Photosensitive composition, film including the same, optical filter, solid-state imaging device, image display device, and infrared sensor

Abstract

To provide a photosensitive composition that enables formation of a film with suppressed drying unevenness and water stains as well as superior adhesion.SOLUTION: A photosensitive composition comprises an alkali-soluble resin, a polymerizable compound, a polymerization initiator, a leveling agent, and an organic solvent. The leveling agent comprises a copolymer having monomer units represented by following general formulas, respectively. The organic solvent comprises an organic solvent with a boiling point of 100°C or more and less than 150°C, and an organic solvent with a boiling point of 150°C or more and less than 230°C.SELECTED DRAWING: Figure 1

Description

[Technical field]

[0001] The present invention relates to a photosensitive composition and its use. [Background technology]

[0002] In recent years, the demand for optical filters used in liquid crystal displays, smartphones, infrared sensors, etc. has increased due to the increased demand. Color filters, which are a type of optical filter, are produced, for example, through the following steps: a step of applying a photosensitive composition to a substrate such as glass and removing the organic solvent from the coating by drying (hereinafter referred to as the drying step); a step of irradiating the coating with ultraviolet light or the like through a photomask having a desired pattern shape to harden the coating (hereinafter referred to as the exposure step); a step of washing and removing the unexposed parts of the coating with a developer (hereinafter referred to as the development step); and a step of heating the film to sufficiently harden the film (hereinafter referred to as the post-baking step) to obtain a pattern of the first color. Then, the same operation is performed using photosensitive compositions of different colors to sequentially form patterns of the second and subsequent colors to produce a color filter.

[0003] In the above-mentioned development step, an alkaline developer is used to wash and remove the unexposed parts. During this process, there is a problem that the exposed parts are chipped or peeled off, causing defects in the pattern. In addition, when a coating film is exposed to an alkaline developer, there is a problem that the coating film discolors (hereinafter referred to as water stains). Therefore, there is a demand for a photosensitive composition that does not cause pattern defects and water stains in the development step. Furthermore, the drying step also causes uneven drying on the coating film, resulting in a non-uniform coating thickness. Furthermore, in recent years, from an environmental standpoint, there has been a demand to reduce the use of fluorine-based compounds in the components of photosensitive compositions used in the production of color filters.

[0004] For example, Patent Document 1 discloses a colored composition containing a polymerizable compound having an alkylene oxide structure as an approach to improving pattern chipping during development. Patent Document 2 discloses a colored photosensitive resin composition that does not cause development stains, the colored photosensitive resin composition containing a colorant, an alkali-soluble resin, a photopolymerizable compound, and a solvent, the alkali-soluble resin containing a monomer of a specific structure, having a molecular weight of 1,2000 to 17,000, and an acid value of 60 to 120 KOHmg / g, and the photopolymerization initiator containing an oxime ester fluorene derivative compound. Patent Document 3 discloses a resist composition containing a fluorine-based surfactant of a specific structure as a resist composition that can obtain a coating film that is less likely to cause water stains. Furthermore, Patent Document 4 discloses a photosensitive resin composition that is excellent in suppressing the occurrence of drying unevenness, and that contains an alkali-soluble resin having a specific structure, a polymerizable compound having a specific structure, a photopolymerization initiator, and a surfactant having a surface tension of 23.0 mN / m or less in a 0.5 mass % propylene glycol monomethyl ether acetate solution. [Prior art documents] [Patent documents]

[0005] [Patent Document 1] JP 2014-142582 A [Patent Document 2] JP 2017-173787 A [Patent Document 3] JP 2016-102212 A [Patent Document 4] International Publication No. 2022 / 124296 Summary of the Invention [Problem to be solved by the invention]

[0006] However, the compositions described in Patent Documents 1 to 4 could not satisfy all of the requirements for adhesion, prevention of water spots, and prevention of uneven drying at a certain level.

[0007] An object of the present invention is to provide a photosensitive composition which is capable of forming a film having excellent adhesion while suppressing uneven drying and water spots. [Means for solving the problem]

[0008] The present invention relates to a photosensitive composition comprising an alkali-soluble resin (A), a polymerizable compound (B), a polymerization initiator (C), a leveling agent (D), and an organic solvent (E), The leveling agent (D) contains a copolymer (D1) having a monomer unit (d1) represented by the following general formula (1) and a monomer unit (d2) represented by the following general formula (2), The photosensitive composition relates to the organic solvent (E) containing an organic solvent (E1) having a boiling point of 100°C or more and less than 150°C, and an organic solvent (E2) having a boiling point of 150°C or more and less than 230°C. General formula (1) [ka] In general formula (1), R1's are each independently an alkyl group having 1 to 6 carbon atoms, or a group represented by -OSi(R5)3 (wherein R5's are each independently an alkyl group having 1 to 3 carbon atoms). Each R2 is independently an alkyl group having 1 to 6 carbon atoms. R3 is an alkyl group having 1 to 6 carbon atoms. R4 is a hydrogen atom or a methyl group. L1 is a divalent organic group or a single bond. n is an integer from 1 to 70. General formula (2) [ka] (In general formula (2), R6 is a hydrogen atom or an alkyl group having 1 to 18 carbon atoms. R7 is a hydrogen atom or a methyl group. m is an integer from 1 to 4. o is an integer from 2 to 200.

[0009] The present invention also relates to the photosensitive composition according to claim 1, wherein the content of the organic solvent (E2) is 0.5 to 40 mass % in 100 mass % of the organic solvent (E).

[0010] The present invention also relates to the photosensitive composition according to claim 1, wherein the alkali-soluble resin (A) contains an alkali-soluble resin (A1) having a monomer unit (a1) whose homopolymer has a glass transition temperature of 0° C. or lower.

[0011] The present invention also relates to any of the above photosensitive compositions, wherein the polymerizable compound (B) comprises one or more compounds selected from the group consisting of a lactone-modified polymerizable compound (B1), a polymerizable compound having an acidic group (B2), and a polymerizable compound having a urethane bond (B3).

[0012] The present invention also relates to any of the above photosensitive compositions, wherein the polymerization initiator (C) comprises one or more compounds selected from the group consisting of a compound (C1) represented by the following general formula (3), a compound (C2) represented by the following general formula (4), and a compound (C3) represented by the following general formula (5):

[0013] General formula (3) [ka]

[0014] (In general formula (3), R1 is an alkyl group having 4 to 20 carbon atoms and having an alicyclic hydrocarbon group. R2 is 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. R3 is a hydrogen atom, a nitro group, a group having an ether bond, or a group having an aromatic ring.

