles) of acrylic acid at 85°C for 10 hours, then toluene, a large amount of water, and an aqueous sodium hydroxide solution in an amount sufficient to neutralize the unreacted acrylic acid were added, the organic layer was removed using a separatory funnel, and the toluene was removed by distillation using an evaporator to obtain specific polymerizable compound (1).

[0411] (Specific polymerizable compounds (2)~(6)) By varying the amounts of ethylene oxide and propylene oxide used, specific polymerizable compounds (2) to (6) were synthesized in the same manner as specific polymerizable compound (1), resulting in the compositions shown in Table 1. In Table 1, "EO:PO" represents the average molar ratio of the number of moles of ethylene oxy groups to the number of moles of propylene oxy groups in the molecule.

[0412] (Specific polymerizable compound (7)) 92.1 parts (1 mole) of glycerin and 2.0 parts of KOH were charged into an autoclave, and dehydration was carried out at 110°C and 1.3 kPa for 30 minutes. After dehydration, the air in the autoclave was replaced with nitrogen, and the temperature inside the autoclave was raised to 130°C, after which 127.7 parts (2.9 moles) of ethylene oxide were charged. After addition reaction and maturation at 130°C, it was cooled to 80°C, and unreacted ethylene oxide in the autoclave was removed at 4.0 kPa for 30 minutes. Next, 75.5 parts (1.3 moles) of propylene oxide were charged. After addition reaction and maturation at 130°C, it was cooled to 80°C, and unreacted propylene oxide in the autoclave was removed at 4.0 kPa for 30 minutes. Next, 3.0 parts of acetic acid were added to the autoclave and held at 80°C for 30 minutes, after which it was removed to obtain precursor 1 of a specific polymerizable compound (7) to which 2.8 moles of ethylene oxy groups and 1.2 moles of propylene oxy groups were added. The obtained precursor 1 was reacted with 158.5 parts (2.2 moles) of acrylic acid at 85°C for 10 hours, then toluene, a large amount of water, and enough caustic to neutralize the unreacted acrylic acid were added, the organic layer was removed using a separatory funnel, and the toluene was removed by distillation using an evaporator to obtain the specific polymerizable compound (7).

[0413] (Specific polymerizable compounds (8)~(12)) By varying the amounts of ethylene oxide and propylene oxide used, specific polymerizable compounds (8) to (12) were synthesized in the same manner as specific polymerizable compound (7), resulting in the compositions shown in Table 1.

[0414] [Table 1]

[0415] (Specific polymerizable compounds (13)~(20)) Diglycerin was replaced with trimethylolpropane, ditrimethylolpropane, pentaerythritol, dipentaerythritol, tri(2-hydroxyethyl) isocyanurate, propylene glycol, bisphenol A, bisphenol F, or sorbitol, and 1.05 times the amount of ethylene oxide and propylene oxide relative to the number of moles of hydroxyl groups in each compound was added to synthesize specific polymerizable compounds (8) to (20) in the same manner as specific polymerizable compound (7), so as shown in Table 2. Note that "EO:PO" in Table 2 is the same as in Table 1.

[0416] [Table 2]

[0417] <Manufacturing of alkali-soluble resins> (Solution of alkali-soluble resin (1) having polymerizable unsaturated group-containing monomer units) 196 parts of cyclohexanone were placed in a reaction vessel, which was a separable four-neck flask fitted with a thermometer, condenser, nitrogen gas inlet tube, dropping tube, and stirrer. The temperature was raised to 80°C while stirring, and the reaction vessel was purged with nitrogen. Next, a mixture of 20.2 parts of methacrylic acid (hereinafter MAA), 21.8 parts of 2-hydroxyethyl methacrylate (hereinafter 2HEMA), 38.9 parts of Aronics M-110 (paracumylphenol EO modified acrylate manufactured by Toagosei Co., Ltd.), 35.8 parts of n-butyl methacrylate (n-BA), 39.0 parts of benzyl methacrylate (BzMA), and 1.0 part of the polymerization initiator 2,2'-azobisisobutyronitrile was added dropwise over 2 hours and the mixture was allowed to react. After the addition was complete, the reaction was continued at 80°C for a further 3 hours. Subsequently, propylene glycol monomethyl ether acetate (hereinafter referred to as PGMAc) was added to the mixture so that the non-volatile content was 30% by mass, thereby obtaining a solution of the alkali-soluble resin (14), which is an alkali-soluble resin. The alkali-soluble resin (1) had an acid value of 81 mgKOH / g and a weight-average molecular weight of 28,000. The amounts are expressed in molar percentage in Table 1.

[0418] (Solution of alkali-soluble resin (2) having polymerizable unsaturated group-containing monomer units) A reaction vessel was prepared by attaching a thermometer, condenser, nitrogen gas inlet tube, and stirrer to a separable four-neck flask. 100 parts of PGMAc were placed in the vessel, and while injecting nitrogen gas into the vessel, it was heated to 120°C. At the same temperature, a mixture of 85.2 parts of GMA (glycidyl methacrylate), 66.1 parts of DCPMA (dicyclopentanyl methacrylate), and 10.4 parts of styrene (hereinafter referred to as St), along with a mixture of 5.0 parts of azobisisobutyronitrile dissolved in PGMAc as a polymerization initiator, was added dropwise over 2.5 hours to carry out the polymerization reaction. After the dropwise addition was complete, the mixture was stirred and reacted at 120°C for a further 2 hours. Next, the flask was purged with air, and 43.2 parts of acrylic acid (hereinafter referred to as AA), 0.3 parts of trisdimethylaminomethylphenol, and 0.3 parts of hydroquinone were added, and the mixture was stirred and reacted at 120°C for 5 hours. Furthermore, 59.3 parts of tetrahydrophthalic anhydride (hereinafter referred to as THPA) and 0.5 parts of triethylamine were added, and the mixture was stirred and reacted at 120°C for 4 hours. Subsequently, PGMAc was added to the solution to prepare the alkali-soluble resin (2) by adjusting the non-volatile content to 30% by mass. The resin had an acid value of 79 mgKOH / g and a weight-average molecular weight of 8,500. The alkali-soluble resin (2) having polymerizable unsaturated group-containing monomer units is an alkali-soluble resin having monomer units represented by the general formula (7) above. (R is a hydrogen atom, L 1 (This is a cyclohexa-4-ene-1,2-diyl group.)

[0419] (Solution of alkali-soluble resin (3) having monomer units containing polymerizable unsaturated groups) Similar to the alkali-soluble resin (2) solution having polymerizable unsaturated group-containing monomer units, alkali-soluble resin (3) having polymerizable unsaturated group-containing monomer units was synthesized by changing the type and amount of monomers used and the amount of polymerization initiator used so that the composition ratio and weight-average molecular weight were as shown in Table 1. Then, PGMAc was added to make the non-volatile content 30% by mass. Note that alkali-soluble resin (3) having polymerizable unsaturated group-containing monomer units is an alkali-soluble resin having monomer units represented by the general formula (7) above. R is a hydrogen atom, L 1 (This is an ethylene group.)

[0420] [Table 3]

[0421] In Table 3, SA represents succinic anhydride.