[0015] General formula (4) [ka]

[0016] (In general formula (4), R4 and R5 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.)

[0017] General formula (5) [ka]

[0018] In general formula (5), R6 and R7 each independently represent a hydrogen atom or an alkyl group having 1 to 8 carbon atoms. R8 is a hydrogen atom or a monovalent substituent.

[0019] The present invention also relates to any of the above photosensitive compositions, wherein the copolymer (D1) is a block copolymer having an A block containing a monomer unit (d1) represented by general formula (1) and a B block containing a monomer unit (d2) represented by general formula (2).

[0020] The present invention also relates to any of the above photosensitive compositions, further comprising a dye (F).

[0021] The present invention also relates to a film formed from any of the above photosensitive compositions.

[0022] The present invention also relates to an optical filter having the film.

[0023] The present invention also relates to a solid-state imaging device having the optical filter.

[0024] The present invention also relates to an image display device having the optical filter.

[0025] The present invention also relates to an infrared sensor having the optical filter. Effect of the Invention

[0026] According to the present invention, it is possible to provide a photosensitive composition capable of forming a film having excellent adhesion while suppressing uneven drying and water stains. The present invention also provides a film, an optical filter, a solid-state imaging device, an image display device, and an infrared sensor using the photosensitive composition. [Brief description of the drawings]

[0027] [Figure 1] FIG. 1 is a schematic cross-sectional view of an infrared sensor having an optical filter of the present invention. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0028] Hereinafter, the embodiment 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 embodiment, and can be modified within the scope of the problem that can be solved.

[0029] In this specification, unless otherwise specified, "(meth)acryloyl", "(meth)acryl", "(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" stands for Color Index (CI; published by The Society of Dyers and Colourists). In this specification, a polymerizable unsaturated group is an ethylenically unsaturated double bond. 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 partial structural state in which a monomer forms a polymer after polymerization. In this specification, for low molecular weight compounds whose molecular weight can be specified, the molecular weight is a calculated value or measured by ESI-MS (electrospray ionization mass spectrometry), and for compounds having a molecular weight distribution, the molecular weight is a polystyrene-equivalent weight average molecular weight measured by gel permeation chromatography using tetrahydrofuran as a solvent. In this specification, the boiling points of organic solvents are values ​​at 1013.25 hPa. In this specification, a numerical range expressed using "to" means a range that includes the numerical values ​​before and after "to" as the lower and upper limits.

[0030] <Photosensitive composition> A photosensitive composition according to one embodiment of the present invention is a photosensitive composition comprising an alkali-soluble resin (A), a polymerizable compound (B), a polymerization initiator (C), a leveling agent (D), and an organic solvent (E), The leveling agent (D) contains a copolymer (D1) having a monomer unit (d1) represented by the following general formula (1) and a monomer unit (d2) represented by the following general formula (2), The organic solvent (E) contains an organic solvent (E1) having a boiling point of 100°C or more and less than 150°C, and an organic solvent (E2) having a boiling point of 150°C or more and less than 230°C. General formula (1) [ka] In general formula (1), R1's are each independently an alkyl group having 1 to 6 carbon atoms, or a group represented by -OSi(R5)3 (wherein R5's are each independently an alkyl group having 1 to 3 carbon atoms). Each R2 is independently an alkyl group having 1 to 6 carbon atoms. R3 is an alkyl group having 1 to 6 carbon atoms. R4 is a hydrogen atom or a methyl group. L1 is a divalent organic group or a single bond. n is an integer from 1 to 70. General formula (2) [ka] (In general formula (2), R6 is a hydrogen atom or an alkyl group having 1 to 18 carbon atoms. R7 is a hydrogen atom or a methyl group. m is an integer from 1 to 4. o is an integer from 2 to 200.

[0031] The mechanism by which the photosensitive composition having the above-mentioned structure can solve the problems of the present invention is not clear, but is speculated as follows.

[0032] Organic solvents (E1) with a boiling point of 100°C or more and less than 150°C (hereinafter simply referred to as organic solvents (E1)) are easy to evaporate during the coating and drying process. Therefore, they do not remain in the film and are unlikely to affect adhesion. However, because they dry quickly, the film loses fluidity and drying unevenness is likely to occur. In addition, crater-like depressions are likely to occur on the surface of the film, and surface defects are likely to occur. On the other hand, organic solvents (E2) with a boiling point of 150°C or more and less than 230°C (hereinafter simply referred to as organic solvents (E2)) are difficult to evaporate during the coating and drying process and remain in the film for a long time. Therefore, even if the non-volatile content in the film increases during the drying process, the film has fluidity, giving time for the film to spread evenly, and drying unevenness is unlikely to occur. However, they remain in large amounts in the film, which is likely to deteriorate adhesion. Therefore, it is speculated that by using organic solvent (E1) and organic solvent (E2) in combination, it is possible to maintain the fluidity of the film from the coating to drying process, suppress drying unevenness, and form a film with excellent adhesion. And, the copolymer (D1) (hereinafter simply referred to as copolymer (D1)) having monomer unit (d1) represented by general formula (1) and monomer unit (d2) represented by general formula (2) is presumed to have a silicone chain in the side chain of the monomer unit (d1) represented by general formula (1), so that the hydrophobic silicone chain is easily oriented on the film surface, suppressing uneven drying and water stains. Also, the monomer unit (d2) represented by general formula (2) has an alkylene oxide chain, so that it is moderately compatible with the alkali-soluble resin (A), suppressing the occurrence of defects such as pinholes.

[0033] Components that are or can be included in the photosensitive composition of one embodiment will be described in detail below.

[0034] [Alkali-soluble resin (A)] The photosensitive composition of the present invention contains an alkali-soluble resin (A).

[0035] The alkali-soluble resin (A) is not particularly limited as long as it dissolves in the alkali developer described below, and any known resin can be used. Examples of the resin include (meth)acrylic resin, styrene resin, styrene / (meth)acrylic resin, epoxy resin, urethane resin, polycarbonate resin, polyester resin, polyether resin, polyimide resin, polyamideimide resin, and cyclic olefin resin.

[0036] The weight average molecular weight (Mw) of the alkali-soluble resin (A) is preferably from 3,000 to 50,000, and more preferably from 4,000 to 40,000.

[0037] The acid value of the alkali-soluble resin (A) is preferably from 30 to 200 mgKOH / g, more preferably from 40 to 180 mgKOH / g.

[0038] The alkali-soluble resin (A) can be used alone or in combination of two or more kinds.

[0039] The content of the alkali-soluble resin (A) is preferably from 1 to 95 mass %, and more preferably from 5 to 80 mass %, in 100 mass % of the nonvolatile content of the photosensitive composition.

[0040] (Alkali-soluble resin (A1) having a monomer unit (a1) having a homopolymer glass transition temperature of 0° C. or lower) From the viewpoints of suppressing drying unevenness, suppressing water stains, and adhesion, the photosensitive composition of the present invention preferably contains, as the alkali-soluble resin (A), an alkali-soluble resin (A1) having a monomer unit (a1) whose homopolymer has a glass transition temperature of 0° C. or lower (hereinafter, also simply referred to as alkali-soluble resin (A1)).

[0041] The alkali-soluble resin (A1) has flexibility. Therefore, the rigid part formed by polymerization of the polymerizable compound (B) described later and the flexible part of the alkali-soluble resin (A1) are present in the film, and it is presumed that the external stress or internal stress can be effectively alleviated, and the adhesion is improved. In addition, because it is flexible, even if the non-volatile content concentration becomes high in the drying process, the film has fluidity and tends to spread uniformly. In addition, it is presumed that the copolymer (D1) is also easily oriented on the surface, and therefore uneven drying and water stains can be suppressed.

[0042] The alkali-soluble resin (A1) is not particularly limited, and any known resin can be used. For example, a monomer forming a monomer unit (a1) having a homopolymer glass transition temperature of 0° C. or lower, and a copolymer with any other copolymerizable monomer can be used.

[0043] The glass transition temperature (hereinafter, also referred to as Tg) may be a measured Tg obtained by actual measurement. Specifically, the measured Tg may be a value measured by differential scanning calorimetry (DSC). However, if measurement is difficult due to decomposition of the resin, etc., the calculated Tg obtained by the following formula is applied. 1 / Tg=W1 / Tg1+W2 / Tg2+······+W n / Tg n Here, the resins to be calculated are W1 to W n n types of monomer components up to W n is the weight fraction of the nth monomer, Tg n is the glass transition temperature (absolute temperature) of the homopolymer of the nth monomer. The glass transition temperature of the homopolymer of each monomer (hereinafter also referred to as homopolymer) is the value shown in "Polymer Handbook, Third edition, John Wiley & Sons, 1989" edited by Brandrup, J. Immergut, EH.

[0044] [Monomer unit (a1) having a homopolymer glass transition temperature of 0°C or lower] Examples of monomers forming the monomer unit (a1) having a homopolymer glass transition temperature of 0° C. or lower include phenoxyethyl acrylate (−22° C.), lauryl acrylate (−3° C.), 2-ethylhexyl acrylate (−50° C.), butoxytriethylene glycol methacrylate (−72° C.), 2-(2-ethoxyethoxy)ethyl acrylate (−67° C.), n-hexyl acrylate (−57° C.), n-butyl acrylate (−48° C.), isobutyl acrylate (−40° C.), ethyl Examples of suitable acrylates include ethyl acrylate (-24°C), lauryl methacrylate (-65°C), n-hexyl methacrylate (-5°C), 2-ethylhexyl methacrylate (-10°C), 2-methoxyethyl acrylate (-50°C), tetrahydrofurfuryl acrylate (-12°C), 2-hydroxyethyl acrylate (-15°C), 4-hydroxybutyl acrylate (-60°C), 2-hydroxypropyl acrylate (-7°C), and 2-acryloyloxyethyl succinic acid (-40°C). Among these, monomers having a homopolymer glass transition temperature of -60 to -10°C are preferred.

[0045] The content of the monomer unit (a1) having a homopolymer glass transition temperature of 0° C. or lower is preferably 1 to 50 mol %, and more preferably 5 to 40 mol %, of all the constituent units of the alkali-soluble resin (A1) from the viewpoints of suppressing uneven drying, suppressing water stains, and adhesion.

[0046] The alkali-soluble resin (A1) may have a monomer unit other than the monomer unit (a1) having a homopolymer glass transition temperature of 0° C. or less. The monomer unit other than the monomer unit (a1) having a homopolymer glass transition temperature of 0° C. or less is not particularly limited, and examples thereof include monomer units formed from a monomer copolymerizable with a monomer having a homopolymer glass transition temperature of 0° C. or less. For example, examples thereof include a polymerizable unsaturated group-containing monomer unit (a2), an acidic group-containing monomer unit (a3), an aliphatic condensed ring structure-containing monomer unit (a4), a hydroxyl group-containing monomer unit (a5), an epoxy group-containing monomer unit (a6), a blocked isocyanate group-containing monomer unit (a7), an aromatic ring-containing monomer unit (a8), and other unit units (a9). Among these, it is preferable to have a polymerizable unsaturated group-containing monomer unit (a2) from the viewpoint of adhesion.

[0047] [Polymerizable unsaturated group-containing monomer unit (a2)] Methods for incorporating the polymerizable unsaturated group-containing monomer unit (a2) into the alkali-soluble resin (A1) include, for example, the following methods (i) to (iii).

[0048] <Method (i)> In the method (i), for example, first, a precursor having an epoxy group-containing monomer unit (a6) described later is synthesized, and then a carboxyl group-containing monomer (modifying compound) is added to the epoxy group of the precursor.

[0049] 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.

[0050] From the viewpoint of developability, the epoxy group of the epoxy group-containing monomer unit (a6) to which a carboxyl group of a carboxyl group-containing monomer has been added may be further reacted with an acid anhydride.

[0051] Examples of the acid anhydride include tetrahydrophthalic anhydride, phthalic anhydride, hexahydrophthalic anhydride, succinic anhydride, and maleic anhydride.

[0052] <Method (ii)> In the method (ii), for example, first, a polymer (precursor) having an acidic group-containing monomer unit (a3) ​​in which the acidic group is a carboxyl group is synthesized, and then an epoxy group-containing monomer (modifying compound) is added to the carboxyl group of the precursor.

[0053] Examples of epoxy group-containing monomers include glycidyl (meth)acrylate, methyl glycidyl (meth)acrylate, 2-glycidoxyethyl (meth)acrylate, 3,4-epoxybutyl (meth)acrylate, and 3,4-epoxycyclohexyl (meth)acrylate.

[0054] <Method (iii)> In the method (iii), for example, a precursor having a hydroxyl group-containing monomer (a5) described later is first synthesized, and then the hydroxyl group of the precursor is reacted with the isocyanate group of an isocyanate group-containing monomer (modifying compound).