[0422] (Solution of alkali-soluble resin (4) containing thermocrosslinkable group monomer units) A flask equipped with a stirrer, dropping funnel, condenser, thermometer, and gas inlet tube was filled with 100 parts of PGMAc, stirred while purging with nitrogen, and heated to 78°C. Next, a mixture of 25.2 parts of Karenz MOI-DEM (2-methyl-1-oxo-2-propenyl)oxyethyl aminocarbonyl malonate, manufactured by Showa Denko, 31.2 parts of 2HEMA, 37.5 parts of DCPMA, 20.7 parts of MAA, and 27.0 parts of methyl methacrylate (hereinafter, MMA), which is a monomer represented by general formula (8), and a mixture of 12.0 parts of 2,2'-azobis(2,4-dimethylvaleronitrile) (polymerization initiator) dissolved in 50 parts of PGMAc was added dropwise to the flask from the dropping funnel and allowed to react. After the dropwise addition was complete, the mixture was stirred at 78°C for 3 hours. Subsequently, PGMAc was added to prepare the alkali-soluble resin (4) solution so that the non-volatile content was 30% by mass. The alkali-soluble resin (4) had an acid value of 74 mgKOH / g and a weight-average molecular weight of 8,000.

[0423] (Solution of alkali-soluble resin (5) containing thermocrosslinkable group monomer units) Alkali-soluble resin (5) was synthesized by replacing a portion of DCPMA with GMA, and achieving the same composition ratio and weight-average molecular weight as alkali-soluble resin (4) as shown in Table 4. Subsequently, PGMAc was added to prepare an alkali-soluble resin (5) solution so that the non-volatile content was 30% by mass. The weight-average molecular weight of the resin was adjusted by changing the amount of polymerization initiator used.

[0424] (Solution of alkali-soluble resin (6) containing thermocrosslinkable group monomer units) A resin was synthesized in the same manner as the alkali-soluble resin (4), with a portion of DCPMA replaced by GMA. Then, the flask was purged with air, and AA, triphenylphosphine, and methylhydroquinone were added and reacted at 110°C for 10 hours. This introduced monomer units (hereinafter, GMA+AA) formed by the reaction of epoxy groups derived from GMA in the resin with carboxyl groups of AA. GMA+AA is a polymerizable unsaturated group-containing monomer unit. Subsequently, PGMAc was added to prepare an alkali-soluble resin (6) solution so that the non-volatile content was 30% by mass.

[0425] (Solution of alkali-soluble resin (7) containing thermocrosslinkable group monomer units) In a four-necked flask equipped with a stirrer, thermometer, dropping funnel, and reflux condenser, 28.5 parts diethyl malate, 0.01 parts 2,6-di-tert-butyl-4-methylphenol, and 0.05 parts dibutyltin dilaurate were added and stirred, then cooled to 15-20°C. The temperature was then maintained at 15-20°C, and 23.3 parts 2-methacryloyloxyethyl isocyanate were added dropwise from the dropping funnel while stirring. After the addition was complete, the mixture was stirred at 25°C for 13 hours to allow the reaction to proceed. The disappearance of the isocyanate group peak was confirmed by IR spectroscopy, yielding the monomer of the above chemical formula (1-3), represented by general formula (8).

[0426] 200 parts of PGMAc were placed in a four-necked flask equipped with a stirrer, thermometer, dropping funnel, reflux condenser, and gas inlet tube. The flask was then stirred while purging with nitrogen and heated to 90°C. Next, a mixture of 41.7 parts of the compound of chemical formula (16), 14 parts of MAA, 86 parts of n-BA, and 76 parts of MMA, and a mixture prepared by adding 24 parts of 2,2'-azobis(isobutyrate)dimethyl (hereinafter referred to as V-601) as a polymerization initiator to 50 parts of PGMAc and dissolving it, were added dropwise to the flask from the dropping funnel. After the dropwise addition was complete, a mixture of 4 parts of V-601 dissolved in 16 parts of PGMAc was added dropwise, and the mixture was allowed to react for 3 hours. Subsequently, PGMAc was added to prepare an alkali-soluble resin (7) solution so that the non-volatile content was 30% by mass.

[0427] (Solution of alkali-soluble resin (8) containing thermocrosslinkable group monomer units) To 100 parts of alkali-soluble resin (7), 0.1 parts of 1,8-diazabicyclo[5.4.0]-undecene-7 were added, and the temperature was raised to 80°C while stirring. The reaction was carried out at 80°C for 30 minutes, and then cooled to terminate the reaction. This yielded alkali-soluble resin (8) having a thermo-crosslinkable group-containing monomer unit formed from the above chemical formula (2-3), which is a monomer represented by general formula (9).

[0428] (Solution of alkali-soluble resin (9) containing thermocrosslinkable group monomer units) In a four-necked flask equipped with a stirrer, thermometer, dropping funnel, and reflux condenser, 190.2 parts of diethyl malate, 0.17 parts of 2,6-di-tert-butyl-4-methylphenol, and 0.33 parts of dibutyltin dilaurate were added and stirred, then cooled to 15-20°C. The temperature was then maintained at 15-20°C, and 141.1 parts of 2-acryloyloxyethyl isocyanate were added dropwise from the dropping funnel while stirring. After the addition was complete, the mixture was stirred at 25°C for 13 hours to allow the reaction to proceed. The disappearance of the isocyanate group peak was confirmed by IR spectroscopy, yielding the monomer of the above chemical formula (1-10), represented by general formula (8).

[0429] 80 parts PGMAc were placed in a flask equipped with a stirrer, dropping funnel, condenser, thermometer, and gas inlet tube, and the mixture was stirred while purging with nitrogen and heated to 78°C. Next, 48.8 parts of the compound of chemical formula (18), 24.7 parts of Karenz MOI-BP (2-[(3,5-dimethylpyrazolyl)carbonylamino]ethyl methacrylate manufactured by Showa Denko Co., Ltd.), 25.5 parts of 2HEMA, 8.6 parts of 2-ethylhexyl acrylate (hereinafter, 2EHA), and 17.4 parts of 2,2'-azobis(2,4-dimethylvaleronitrile) (polymerization initiator) were mixed and added dropwise to the flask from the dropping funnel. After the addition was complete, the mixture was stirred at 78°C for 3 hours to allow the reaction to proceed, then 0.2 parts of 1,8-diazabicyclo[5.4.0]-undecene-7 were added, and the mixture was stirred at 78°C for another 30 minutes. This resulted in the synthesis of a thermobridgeable group-containing monomer unit formed from the compound of chemical formula (2-4) above, which is a monomer represented by general formula (9).

[0430] Next, 9.9 parts of succinic anhydride (hereinafter referred to as SA) and 0.5 parts of lithium naphthenate (catalyst) were added, and the mixture was stirred at 78°C for 1 hour. This introduced monomer units (hereinafter referred to as 2HEMA+SA) in which SA was added to the hydroxyl group of 2HEMA. 2HEMA+SA is an acidic group-containing monomer unit. Subsequently, PGMAc was added to prepare an alkali-soluble resin (9) solution so that the non-volatile content was 30% by mass.

[0431] (Solution of alkali-soluble resin (10) having monomer units containing a thermocrosslinkable group) By substituting Karenz MOI-BP with Karenz MOI-BM (2-[O-(1'-methylpropyleneamino)carboxyamino]ethyl methacrylate manufactured by Showa Denko Corporation), alkali-soluble resin (10) was synthesized to have the same composition ratio and weight-average molecular weight as described in Table 4, similar to alkali-soluble resin (9). Subsequently, PGMAc was added to prepare an alkali-soluble resin (10) solution so that the non-volatile content was 30% by mass.

[0432] (Solution of alkali-soluble resin (11) having monomer units containing a thermocrosslinkable group) A flask equipped with a stirrer, dropping funnel, condenser, thermometer, and gas inlet tube was filled with 70 parts PGMAc, stirred while purging with nitrogen, and heated to 90°C. Next, a mixture of 20.7 parts 2-(acetoacetoxy)ethyl methacrylate (hereinafter referred to as 2AAEM), a monomer represented by general formula (10), 26.7 parts MAA, and 52.6 parts DCPMA, and a mixture of 5.0 parts V-601 dissolved in 30 parts PGMAc were added dropwise to the flask from the dropping funnel. After the dropwise addition was complete, the mixture was stirred and allowed to react at 90°C for 6 hours. Subsequently, the mixture was cooled to 40°C, and 0.12 parts of 4-methoxyphenol, 17.6 parts of 3,4-epoxycyclohexylmethyl acrylate (hereinafter referred to as ECHA), and 4.7 parts of triphenylphosphine were added. The temperature was then raised to 110°C, and the mixture was stirred and reacted for 10 hours. This introduced monomer units (hereinafter referred to as MAA+ECHA) in which the epoxy group of ECHA was added to the carboxyl group of MAA. MAA+ECHA is a monomer unit containing polymerizable unsaturated groups. Subsequently, PGMAc was added to prepare an alkali-soluble resin (11) solution so that the non-volatile content was 30% by mass.

[0433] (Solution of alkali-soluble resin (12) having monomer units containing a thermocrosslinkable group) 300 parts of PGMAc were added to a flask equipped with a stirrer, dropping funnel, condenser, thermometer, and gas inlet tube. The mixture was then stirred while purging with nitrogen and heated to 105°C. Next, a mixture of 106.9 parts of 3-methacryloyloxypropyltrimethoxysilane (hereinafter referred to as monomer A), which is a monomer represented by general formula (11), 40.8 parts of MAA, and 125 parts of MMA, along with 27.3 parts of V-601, was added dropwise to the flask using the dropping funnel. After the addition was complete, the mixture was allowed to react at 105°C for 2 hours with stirring. Subsequently, PGMAc was added to adjust the non-volatile content to 30% by mass, and an alkali-soluble resin (12) solution was prepared.

[0434] (Solution of alkali-soluble resin (13) having monomer units containing a thermocrosslinkable group) By replacing monomer A with 3-methacryloyloxypropylmethyldiethoxysilane (hereinafter referred to as monomer B), alkali-soluble resin (13) was synthesized in the same manner as alkali-soluble resin (12) to have the composition ratio and weight-average molecular weight shown in Table 4. Subsequently, PGMAc was added to prepare an alkali-soluble resin (13) solution so that the non-volatile content was 30% by mass.

[0435] (Solution of alkali-soluble resin (14) having monomer units containing a thermocrosslinkable group) A flask equipped with a stirrer, dropping funnel, condenser, thermometer, and gas inlet tube was filled with 100 parts PGMAc, stirred while purging with nitrogen, and heated to 90°C. Next, a mixture of 35 parts tert-butyl methacrylate (hereinafter, tBMA), 5 parts 2AAEM, 10 parts N-benzylmaleimide (hereinafter, BzMI), 20 parts 2HEMA, 17.1 parts MAA, and 2 parts t-butyl peroxy-2-ethylhexanoate (polymerization initiator), which are monomers represented by general formula (12), and a mixture of 0.6 parts n-dodecyl mercaptan mixed with 20 parts PGMAc were added dropwise to the flask from the dropping funnel. After the addition was complete, the temperature was maintained at 90°C for 30 minutes, then the temperature was raised to 115°C and stirred for 90 minutes to allow the reaction to proceed. Subsequently, PGMAc was added to prepare an alkali-soluble resin (14) solution so that the non-volatile content was 30% by mass.

[0436] (Solution of alkali-soluble resin (15) containing thermocrosslinkable group monomer units) Karenz MOI-DEM was replaced with Karenz MOI-BP, and alkali-soluble resin (15) was synthesized to have the same composition ratio and weight-average molecular weight as alkali-soluble resin (4) as shown in Table 5. Subsequently, PGMAc was added to adjust the non-volatile content to 30%, thereby preparing the alkali-soluble resin (15) solution.

[0437] (Solution of alkali-soluble resin (16) having monomer units containing a thermocrosslinkable group) Karenz MOI-DEM was replaced with GMA, and alkali-soluble resin (16) was synthesized to have the same composition ratio and weight-average molecular weight as alkali-soluble resin (4) as shown in Table 5. Subsequently, PGMAc was added to prepare an alkali-soluble resin (16) solution so that the non-volatile content was 30% by mass.

[0438] (Solution of alkali-soluble resin (17) having monomer units containing a thermocrosslinkable group) Karenz MOI-DEM is 3,4-epoxytricyclo[5.2.1.0 2,6 ] Decane-8-yl acrylate (hereinafter referred to as monomer C) and 3,4-epoxytricyclo[5.2.1.0 2,6 Instead of a mixture of decane-9-yl acrylate (hereinafter referred to as monomer D) (molar ratio 1:1), an alkali-soluble resin (17) was synthesized to have the composition ratio and weight-average molecular weight listed in Table 5, similar to the alkali-soluble resin (4). Subsequently, PGMAc was added to prepare an alkali-soluble resin (17) solution so that the non-volatile content was 30% by mass.

[0439] [Table 4]

[0440] [Table 5]

[0441] The amounts of each component in Tables 4 and 5 are expressed in mole percent. Resins (1) to (17) in Tables 4 and 5 refer to alkali-soluble resins (1) to (17).