[0055] Examples of the isocyanate group-containing monomer include 2-(meth)acryloylethyl isocyanate, 2-(meth)acryloyloxyethyl isocyanate, and 1,1-bis[methacryloyloxy]ethyl isocyanate.

[0056] From the viewpoint of adhesion, the content of the polymerizable unsaturated group-containing monomer unit (a2) is preferably from 5 to 80 mol %, and more preferably from 30 to 80 mol %, of all the constituent units of the alkali-soluble resin (A1).

[0057] [Acidic group-containing monomer unit (a3)] Examples of the acidic group-containing monomer 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-styrenesulfonic acid, vinylsulfonic acid, 2-acrylamido-2-methylpropanesulfonic acid, tert-butylacrylamidosulfonic acid, and 2-(meth)acryloyloxyethyl acid phosphate. The acidic group-containing monomers can be used alone or in combination of two or more kinds.

[0058] In addition, the method of introducing the acidic group-containing monomer unit (a3) ​​into the alkali-soluble resin (A1) may be a method of adding an acid anhydride (modifying compound) to the hydroxyl group contained in the resin (precursor) other than the method of copolymerizing the acidic group-containing monomer. Examples of the acid anhydride include succinic anhydride, phthalic anhydride, and 1,2,3,6-tetrahydrophthalic anhydride.

[0059] [Aliphatic condensed ring structure-containing monomer unit (a4)] From the viewpoint of resistance, the alkali-soluble resin (A1) preferably contains an aliphatic fused ring structure-containing monomer unit (a4).

[0060] Examples of the aliphatic condensed ring structure-containing monomer include isobornyl (meth)acrylate, dicyclopentanyl (meth)acrylate, dicyclopentenyl (meth)acrylate, dicyclopentanyloxyethyl (meth)acrylate, dicyclopentenyloxyethyl (meth)acrylate, adamantyl (meth)acrylate, etc. Among these, dicyclopentanyl (meth)acrylate, dicyclopentenyl (meth)acrylate, and dicyclopentanyloxyethyl (meth)acrylate are preferred. The aliphatic fused ring structure-containing monomers can be used alone or in combination of two or more kinds.

[0061] From the viewpoint of resistance, the content of the aliphatic fused ring structure-containing monomer unit (a4) is preferably 1 to 40 mol % in all the constituent units of the alkali-soluble resin (A1).

[0062] [Hydroxyl group-containing monomer unit (a5)] 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 phthalate. The hydroxyl group-containing monomers can be used alone or in combination of two or more kinds.

[0063] The method for introducing the hydroxyl group-containing monomer unit (a5) into the alkali-soluble resin (A1) may include, other than copolymerizing a hydroxyl group-containing monomer, a method for adding a compound having a carboxyl group (modifying compound) to an epoxy group contained in the resin (precursor), or a method for adding a compound having an epoxy group (modifying compound) to a carboxyl group contained in the resin (precursor).

[0064] [Epoxy group-containing monomer unit (a6)] Examples of the epoxy group-containing monomer include oxiranyl (meth)acrylate, glycidyl (meth)acrylate, 2-methylglycidyl (meth)acrylate, 2-ethylglycidyl (meth)acrylate, 2-oxiranylethyl (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. The epoxy group-containing monomers can be used alone or in combination of two or more kinds.

[0065] [Blocked isocyanate group-containing monomer unit (a7)] The blocked isocyanate group-containing monomer is a compound in which the isocyanate group in the isocyanate group-containing monomer is protected with a compound that is eliminated by heat (hereinafter, also referred to as a blocking agent). The elimination temperature of the blocking agent is preferably 60 to 160°C, more preferably 80 to 140°C.

[0066] Examples of isocyanate group-containing monomers include 2-isocyanatoethyl (meth)acrylate, 2-isocyanatopropyl (meth)acrylate, 3-isocyanatopropyl (meth)acrylate, 2-isocyanato-1-methylethyl (meth)acrylate, 2-isocyanato-1,1-dimethylethyl (meth)acrylate, 4-isocyanatocyclohexyl (meth)acrylate, and methacryloyl isocyanate. Also usable are equimolar reaction products of 2-hydroxyalkyl (meth)acrylate and diisocyanate compound. Among these, 2-isocyanatoethyl (meth)acrylate and 2-isocyanatopropyl (meth)acrylate are preferred.

[0067] Examples of the blocking agent include oxime compounds, lactam compounds, phenol compounds, alcohol compounds, amine compounds, active methylene compounds, pyrazole compounds, mercaptan compounds, imidazole compounds, imide compounds, urea compounds, imine compounds, and bisulfite compounds.

[0068] Examples of the oxime compound include formaldoxime, acetaldoxime, acetoxime, methyl ethyl ketoxime, methyl isobutyl ketoxime, cyclohexanone oxime, benzophenone oxime, etc. Among these, methyl ethyl ketoxime is preferred. Examples of the lactam compound include ε-caprolactam, δ-valerolactam, γ-butyrolactam, and β-propiolactam. Examples of phenolic compounds include phenol, cresol, 2,6-xylenol, 3,5-xylenol, ethylphenol, p-tert-butylphenol, nonylphenol, methyl 2-hydroxybenzoate, methyl 4-hydroxybenzoate, p-naphthol, p-nitrophenol, etc. Among these, 3,5-xylenol, methyl 2-hydroxybenzoate, and methyl 4-hydroxybenzoate are preferred. Examples of the alcohol compound include methanol, ethanol, propanol, butanol, ethylene glycol, methyl cellosolve, butyl cellosolve, methyl carbitol, benzyl alcohol, phenyl cellosolve, and furfuryl alcohol. Examples of the amine compound include diphenylamine, phenylnaphthylamine, aniline, and carbazole. Examples of the active methylene compound include dimethyl malate, diethyl malate, dimethyl malonate, diethyl malonate, dibutyl malonate, di-tert-butyl malonate, methyl acetoacetate, ethyl acetoacetate, and acetylacetone, with diethyl malate and diethyl malonate being preferred. Examples of the pyrazole compound include pyrazole, methylpyrazole, and 3,5-dimethylpyrazole, with 3,5-dimethylpyrazole being preferred. Examples of the mercaptan compound include butyl mercaptan, thiophenol, and tert-dodecyl mercaptan. Examples of the imidazole compound include imidazole, 2-methylimidazole, 2-ethylimidazole, 1,2-dimethylimidazole, 2-ethyl-4-methylimidazole, and 1-benzyl-2-phenylimidazole. Examples of the imide compound include succinimide, maleimide, maleimide, and phthalimide. Examples of the urea compound include urea, thiourea, and ethyleneurea. Examples of the imine compound include ethyleneimine and polyethyleneimine. Examples of the bisulfite compound include sodium bisulfite and potassium bisulfite.

[0069] The blocking agents can be used alone or in combination of two or more kinds.

[0070] The blocking agent is preferably one or more selected from the group consisting of oxime compounds, lactam compounds, phenol compounds, alcohol compounds, amine compounds, active methylene compounds, pyrazole compounds, mercaptan compounds, imidazole compounds, and imide compounds, and from the viewpoint of the protection reaction and the deprotection reaction, is more preferably one or more selected from the group consisting of oxime compounds, phenol compounds, active methylene compounds, and pyrazole compounds.

[0071] Examples of the blocked isocyanate group-containing monomer include the following compounds and acrylate compounds thereof, but the present invention is not limited thereto. The blocked isocyanate group-containing monomers can be used alone or in combination of two or more kinds.

[0072] [ka]

[0073] Commercially available blocked isocyanate group-containing monomers include Karenz MOI-DEM (blocking agent desorption temperature: 85 to 95°C), MOI-BP (blocking agent desorption temperature: 105 to 115°C), and MOI-BM (125 to 135°C), all manufactured by Showa Denko K.K.

[0074] [Aromatic ring-containing monomer unit (a8)] Examples of aromatic ring-containing monomers include styrene, α-methylstyrene, vinylnaphthalene, phenyl(meth)acrylate, benzyl(meth)acrylate, paracumylphenol ethylene oxide (EO) or propylene oxide (PO) modified (meth)acrylate, phenol EO or PO modified (meth)acrylate, nonylphenol EO or PO modified (meth)acrylate, N-phenylmaleimide, and N-benzylmaleimide. The aromatic ring-containing monomers can be used alone or in combination of two or more kinds.

[0075] [Other monomer units (a9)] Examples of other monomers include acrylic acid esters such as methyl (meth)acrylate, ethyl methacrylate, n-propyl methacrylate, isopropyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, tert-butyl methacrylate, and cyclohexyl (meth)acrylate; (Meth)acrylamides such as (meth)acrylamide, N,N-dimethyl(meth)acrylamide, N,N-diethyl(meth)acrylamide, N-isopropyl(meth)acrylamide, diacetone(meth)acrylamide, or acryloylmorpholine; Vinyl ethers such as ethyl vinyl ether, n-propyl vinyl ether, isopropyl vinyl ether, n-butyl vinyl ether, or isobutyl vinyl ether; vinyl acetate or vinyl propionate or other vinyl fatty acids; N-substituted maleimides such as methylmaleimide, ethylmaleimide, 1,2-bismaleimidoethane 1,6-bismaleimidohexane, 3-maleimidopropionic acid, and 6,7-methylenedioxy-4-methyl-3-maleimidocoumarin; Examples of such dimethyl-2,2'-[oxybis(methylene)]bis-2-propenoate include diethyl-2,2'-[oxybis(methylene)]bis-2-propenoate, di(n-propyl)-2,2'-[oxybis(methylene)]bis-2-propenoate, di(isopropyl)-2,2'-[oxybis(methylene)]bis-2-propenoate, and di(2-ethylhexyl)-2,2'-[oxybis(methylene)]bis-2-propenoate. The other monomers can be used alone or in combination of two or more.

[0076] The alkali-soluble resin (A1) can be used alone or in combination of two or more kinds.

[0077] The content of the alkali-soluble resin (A1) is preferably 10 to 100 mass %, more preferably 15 to 100 mass %, in 100 mass % of the alkali-soluble resin (A) from the viewpoints of suppressing drying unevenness, suppressing water stains, and adhesion.

[0078] (Alkali-soluble resin (A2) other than alkali-soluble resin (A1)) From the viewpoint of durability, the photosensitive composition of the present invention preferably contains an alkali-soluble resin (A2) other than the alkali-soluble resin (A1) as the alkali-soluble resin (A), which is hereinafter also simply referred to as the alkali-soluble resin (A2). However, the alkali-soluble resin (A2) does not contain a monomer unit (a1) whose homopolymer has a glass transition temperature of 0° C. or lower.

[0079] Examples of the alkali-soluble resin (A2) include resins having the above-mentioned monomer units (a2) to (a9). Among these, from the viewpoint of durability, it is preferable to have at least one selected from the group consisting of an aliphatic condensed ring structure-containing monomer unit (a4) having a homopolymer glass transition temperature of 80° C. or higher and an aromatic ring-containing monomer unit (a8) having a homopolymer glass transition temperature of 80° C. or higher. Examples of monomers which form monomer units having a homopolymer glass transition temperature of 80° C. or higher among the aliphatic fused ring structure-containing monomer unit (a4) and the aromatic ring-containing monomer unit (a8) include isobornyl acrylate, isobornyl methacrylate, adamantyl acrylate, adamantyl methacrylate, 2-methyl-2-adamantyl methacrylate, 2-ethyl-2-adamantyl methacrylate, dicyclopentenyl acrylate, dicyclopentenyl methacrylate, dicyclopentanyl acrylate, dicyclopentanyl methacrylate, styrene, α-methylstyrene, and vinylnaphthalene.

[0080] The total content of the aliphatic fused ring structure-containing monomer unit (a4) having a homopolymer glass transition temperature of 80° C. or higher and the aromatic ring-containing monomer unit (a8) having a homopolymer glass transition temperature of 80° C. or higher is preferably 5 to 60 mol %, more preferably 5 to 50 mol %, of all the constituent units of the alkali-soluble resin (A2).

[0081] The weight average molecular weight (Mw) of the alkali-soluble resin (A2) is preferably from 3,000 to 12,000, and more preferably from 4,000 to 10,000, from the viewpoint of resistance.

[0082] The alkali-soluble resin (A2) can be used alone or in combination of two or more kinds.

[0083] The content of the alkali-soluble resin (A2) is preferably 5% by mass or more, and more preferably 10 to 85% by mass, in 100% by mass of the alkali-soluble resin (A).

[0084] [Polymerizable compound (B)] The photosensitive composition of the present invention contains a polymerizable compound (B).

[0085] The polymerizable compound (B) may be a monomer or oligomer having a polymerizable unsaturated group. Examples of the polymerizable unsaturated group include a vinyl group, a (meth)allyl group, a (meth)acryloyl group, and a (meth)acryloyloxy group having an ethylenically unsaturated double bond.