[0442] <Production of compounds containing blocked isocyanate groups> (Preparation of a solution containing a blocked isocyanate group (1)) In a four-necked flask equipped with a thermometer, stirring blades, and reflux condenser, 100 parts by mass of hexamethylene diisocyanate (hereinafter referred to as HDI) were charged under a nitrogen stream. The reactor temperature was maintained at 60°C under stirring, and 0.095 parts by mass of trimethylbenzylammonium hydroxide were added to carry out the reaction. After 4.5 hours, sampling was performed, and when the conversion rate reached 40% by mass, 0.02 parts by mass of phosphoric acid were added to stop the reaction. After filtering the reaction solution, unreacted HDI was removed using a thin-film evaporator to obtain isocyanurate-type polyisocyanate (hereinafter referred to as "precursor (1)"). The obtained precursor (1) had an NCO content of 22.0% by mass, a number-average molecular weight of 655, and an average number of isocyanate groups of 3.43. Furthermore, regarding the obtained precursor (1)... 1 1H-NMR analysis confirmed the presence of isocyanurate groups. In a four-necked flask equipped with a thermometer, stirring blades, and reflux condenser, 100 parts by mass of the above precursor (1) and diethyl malonate (100 mol% relative to 100 mol% of NCO groups) were charged under a nitrogen stream, and butyl acetate was added to prepare the solution to have a non-volatile content of 60% by mass. Then, while stirring, 1.0 part by mass of a methanol solution containing sodium methylate (28% by mass relative to the total mass of the solution) was added dropwise, and the external bath was adjusted to bring the solution temperature to 55°C. The blocking reaction was carried out at 55°C for 5 hours to obtain a blocked isocyanate group-containing compound (1) solution with a non-volatile content of 60% by mass, containing the structure shown in (X-1) above as the blocked isocyanate group.

[0443] (Preparation of a solution containing a blocked isocyanate group (2)) In a four-necked flask equipped with a thermometer, stirring blades, and reflux condenser, 100 parts by mass of the above precursor (1), diethyl malonate (70 mol% relative to 100 mol% of NCO groups), and dibutyl malonate (30 mol% relative to 100 mol% of NCO groups) were charged under a nitrogen stream, and butyl acetate was added to prepare the solution to have a non-volatile content of 60% by mass. Next, while stirring, 1.0 part by mass of a methanol solution containing sodium methylate (28% by mass relative to the total mass of the solution) was added dropwise, and the external bath was adjusted to bring the solution temperature to 55°C. The blocking reaction was carried out at 55°C for 5 hours to obtain a blocked isocyanate group-containing compound (2) solution with a non-volatile content of 60% by mass, containing the structure shown in (X-1) and the structure shown in (X-8) as blocked isocyanate groups in a molar ratio of 70:30.

[0444] (Preparation of a solution containing a blocked isocyanate group (3)) In a four-necked flask equipped with a thermometer, stirring blades, and reflux condenser, 100 parts by mass of the above precursor (1), diethyl malonate (30 mol% relative to 100 mol% of NCO groups), and dibutyl malonate (70 mol% relative to 100 mol% of NCO groups) were charged under a nitrogen stream, and butyl acetate was added to prepare the solution to have a non-volatile content of 60% by mass. Next, while stirring, 1.0 part by mass of a methanol solution containing sodium methylate (28% by mass relative to the total mass of the solution) was added dropwise, and the external bath was adjusted to bring the solution temperature to 55°C. The blocking reaction was carried out at 55°C for 5 hours to obtain a blocked isocyanate group-containing compound (3) solution with a non-volatile content of 60% by mass, containing the structure shown in (X-1) and the structure shown in (X-8) as blocked isocyanate groups in a molar ratio of 30:70.

[0445] (Preparation of a solution containing a blocked isocyanate group (4)) In a four-necked flask equipped with a thermometer, stirring blade, and reflux condenser, 100 parts by mass of precursor (1), diisopropyl malonate (70 mol% relative to 100 mol% of NCO groups), and di-tert-butyl malonate (30 mol% relative to 100 mol% of NCO groups) were charged under a nitrogen stream. Butyl acetate was then added to prepare the solution to have a non-volatile content of 60% by mass. Next, while stirring, 1.0 part by mass of a methanol solution containing sodium methylate (28% by mass relative to the total mass of the solution) was added dropwise. The external bath was then adjusted to bring the solution temperature to 55°C, and the blocking reaction was carried out at 55°C for 5 hours to obtain a blocked isocyanate group-containing compound (4) solution with a non-volatile content of 60% by mass, containing the structure shown in (X-4) and the structure shown in (X-7) as blocked isocyanate groups in a molar ratio of 70:30.

[0446] <Manufacturing of silane coupling agents> (Specific SC agent (1)) 116 parts of hydroxyethyl acrylate were placed in a 1 L separable flask equipped with a stirrer, reflux condenser, dropping funnel, and thermometer, and heated to 80°C while stirring. 205 parts of 3-isocyanate propyltrimethoxysilane were added dropwise, and the mixture was reacted at 80°C for 4 hours. Subsequently, IR measurement confirmed that the absorption peak derived from the isocyanate group of the starting material had completely disappeared, and instead, an absorption peak derived from the urethane bond had been generated, yielding a specific SC agent (1) whose main component is represented by the following chemical formula (4). As a minor component, the mixture contains 2-10 condensates of chemical formula (4) (compounds where n in general formula (17) is 2-10).

[0447] Chemical formula (4) [ka]

[0448] (Specific SC agent (2)) 524 parts of dipentaerythritol pentaacrylate were charged into a 1 L separable flask equipped with a stirrer, reflux condenser, dropping funnel, and thermometer, and heated to 80°C while stirring. 205 parts of 3-isocyanate propyltrimethoxysilane were added dropwise, and the mixture was reacted at 80°C for 4 hours. Subsequently, IR measurement confirmed that the absorption peak derived from the isocyanate group of the starting material had completely disappeared, and instead, an absorption peak derived from the urethane bond had been generated, yielding a specific SC agent (2) whose main component is represented by the following chemical formula (5). As a minor component, the mixture contains 2-10 condensates of chemical formula (5) (compounds where n in general formula (17) is 2-10).

[0449] Chemical formula (5) [ka]

[0450] (Specific SC agent (3)) 298 parts of pentaerythritol triacrylate were charged into a 1 L separable flask equipped with a stirrer, reflux condenser, dropping funnel, and thermometer, and heated to 80°C while stirring. 205 parts of 3-isocyanate propyltrimethoxysilane were added dropwise, and the mixture was reacted at 80°C for 4 hours. Subsequently, IR measurement confirmed that the absorption peak derived from the isocyanate group of the starting material had completely disappeared, and instead, an absorption peak derived from the urethane bond had been generated, yielding a specific SC agent (3) whose main component is represented by the following chemical formula (6). As a minor component, the mixture contains 2-10 condensates of chemical formula (6) (compounds where n in general formula (17) is 2-10).

[0451] Chemical formula (6) [ka]

[0452] (Specific SC agent (4)) 116 parts of hydroxyethyl acrylate were placed in a 1 L separable flask equipped with a stirrer, reflux condenser, dropping funnel, and thermometer, and heated to 80°C while stirring. 247 parts of 3-isocyanate-propyltriethoxysilane were added dropwise, and the mixture was reacted at 80°C for 4 hours. Subsequently, IR measurement confirmed that the absorption peak derived from the isocyanate group of the starting material had completely disappeared, and instead, an absorption peak derived from the urethane bond had been generated, yielding a specific SC agent (4) whose main component is represented by the following chemical formula (7). As a minor component, the mixture contains 2-10 condensates of chemical formula (7) (compounds where n in general formula (17) is 2-10).

[0453] Chemical formula (7) [ka]

[0454] The specified SC agents (1) to (4) are silane coupling agents having an alkoxysilyl group, a (meth)acryloyl group, and a urethane bond.

[0455] <Manufacturing of colorants> (Coloring agent (D1)) 67.3 parts of methyl ethyl ketone (MEK) were charged into a four-necked separable flask equipped with a thermometer, stirrer, distillation tube, and condenser, and the temperature was raised to 75°C under a nitrogen stream. Separately, 34.0 parts of MMA, 28.0 parts of n-BA, 28.0 parts of 2-ethylhexyl methacrylate (2-EHMA), 10.0 parts of dimethylaminoethyl methacrylate (DM), 6.5 parts of 2,2'-azobis(2,4-dimethylvaleronitrile), and 25.1 parts of MEK were homogenized and then placed in a dropping funnel, which was attached to the four-necked separable flask, and added dropwise over 2 hours. Two hours after the end of the dropwise addition, the polymerization yield was confirmed to be 98% or higher based on the non-volatile content, and the weight-average molecular weight was confirmed to be 6,830, and the mixture was cooled to 50°C. To this, 3.2 parts of methyl chloride and 22.0 parts of ethanol were added, and the mixture was reacted at 50°C for 2 hours. Then, the temperature was increased to 80°C over 1 hour, and the mixture was reacted for 2 hours to obtain salt-forming resin 1. Next, 30 parts of salt-forming resin 1 (calculated on a non-volatile content basis) were added to 2,000 parts of water, and after thorough stirring and mixing, the mixture was heated to 60°C. Meanwhile, an aqueous solution was prepared by dissolving 10 parts of CI Acid Red 52 in 90 parts of water, and this was gradually added dropwise to the salt-forming resin 1 solution. After the dropwise addition, the reaction was carried out at 60°C for 120 minutes with stirring. To confirm the endpoint of the reaction, a sample was taken and the reaction solution was dropped onto filter paper; the point at which the bleeding stopped was considered the endpoint. After cooling to room temperature with stirring, suction filtration was performed, and after washing with water, the salt-forming compound remaining on the filter paper was dried in a dryer to remove moisture and obtain a coloring agent (D1), which is a salt-forming compound of CI Acid Red 52 and salt-forming resin 1. The content of components derived from CI Acid Red 52 in the salt-forming compound was 25% by mass.

[0456] (Coloring agent (D2)) Colorant (D2) was prepared in the same manner as colorant (D1), except that CI Acid Red 52 was replaced with CI Acid Red 289. At this time, the content of the component derived from CI Acid Red 289 in the salt-forming compound was 25% by mass.

[0457] (Coloring agent (D3)) In a reactor equipped with a gas inlet pipe, condenser, stirring blades, and thermometer, 18.2 parts of MMA, 14.8 parts of n-BA, 14.8 parts of 2-EHMA, 10.0 parts of MAA, 15.0 parts of 3-ethyl-3-methacryloxymethyloxetane, and 15.0 parts of tBMA were charged. The mixture was stirred at 50°C for 1 hour while flowing nitrogen, and the system was purged with nitrogen. Next, 2.1 parts of ethyl bromoisobutyrate, 1.9 parts of cuprous chloride, and 62.3 parts of PGMAc were charged, and the temperature was raised to 100°C under a nitrogen stream to start polymerization of the first block. After 4 hours of polymerization, the polymerization solution was sampled and the non-volatile content was measured. Based on the non-volatile content, it was confirmed that the polymerization conversion rate was 98% or higher. Next, 8.1 parts of PGMAc and 12.2 parts of dimethylaminoethylmethyl chloride methacrylate as the second block monomer were added to the reaction apparatus, and the reaction was continued while stirring at 100°C under a nitrogen atmosphere. Two hours after the addition of dimethylaminoethylmethyl chloride methacrylate, the polymerization solution was sampled and its non-volatile content was measured. Based on the non-volatile content, it was confirmed that the polymerization conversion rate of the second block was 98% or higher, and after cooling to 50°C, methanol was added to obtain salt-forming resin 2. Next, 30 parts of salt-forming resin 2 (calculated on a non-volatile content basis) were added to 2,000 parts of water, and after thorough stirring and mixing, the mixture was heated to 60°C. Meanwhile, an aqueous solution was prepared by dissolving 10 parts of CI Acid Red 463 in 90 parts of water, and this was gradually added dropwise to the salt-forming resin 2 solution. After addition, the mixture was stirred at 60°C for 120 minutes to allow the reaction to proceed thoroughly. The endpoint of the reaction was confirmed by dropping the reaction solution onto filter paper; the point at which the seepage stopped was considered the endpoint, and it was determined that a salt-forming compound had been obtained. After cooling to room temperature while stirring, suction filtration was performed, and after washing with water, the salt-forming compound remaining on the filter paper was dried in a dryer to remove moisture and obtain a coloring agent (D3), which is a salt-forming compound of CI Acid Red 463 and salt-forming resin 2. At this time, the content of components derived from CI Acid Red 463 in the salt-forming compound was 25% by mass.

[0458] (Coloring agent (D4)) A compound represented by the following chemical formula (A3) was obtained by the method described in paragraphs 0132 to 0136 of Japanese Patent Publication No. 2020-122971.

[0459] [ka]

[0460] A 100 mL three-necked flask, fitted with a stirring bar, reflux condenser, and thermometer, was thoroughly purged with nitrogen and charged with 15.0 parts of cyclohexanone. The flask was then heated to an internal temperature of 70 ± 2 °C under a nitrogen stream. To this, a solution prepared by mixing 9.0 parts (10.0 mmol) of the compound represented by the above chemical formula (A3), 1.0 part (11.6 mmol) of MAA, 5.0 parts (50.0 mmol) of MMA, 2.02 parts (8.13 mmol) of the polymerization initiator 2,2'-azobis(2,4-dimethylvaleronitrile) (Wako Pure Chemical Industries, trade name V-65) and 45.0 g of cyclohexanone was added dropwise over 2 hours using a pump while maintaining an internal temperature of 70 ± 2 °C. After the dropwise addition was complete, stirring was continued for another hour at the same temperature. Subsequently, a solution of 0.728 parts (2.71 mmol) of 2,2'-azobis(2,4-dimethylvaleronitrile) dissolved in 1.16 parts of cyclohexanone was added to the reaction mixture all at once, and the mixture was stirred at the same temperature for 3 hours. The reaction solution was cooled to room temperature and added dropwise to a large amount of hexane. The resulting colored solid was dried under reduced pressure at 50°C to obtain 14.4 parts of copolymer (96% yield). The obtained copolymer had a mass of 5,300. This polymer was designated as colorant (D4). Colorant (D4) is the aforementioned specific dye polymer.