[0086] The polymerizable compound (B) is not particularly limited, and a known compound can be used. For example, lactone-modified polymerizable compound (B1), polymerizable compound having an acidic group (B2), polymerizable compound having a urethane bond (B3), polymerizable compound having an amine structure (B4), polymerizable compound having a hydroxyl group (B5), polymerizable compound having a dendrimer structure or hyperbranch structure (B6), and other polymerizable compounds (B7) can be mentioned. In particular, it is preferable that the polymerizable compound (B) contains at least one selected from the group consisting of a lactone-modified polymerizable compound (B1), a polymerizable compound (B2) having an acidic group, and a polymerizable compound (B3) having a urethane bond.

[0087] The polymerizable compound (B) can be used alone or in combination of two or more kinds.

[0088] The content of the polymerizable compound (B) is preferably from 1 to 80 mass %, and more preferably from 5 to 70 mass %, based on 100 mass % of the nonvolatile content of the photosensitive composition.

[0089] (Lactone-modified polymerizable compound (B1)) From the viewpoint of suppressing water stains, the polymerizable compound (B) preferably contains a lactone-modified polymerizable compound (B1).

[0090] The lactone-modified polymerizable compound (B1) is a compound having a structure modified with lactone in the molecule. It is presumed that the lactone-modified structural portion is highly hydrophobic and has low affinity with an alkaline developer, which can suppress water stains.

[0091] The lactone-modified polymerizable compound (B1) can be obtained by esterifying a polyhydric alcohol such as trimethylolethane, ditrimethylolethane, trimethylolpropane, ditrimethylolpropane, pentaethylthritol, tripentaerythritol, glycerin, diglycerol, or trimetrolmelamine with (meth)acrylic acid and ε-caprolactone or other lactone compound. The lactone-modified polymerizable compound (B1) is preferably a compound represented by the following general formula (6).

[0092] General formula (6) [ka]

[0093] In general formula (6), all of the six R's are groups represented by the following general formula (7), or one to five of the six R's are groups represented by the following general formula (7) and the remainder are groups represented by the following general formula (8).

[0094] General formula (7) [ka]

[0095] In general formula (7), R 1 represents a hydrogen atom or a methyl group, m is an integer of 1 or 2, and * is a bond bonding to the oxygen atom of general formula (6).

[0096] General formula (8) [ka]

[0097] In general formula (8), R 1 represents a hydrogen atom or a methyl group, and * represents a bond bonding to the oxygen atom in general formula (6).

[0098] The lactone-modified polymerizable compound (B1) is commercially available as, for example, the KAYARAD DPCA series manufactured by Nippon Kayaku Co., Ltd. For example, DPCA-20 (in the general formulas (6) to (8), m=1, the number of groups represented by the general formula (7)=2, R 1 are all hydrogen atoms), DPCA-30 (in the general formulas (6) to (8), m=1, the number of groups represented by the general formula (7)=3, R 1 are all hydrogen atoms), DPCA-60 (in the general formulas (6) to (8), m=1, the number of groups represented by the general formula (7)=6, R 1 are all hydrogen atoms), DPCA-120 (in the general formulas (6) to (8), m=2, the number of groups represented by the general formula (7)=6, R 1 are all hydrogen atoms).

[0099] From the viewpoint of suppressing water stains, the lactone-modified polymerizable compound (B1) is preferably such that m=1 in the general formulas (6) to (8), the number of groups represented by the general formula (7) is 2 to 6, R 1 are all hydrogen atoms, and in the general formulas (6) to (8), m=1, the number of groups represented by the general formula (7)=2 or 3, R 1 A compound in which all are hydrogen atoms is more preferred.

[0100] The lactone-modified polymerizable compounds (B1) can be used alone or in combination of two or more kinds.

[0101] The content of the lactone-modified polymerizable compound (B1) is preferably from 5 to 90 mass %, and more preferably from 10 to 85 mass %, in 100 mass % of the polymerizable compound (B) from the viewpoint of suppressing water stains.

[0102] (Polymerizable compound (B2) having an acidic group) From the viewpoint of adhesion, the polymerizable compound (B) preferably contains a polymerizable compound (B2) having an acidic group. It is presumed that the presence of an acidic group improves solubility in an alkaline developer, and development is completed in a short time, thereby suppressing chipping and peeling of the pattern. The polymerizable compound (B2) having an acidic group is a polymerizable compound that does not have a urethane bond.

[0103] Examples of the acidic group of the polymerizable compound (B2) having an acidic group include a sulfonic acid group, a carboxyl group, a phosphoric acid group, etc. Among these, the carboxyl group is preferred.

[0104] Examples of the polymerizable compound (B2) having an acidic group include esters of free hydroxyl group-containing poly(meth)acrylates of polyhydric alcohols and (meth)acrylic acid with dicarboxylic acids; esters of polycarboxylic acids with monohydroxyalkyl (meth)acrylates; and the like.

[0105] Examples of the polyhydric alcohol include ethylene glycol, propylene glycol, polyethylene glycol, polypropylene glycol, glycerin, trimethylolpropane, ditrimethylolpropane, pentaerythritol, and dipentaerythritol.

[0106] Examples of the dicarboxylic acids include malonic acid, succinic acid, maleic acid, glutaric acid, phthalic acid, itaconic acid, and the like.

[0107] Examples of the polyvalent carboxylic acid 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.

[0108] Commercially available products of the polymerizable compound (B2) having an acidic group include Aronix M-5300, M-5400, M-510, M-520, and M-521 manufactured by Toagosei Co., Ltd., and β-CEA manufactured by Daicel-Allnex Corporation.

[0109] The polymerizable compound (B2) having an acidic group can be used alone or in combination of two or more kinds.

[0110] The content of the polymerizable compound (B2) having an acidic group is preferably from 5 to 90 mass %, and more preferably from 10 to 85 mass %, in 100 mass % of the polymerizable compound (B) from the viewpoint of adhesion.

[0111] (Polymerizable compound having a urethane bond (B3)) From the viewpoint of suppressing drying unevenness and adhesion, the photosensitive composition of the present invention preferably contains a polymerizable compound (B3) having a urethane bond as the polymerizable compound (B). The polymerizable compound (B3) having a urethane bond forms a chemical crosslinked structure due to the reaction of the polymerizable portion in the coating film as well as a physical crosslinked structure due to intermolecular hydrogen bonds at the urethane bond portion. The molecular cohesive energy of the intermolecular hydrogen bonds at the urethane bond portion is larger than the cohesive energy of other organic structures such as ether bonds. Therefore, it is presumed that the pattern is strengthened by the interaction between the urethane bonds. In addition, the interaction between the urethane bonds has a weaker binding force than chemical bonds and has moderate flexibility. Therefore, it is presumed that the drying unevenness is suppressed and the adhesion is improved.

[0112] Examples of the polymerizable compound (B3) having a urethane bond include urethane (meth)acrylates obtained by reacting a (meth)acrylate having a hydroxyl group with a polyfunctional isocyanate, and urethane (meth)acrylates obtained by reacting a polyhydric alcohol with a polyfunctional isocyanate and further reacting the polyhydric alcohol with a (meth)acrylate having a hydroxyl group.

[0113] Examples of the hydroxyl group-containing (meth)acrylate include 2-hydroxyethyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, trimethylolpropane di(meth)acrylate, pentaerythritol tri(meth)acrylate, ditrimethylolpropane tri(meth)acrylate, dipentaerythritol penta(meth)acrylate, dipentaerythritol ethylene oxide (EO)-modified penta(meth)acrylate, dipentaerythritol propylene oxide (PO)-modified penta(meth)acrylate, dipentaerythritol caprolactone-modified penta(meth)acrylate, glycerol mono(meth)acrylate, glycerol di(meth)acrylate, 2-hydroxy-3-acryloylpropyl methacrylate, a reaction product of an epoxy group-containing compound and a carboxy(meth)acrylate, and a hydroxyl group-containing polyol polyacrylate.

[0114] Examples of the polyfunctional isocyanate include aromatic diisocyanates such as tolylene diisocyanate, diphenylmethylene diisocyanate, and xylene diisocyanate, aliphatic diisocyanates such as trimethylene diisocyanate, tetramethylene diisocyanate, and hexamethylene diisocyanate, and alicyclic diisocyanate such as isophorone diisocyanate, as well as biuret forms, isocyanurate forms, and trimethylolpropane adducts thereof.

[0115] From the viewpoint of developability, the polymerizable compound (B3) having a urethane bond preferably further has an acidic group. Examples of the acidic group include a sulfonic acid group, a carboxyl group, and a phosphoric acid group. Among these, a carboxyl group is preferred.

[0116] The method for introducing an acidic group into the polymerizable compound (B3) having a urethane bond can be, for example, synthesized by first reacting the above-mentioned hydroxyl group-containing (meth)acrylate with the above-mentioned polyfunctional isocyanate, and then adding a mercapto compound having a carboxyl group to the product.

[0117] Examples of the mercapto compound having a carboxyl group include mercaptoacetic acid, 2-mercaptopropionic acid, 3-mercaptopropionic acid, o-mercaptobenzoic acid, 2-mercaptonicotinic acid, and mercaptosuccinic acid.

[0118] Commercially available polymerizable compounds (B3) having a urethane bond include, for example, AH-600, UA-306H, UA-306T, UA-306I, UA-510H, and UF-8001G manufactured by Kyoeisha Chemical Co., Ltd., UA-1100H, U-6LPA, UA-33H, U-10HA, and U-15HA manufactured by Shin-Nakamura Chemical Co., Ltd., and EBECRYL1290 and KRM8452 manufactured by Daicel-Allnex Corporation.

[0119] The polymerizable compound (B3) having a urethane bond can be used alone or in combination of two or more kinds.

[0120] The content of the polymerizable compound (B3) having a urethane bond is preferably 5 to 90 mass %, more preferably 10 to 85 mass %, in 100 mass % of the polymerizable compound (B) from the viewpoints of preventing drying unevenness and adhesion.

[0121] (Polymerizable compound having an amine structure (B4)) The amine structure of the polymerizable compound (B4) having an amine structure may be any of primary amine, secondary amine, and tertiary amine structures, but is preferably a secondary or tertiary amine structure, but does not include an amide structure, an imide structure, or a urethane structure in which a carbonyl group is directly bonded to a nitrogen atom.

[0122] Examples of the polymerizable compound (B4) having an amine structure include tris(acryloyloxyethyl)amine, tris(methacryloyloxyethyl)amine, tris(2-hydroxy-3-methacryloyloxypropyl)amine, and a Michael addition reaction product of a (meth)acrylate compound (X) and an amine compound (Y).

[0123] Examples of the (meth)acrylate compound (X) include glycerin tri(meth)acrylate, trimethylolpropane tri(meth)acrylate, pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, ditrimethylolpropane tri(meth)acrylate, ditrimethylolpropane tetra(meth)acrylate, dipentaerythritol tetra(meth)acrylate, dipentaerythritol penta(meth)acrylate, dipentaerythritol hexa(meth)acrylate, diglycerol tri(meth)acrylate, trimethylolpropane tri(meth)acrylate, penta ...hexa(meth)acrylate, diglycerol tri(meth)acrylate, trimethylolpropane tri(meth)acrylate, pentaerythritol hexa(meth)acrylate, diglycerol tri(meth)acrylate, trimethylolpropane tri(meth)acrylate, pentaerythritol hexa(meth)acrylate, diglycerol tri(meth)acrylate, trimethylolpropane tri(meth)acrylate, pentaerythritol hexa(meth)acrylate, diglycerol tri(meth)acrylate, trimethylolpropane tri(meth)acrylate, pentaerythritol hexa(meth)acrylate, diglycerol tri(meth)acrylate, trimethylolpropane tri(meth)acrylate, Examples of the alkylene oxide-modified tetra(meth)acrylate include phosphorus tri(meth)acrylate, diglycerol tetra(meth)acrylate, trimethylolpropane alkylene oxide-modified tri(meth)acrylate, ditrimethylolpropane alkylene oxide-modified tri- and tetra(meth)acrylate, pentaerythritol alkylene oxide-modified tri- and tetra(meth)acrylate, diglycerol alkylene oxide-modified tri- and tetra(meth)acrylate, and dipentaerythritol alkylene oxide-modified tetra-, penta- and hexa(meth)acrylate. Examples of the alkylene oxide unit in the alkylene oxide modification include ethylene oxide, propylene oxide, and butylene oxide. The (meth)acrylate compound (X) also includes a (meth)acrylate compound having an acidic group.

[0124] The (meth)acrylate compounds (X) can be used alone or in combination of two or more.