[0461] (Yellow pigment (y)) In a reaction vessel, 46.2 parts of diazobarbituric acid and 38.4 parts of barbituric acid were added to 1,100 parts of distilled water at 85°C. Next, an aqueous potassium hydroxide solution was added to adjust the pH to approximately 5, and the mixture was stirred for 90 minutes to synthesize an azobarbituric acid precursor. 0.3 moles of the obtained azobarbituric acid precursor were mixed with 1,500 parts of distilled water at 82°C, and 10 parts of 30% hydrochloric acid were added dropwise, followed by the addition of 0.6 moles of melamine. Next, 0.195 moles of nickel chloride solution, 0.09 moles of zinc chloride solution, and 0.015 moles of copper chloride solution were added dropwise, and the mixture was stirred at 82°C for 3 hours to allow the reaction to proceed. After that, potassium hydroxide was added to adjust the pH to approximately 5.2, and 100 parts of distilled water were added and the temperature was raised to 90°C. Next, 21 parts of 30% hydrochloric acid were added dropwise, and the mixture was stirred for 12 hours to allow the reaction to proceed. After that, potassium hydroxide was added to adjust the pH to approximately 5, and the product was collected by filtration. The product was washed with deionized water and filtered. After drying at 80°C, it was ground to obtain a yellow pigment (y) with a molar ratio of Ni, Zn, and Cu of 65:30:5. The yellow pigment (y) is a pigment comprising at least one anion selected from the group consisting of mono, di, tri, and tetraanions of the azo compound represented by the general formula (13) and the azo compound with a tautomer structure thereof, at least two metal ions selected from Cd, Co, Al, Cr, Sn, Pb, Zn, Fe, Ni, Cu, and Mn, and a compound represented by the general formula (14).

[0462] <Manufacturing of near-infrared absorbing dyes> (Manufacturing of near-infrared absorbing dye (a)) A near-infrared absorbing dye (a) represented by the following chemical formula (8) was obtained by the method described in Japanese Patent Publication No. 2022-96687.

[0463] (Manufacturing of near-infrared absorbing dye (b)) A near-infrared absorbing dye (b) represented by the following chemical formula (9) was obtained by the method described in Japanese Patent Publication No. 2022-96687.

[0464] [ka]

[0465] Near-infrared absorbing dye (a) and near-infrared absorbing dye (b) were mixed in a 1:1 ratio to obtain near-infrared absorbing dye (1).

[0466] (Manufacturing of near-infrared absorbing dye (2)) Using the method described in Japanese Patent Publication No. 2022-72558, a micronized near-infrared absorbing dye (c1) represented by the following chemical formula (10), a near-infrared absorbing dye (c2) represented by the following chemical formula (11), and a near-infrared absorbing dye (c3) represented by the following chemical formula (12) were obtained. Furthermore, the above near-infrared absorbing dyes (c1), (c2), and (c3) were mixed in a mass ratio of 1:1:1 to obtain a near-infrared absorbing dye (2).

[0467] [ka]

[0468] (Manufacturing of near-infrared absorbing dyes (3)) Following the description in International Publication No. 2019 / 058882, a near-infrared absorbing dye (3) represented by chemical formula (13) was obtained.

[0469] Chemical formula (13) [ka]

[0470] <Manufacturing of Dispersed Resins> (Acidic group-containing dispersion resin (1) solution) In a reaction vessel equipped with a gas inlet tube, thermometer, condenser, and stirrer, 10 parts MAA, 100 parts MMA, 70 parts iso-butyl methacrylate, 20 parts BzMA, and 50 parts PGMAc were charged and the mixture was purged with nitrogen gas. The reaction vessel was heated to 50°C and stirred, and 12 parts 3-mercapto-1,2-propanediol were added. The temperature was raised to 90°C, and the reaction was carried out for 7 hours while adding a solution of 0.1 parts 2,2'-azobisisobutyronitrile added to 90 parts PGMAc. After confirming that more than 95% had reacted by measuring the non-volatile content, 19 parts pyromellitic anhydride, 50 parts PGMAc, 50 parts cyclohexanone, and 0.4 parts of the catalyst 1,8-diazabicyclo-[5.4.0]-7-undecene were added, and the reaction was carried out at 100°C for 7 hours. The reaction was terminated after confirming that more than 98% of the acid anhydride had been half-esterified by measuring the acid value. After cooling, PGMAc was added to achieve a non-volatile content of 30% by mass to obtain an acidic group-containing dispersion resin (1) solution. The obtained resin had an acid value of 70 mgKOH / g and a weight-average molecular weight of 8,500.

[0471] (Solution of basic group-containing dispersion resin (2)) In a reactor equipped with a gas inlet pipe, condenser, stirring blades, and thermometer, 40 parts MMA, 10 parts n-BA, and 13.2 parts tetramethylethylenediamine as catalyst were charged, and the reactor was purged with nitrogen and stirred at 50°C for 1 hour. Next, 9.3 parts ethyl bromoisobutyrate as a polymerization initiator, 5.6 parts cuprous chloride as catalyst, and 100 parts PGMAc were charged, and the temperature was raised to 110°C under a nitrogen atmosphere to start polymerization of the first block (block B). After 4 hours of polymerization, a polymerization conversion rate of 98% or higher was confirmed by sampling. Next, 50 parts PGMAc, 40 parts dimethylaminoethyl methacrylate as the monomer for the second block (block A), and 10 parts methacryloyloxyethyl benzyldimethylammonium chloride were added to the reactor, and the reaction was carried out for 2 hours while stirring at 110°C under a nitrogen atmosphere. Subsequently, a polymerization conversion rate of 98% or higher was confirmed by sampling. After cooling, PGMAc was added to obtain a basic group-containing dispersion resin (2) solution so that the non-volatile content was 30% by mass. The amine value of the resin was 169.8 mgKOH / g.

[0472] <Dispersion manufacturing> (Dispersion (1)) After uniformly stirring and mixing the following raw materials, the mixture was dispersed for 3 hours using 0.5 mm diameter zirconia beads in an Eiger mill (Eiger Japan's "Mini Model M-250 MKII"), and then filtered through a 1.0 μm pore size filter to prepare dispersion (1). The non-volatile content was 20% by mass. Coloring agent (1): 14.0 parts Dispersed resin (1) solution: 16.7 parts Pigment derivative (1): 1.0 part Solvent (propylene glycol monomethyl ether acetate): 68.3 parts

[0473] (Dispersion 2~16) Dispersions 2-12 with a non-volatile content of 20% were prepared in the same manner as dispersion 1, except that the raw materials and quantities were changed as listed in Tables 6-7. The values ​​in the tables represent the non-volatile content ratio.

[0474] [Table 6]

[0475] [Table 7]

[0476] The abbreviations used in Tables 4 and 5 are as follows:

[0477] [Coloring agent] Coloring agent (1): A mixture of CI Pigment Blue 15:6 (manufactured by Toyo Color Co., Ltd., "Lionol Blue ES") and CI Pigment Blue 15:3 (manufactured by Toyo Color Co., Ltd., "Lionol Blue FG7351") in a mass ratio of 1:1. Coloring agent (2): CI Pigment Violet 19 (HOSTAPERM RED E2B 70, manufactured by Heubach Color Japan, β-type crystal) Coloring agent (3): CI Pigment Violet 23 (manufactured by Toyo Color Co., Ltd., "Lionogen Violet FG6140") Coloring agent (4): CI Pigment Red 264 (BASF Japan, "Irgazine Rubin L4025") Coloring agent (5): A mixture of CI Pigment Green 58 (manufactured by DIC, FASTOGEN Green A110) and CI Pigment Green 59 (manufactured by DIC) in a mass ratio of 1:1. Coloring agent (6): The yellow pigment (y) described above.

[0478] The colorants (1) to (6) and near-infrared absorbing dyes (1) to (3) were all micronized by salt milling, thoroughly washed, and dried before use.

[0479] Pigment derivatives: Compounds shown in (1) to (4) below. [ka] JPEG2026068945000072.jpg25130JPEG2026068945000073.jpg54129JPEG2026068945000074.jpg32130

[0480] <Manufacturing of photosensitive compositions> [Example 1] The following raw materials were mixed and stirred in the following proportions, and filtered through a 1.0 μm pore size filter to obtain a photosensitive composition with 15% non-volatile content. Specific polymerizable compound (1): 2.25 parts Polymerizable compound (1): 0.45 part Polymerizable compound (3): 1.80 parts Dispersion (1): 17.14 parts Dispersion (2): 1.14 parts Dispersion (3): 1.00 parts Dye (D1): 1.20 parts Alkali-soluble resin (1) solution: 3.30 parts Alkali-soluble resin (4) solution: 3.30 parts Specific polymerization initiator having a phosphine oxide structure: 0.72 parts Specific polymerization initiator having an oxime ester structure: 0.18 parts Leveling agent (1) solution: 1.00 part Solvent (1): 57.95 parts Solvent (2): 5.00 parts Blocked isocyanate group-containing compound (2) solution: 2.50 parts Epoxy group-containing compound (1): 0.75 part Specific SC agent (1): 0.15 parts Compound (1) represented by general formula (5): 0.0060 parts UV absorber (1): 0.15 parts

[0481] [Examples 2-82 and Comparative Examples 1-3] The photosensitive compositions of Examples 2-82 and Comparative Examples 1-3 were prepared in the same manner as in Example 1, except that the raw materials and quantities of the photosensitive composition of Example 1 were changed to those listed in Tables 8-16.

[0482] [Table 8]

[0483] [Table 9]

[0484] [Table 10]

[0485] [Table 11]

[0486] [Table 12]

[0487] [Table 13]

[0488] [Table 14]

[0489] [Table 15]

[0490] [Table 16]

[0491] In Tables 8 to 16, "Specific Polymerization Initiator 1" refers to a specific polymerization initiator having a phosphine oxide structure, and "Specific Polymerization Initiator 2" refers to a specific polymerization initiator having an oxime ester structure.

[0492] [Polymerizable compound] Polymerizable compound (1): CN9906NS (manufactured by Arkema, a polymerizable compound having an amine structure) Polymerizable compound (2): Aronics MT-3041 (manufactured by Toagosei Co., Ltd., a polymerizable compound having an amine structure) Polymerizable compound (3): Aronics M-306 (manufactured by Toagosei Co., Ltd., a hydroxyl group-containing polymerizable compound, a mixture of pentaerythritol triacrylate and pentaerythritol tetraacrylate) Polymerizable compound (4): Aronics M-510 (manufactured by Toagosei Co., Ltd., an acid group-containing polymerizable compound) Polymerizable compound (5): UA-306H (manufactured by Kyoeisha Chemical Co., Ltd., a polymerizable compound containing urethane bonds) Polymerizable compound (6): Kayarad DPCA-60 (manufactured by Nippon Kayaku Co., Ltd., lactone-modified polymerizable compound) Polymerizable compound (7): Aronics M-350 (manufactured by Toagosei Co., Ltd., trimethylolpropane triacrylate having an ethyleneoxy group) Polymerizable compound (8): Arronix M-321 (manufactured by Toagosei Co., Ltd., trimethylolpropane triacrylate having a propyleneoxy group)

[0493] [Polymerization initiator] (Specific oxime ester compounds) Specific oxime ester compound (1): The above-mentioned compound (Ini-3) (a specific polymerization initiator having an oxime ester structure, with an absorption peak at 368 nm) Specific oxime ester compound (2): The above-mentioned compound (Ini-15) (a specific polymerization initiator having an oxime ester structure, with an absorption peak at 379 nm) (Specific polymerization initiators other than specific oxime ester compounds) Specific polymerization initiator (1): The above-mentioned compound (Ini-16) (a specific polymerization initiator having a phosphine oxide structure, with an absorption peak at 380 nm) Specific polymerization initiator (2): The above-mentioned compound (Ini-17) (a specific polymerization initiator having a phosphine oxide structure, with an absorption peak at 370 nm) (Oximeter compounds other than specified oximeter compounds) Oxime ester compound (1): The above compound (Ini-1) (a compound having an indole structure) Oxime ester compound (2): The above compound (Ini-2) (a compound having a carbazole structure) Oxime ester compound (3): The above compound (Ini-4) (a compound having a benzofuran structure) Oxime ester compound (4): The above compound (Ini-7) (a compound having a carbazole structure) Oxime ester compound (5): The above-mentioned compound (Ini-6) (a compound having a carbazole structure)

[0494] [Leveling agent] Leveling agent (1) solution: BYK-330 (manufactured by Bic Chemie) was diluted with PGMAc to a non-volatile content of 1%.

[0495] [solvent] Solvent (1): Propylene glycol monomethyl ether acetate Solvent (2): Propylene glycol monomethyl ether

[0496] [Compounds containing blocked isocyanate groups] • Blocked isocyanate group-containing compound (5) solution: BI7982 (manufactured by Baxenden Chemical, a compound blocked with a pyrazole compound, 70% by mass of non-volatile content) was diluted with PGMAc to a non-volatile content of 60%. • Blocked isocyanate group-containing compound (6) solution: BI7984 (manufactured by Baxenden Chemical, a compound blocked with an oxime compound, 75% by mass of non-volatile content) was diluted with PGMAc to a non-volatile content of 60%.

[0497] [Epoxy group-containing compound] Epoxy group-containing compound (1): EHPE-3150 (manufactured by Daicel Corporation, compound represented by general formula (50))

[0498] [Silane coupling agent] Other SC agents (1): KBM-5103 (manufactured by Shin-Etsu Silicone Co., Ltd., 3-acryloxypropyltrimethoxysilane)

[0499] [Compounds represented by general formula (5)] Compound (1): Methylhydroquinone (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) Compound (2): tert-butylhydroquinone (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.)

[0500] [Compounds represented by general formula (6)] Compound (3): 2,6-di-tert-butyl-4-methylphenol (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) Compound (4): p-Methoxyphenol (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.)

[0501] Other polymerization inhibitors (1): 4-methylcatechol (manufactured by Tokyo Chemical Industry Co., Ltd.)

[0502] [UV absorber] UV absorber (1): The above-mentioned compound (UVA-1), a compound represented by general formula (15). UV absorbers (2): The above-mentioned compounds (UVA-3), compounds represented by general formula (15) UV absorbers (3): The above-mentioned compounds (UVA-5), compounds represented by general formula (16) UV absorbers (4): The above-mentioned compounds (UVA-7), compounds represented by general formula (16) UV absorber (5): Tinuvin 326 (manufactured by BASF), a compound having a benzotriazole skeleton.

[0503] <Evaluation of photosensitive compositions> The obtained photosensitive compositions were evaluated as follows. The evaluation results are shown in Table 17.

[0504] [Evaluation of Contact Hole Formation (1) (Taper Angle)] The obtained photosensitive compositions were coated onto 100 mm x 100 mm glass substrates (Corning Eagle 2000) with a thickness of 0.7 mm using a spin coater to achieve a post-bake film thickness of 3.5 μm. Then, they were heated and dried on a hot plate at 90°C for 1 minute. A mask with a pattern having an aperture diameter of φ30 μm was exposed to a high-pressure mercury lamp at 100 mJ / cm² with an exposure gap of 200 μm. 2 The substrate was irradiated with ultraviolet light. Furthermore, after cooling the substrate to room temperature, it was spray-developed using a potassium hydroxide solution (concentration 0.04%) at 23°C, washed with deionized water, air-dried with clean air, and post-baked in a clean oven at 230°C for 30 minutes to obtain an evaluation glass substrate. Spray development was performed for the shortest possible time while still allowing pattern formation without any remaining development residue. The glass was cut into 1 cm squares to include the area where the contact holes were formed, and the cross-sectional shape of the contact holes was observed using a scanning electron microscope (S-3000) manufactured by Hitachi High-Technologies Corporation at an acceleration voltage of 10 kV and an observation magnification of 10,000x, and the taper angle of the contact holes was evaluated. The evaluation criteria are as follows, with a score of 2 or higher indicating practical usability. [Evaluation Criteria] 3: Tapered shape is between 60 and 90 degrees 2: Tapered shape is 40 degrees or more but less than 60 degrees 1: Taper shape is 0 degrees or more but less than 40 degrees, or more than 90 degrees.

[0505] [Evaluation of Contact Hole Formability (2) (Contact Hole Shape)] The glass substrates with the hardened film prepared for the evaluation of contact hole formation (1) were observed using an optical microscope (Olympus BX-51) (magnification: 100x) to evaluate the shape of the contact holes. The evaluation criteria are as follows, with a score of 2 or higher indicating practical usability. [Evaluation Criteria] 3: The contact hole is perfectly circular. 2: The contact hole is a slightly distorted circular shape. 1: The contact hole is a distorted circular shape.

[0506] [Evaluation of contact hole formation (3) (residue)] The evaluation glass substrate obtained in the evaluation of contact hole formation (1) was cut into 1 cm squares so as to include the area where contact holes were formed. The presence or absence of residue in the contact holes was evaluated using a Hitachi High-Technologies scanning electron microscope (S-3000) at an acceleration voltage of 10 kV and observation magnifications of 5000x and 15000x. The evaluation criteria are as follows, with a score of 2 or higher indicating practical usability. [Evaluation Criteria] 3: No residue was observed at an observation magnification of 15,000x. 2: No residue is visible at an observation magnification of 5000x, but residue is visible at an observation magnification of 15000x. 1: Residue was observed at an observation magnification of 5000x.

[0507] [Evaluation of ITO Crack] The obtained photosensitive compositions were coated onto 100 mm x 100 mm glass substrates (Corning Eagle 2000) with a thickness of 0.7 mm using a spin coater to achieve a post-bake film thickness of 3.5 μm. Then, they were heated and dried on a hot plate at 90°C for 1 minute. A high-pressure mercury lamp at 100 mJ / cm² was used without a photomask. 2 The substrate was irradiated with ultraviolet light. Furthermore, after cooling the substrate to room temperature, it was spray-developed for 40 seconds using a potassium hydroxide solution (concentration: 0.04 mass%) at 23°C, washed with deionized water, air-dried with clean air, and post-baked in a clean oven at 230°C for 30 minutes to obtain an evaluation glass substrate. A 120 nm thick ITO film was deposited on the hardened film of the obtained evaluation glass substrate using a sputtering apparatus (ULVAC: CS-200). This film was immersed in NMP at 25°C, and the substrate was visually observed four times at 15 minutes, 30 minutes, 45 minutes, and 60 minutes to check for cracks in the ITO film. The evaluation criteria are as follows: A score of 3 or higher indicates that it is usable. [Evaluation Criteria] 5: No ITO cracks after 60 minutes of immersion. 4: No ITO cracks after 45 minutes of immersion, ITO cracks present after 60 minutes of immersion. 3: No ITO cracks after 30 minutes of immersion, ITO cracks present after 45 minutes of immersion. 2: No ITO cracks after 15 minutes of immersion, ITO cracks present after 30 minutes of immersion. 1: ITO cracks were observed after 15 minutes of immersion.

[0508] [Table 17]

Claims

1. A photosensitive composition comprising a colorant, a polymerization initiator, and a polymerizable compound, A photosensitive composition comprising a polymerizable compound containing an ethyleneoxy group and a propyleneoxy group.

2. The photosensitive composition according to claim 1, wherein the molar ratio of the ethyleneoxy group and the propyleneoxy group is 95:5 to 5:

95.

3. The photosensitive composition according to claim 1, wherein the polymerizable compound containing the ethyleneoxy group and the propyleneoxy group comprises one selected from the group consisting of a trimethylolpropane skeleton, a ditrimethylolpropane skeleton, a pentaerythritol skeleton, a dipentaerythritol skeleton, a glycerin skeleton, a diglycerin skeleton, an isocyanurate skeleton, an alkylene glycol skeleton, a bisphenol skeleton, and a sorbitol skeleton.

4. The photosensitive composition according to claim 1, comprising an alkali-soluble resin, wherein the alkali-soluble resin comprises at least one monomer unit selected from (a) or (b) below. (a) Polymerizable unsaturated group-containing monomer units (b) Monomer units containing thermally crosslinkable groups

5. The photosensitive composition according to claim 1, wherein the polymerization initiator comprises an oxime ester compound.

6. The photosensitive composition according to claim 1, wherein the polymerization initiator comprises a polymerization initiator having an absorption peak at a wavelength of 367 nm or higher.

7. Furthermore, the photosensitive composition according to claim 1, comprising a compound represented by general formula (5) or general formula (6). 【Transformation 58】 (In general formula (5), R １ This represents a hydrocarbon group with 1 to 4 carbon atoms. In general formula (6), R １ R represents a hydrocarbon group having 1 to 4 carbon atoms, or an alkoxy group having 1 to 4 carbon atoms. ２ Each of these independently represents either a hydrogen atom or a hydrocarbon group having 1 to 4 carbon atoms.

8. The photosensitive composition according to claim 1, wherein the polymerizable compound further comprises at least one selected from the group consisting of polymerizable compounds having an amine structure and polymerizable compounds having a urethane bond.

9. The photosensitive composition according to claim 1, wherein the coloring agent comprises at least one selected from (A) or (B) below. (A) Dye, and salt-forming compound of the dye and a resin that forms a salt (B) Dye polymer having a dye monomer having a dye residue and an ethylenically unsaturated group as a structural unit.

10. A film formed from the photosensitive composition according to any one of claims 1 to 9.

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

12. A color filter having the film described in claim 10.

13. A solid-state image sensor having the optical filter described in claim 10.

14. An image display device having the optical filter described in claim 10.

15. An infrared sensor having the optical filter described in claim 10.

Images