[0125] Examples of the amine compound (Y) include primary amines such as n-propylamine, n-butylamine, n-hexylamine, benzylamine, aminocaproic acid, monoethanolamine, 2-(2-aminoethoxy)ethanol, o-aminophenol, m-aminophenol, and p-aminophenol; Examples of the secondary amines include dimethylamine, diethylamine, dipropylamine, diisopropylamine, dibutylamine, cyclohexylamine, morpholine, piperidine, 1-methylpiperazine, proline, N-merylethanolamine, N-acetylethanolamine, diethanolamine, 3-anilinephenol, and 4-anilinephenol.

[0126] The amine compound (Y) can be used alone or in combination of two or more kinds.

[0127] The method for producing the Michael addition reaction product of the (meth)acrylate compound (X) and the amine compound (Y) is not particularly limited, and a known method can be used. For example, the methods described in International Publication No. 2006 / 075754, JP-A-2008-545859, JP-A-2017-066347, etc. can be mentioned.

[0128] The polymerizable compound (B4) having an amine structure may have an acidic group and / or a hydroxyl group. Examples of a method for introducing an acidic group and / or a hydroxyl group include a method of using a compound having an acidic group and / or a hydroxyl group in the (meth)acrylate compound (X) or the amine compound (Y), and a method of adding an acid anhydride after a Michael addition reaction.

[0129] Commercially available polymerizable compounds (B4) having an amine structure include, for example, ARONIX MT-3041 and 3042 manufactured by Toagosei Co., Ltd., EBECRYL 80 and 7100 manufactured by Daicel-Allnex Corporation, and CN371NS, 372, 374, 383 and 386 manufactured by Arkema.

[0130] The polymerizable compound (B4) having an amine structure may further have a urethane bond. The urethane bond may be introduced, for example, by a urethane reaction between the Michael addition reaction product (precursor) of the above-mentioned (meth)acrylate compound (X) and the above-mentioned amine compound (Y) having a hydroxyl group and the polyisocyanate compound (Z).

[0131] Examples of the polyisocyanate compound (Z) include polyisocyanate compounds having an aliphatic structure, such as butane-1,4-diisocyanate, hexamethylene diisocyanate, isopropylene diisocyanate, methylene diisocyanate, and 2,2,4-trimethylhexamethylene diisocyanate; Polyisocyanate compounds having an alicyclic structure, such as cyclohexane-1,4-diisocyanate, isophorone diisocyanate, dimethylcyclohexyl diisocyanate, methylcyclohexyl diisocyanate, dicyclohexylmethane-4,4'-diisocyanate, 1,3-bis(isocyanatemethyl)cyclohexane, methylcyclohexane diisocyanate, norbornane diisocyanate, and bis(isocyanatemethyl)cyclohexane; Examples of the polyisocyanate compound include polyisocyanate compounds having an aromatic structure, such as 1,5-naphthylene diisocyanate, 4,4'-diphenylmethane diisocyanate, 4,4'-diphenyldimethylmethane diisocyanate, 4,4'-dibenzyl isocyanate, dialkyl diphenylmethane diisocyanate, tetraalkyl diphenylmethane diisocyanate, 1,3-phenylene diisocyanate, 1,4-phenylene diisocyanate, 2,4-toluene diisocyanate, 2,6-toluene diisocyanate, xylylene diisocyanate, m-tetramethyl xylylene diisocyanate, 4,4-diphenylmethane diisocyanate, tolylene diisocyanate, bischloromethyl diphenylmethane diisocyanate, 2,6-diisocyanate-benzyl chloride, and bis(isocyanate methyl)benzene. Further, biuret, isocyanurate, adduct and allophanate forms of these compounds are also included.

[0132] The polyisocyanate compounds (Z) can be used alone or in combination of two or more kinds.

[0133] The method of the urethane reaction between the precursor and the polyisocyanate compound (Z) is not particularly limited, and a known method can be used. For example, the method described in JP-A-2018-517797 can be mentioned.

[0134] The polymerizable compound (B4) having an amine structure can be used alone or in combination of two or more kinds.

[0135] (Polymerizable compound having a hydroxyl group (B5)) Examples of the polymerizable compound (B5) having a hydroxyl group include 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, EO isocyanuric acid, or the like. Examples of such acrylic acid esters include PO-modified (meth)acrylate, isocyanuric acid EO or PO-modified di(meth)acrylate, pentaerythritol tri(meth)acrylate, dipentaerythritol penta(meth)acrylate, polypentaerythritol penta(meth)acrylate, dipentaerythritol EO or PO-modified penta(meth)acrylate, and dipentaerythritol caprolactone-modified penta(meth)acrylate; and epoxy (meth)acrylates obtained by reacting the epoxy group of an epoxy compound with the carboxyl group of (meth)acrylic acid.

[0136] Examples of commercially available polymerizable compounds (B5) having a hydroxyl group include KAYARAD R-128H and R-167 manufactured by Nippon Kayaku Co., Ltd., ARONIX M-5700 and M-920 manufactured by Toagosei Co., Ltd., NK Ester 701A manufactured by Shin-Nakamura Chemical Co., Ltd., Light Ester HOP(N), HOA(N), HOP-A(N), HOB(N), and G-201P, Epoxy Ester M-600A, 40EM, 70PA, 200PA, 80MFA, 3002M(N), 3002A(N), and 3000A manufactured by Kyoeisha Chemical Co., Ltd., and OGSOL GA-5060P and GA-2800 manufactured by Osaka Gas Chemical Co., Ltd.

[0137] The polymerizable compound (B5) having a hydroxyl group can be used alone or in combination of two or more kinds.

[0138] (Polymerizable compound (B6) having a dendrimer structure or a hyperbranched structure) A compound having a dendrimer structure has a chemical structure in which the core-constituting chemical structure (hereinafter also referred to as the core portion) is regularly branched outward, and a polymerizable unsaturated group is bonded to the end of the branch, and the compound has a highly controlled spherical chemical structure and molecular weight. The hyperbranched structure has a chemical structure similar to that of the dendrimer structure.

[0139] Commercially available polymerizable compounds (B6) having a dendrimer structure or a hyperbranched structure include, for example, Viscoat #1000LT (dendrimer structure, average number of acryloyl groups: 14) and SIRUS-501 (dendrimer structure, average number of acryloyl groups: 18) manufactured by Osaka Organic Chemical Industry Co., Ltd., Miramer SP-1106 (dendrimer structure, average number of acryloyl groups: 18) and SP-1108 (dendrimer structure, average number of acryloyl groups: 13) manufactured by Miwon Specialty Chemical Co., Ltd., CN2301 (hyperbranched structure, average number of acryloyl groups: 9), CN2302 (hyperbranched structure, average number of acryloyl groups: 16), CN2303 (hyperbranched structure, average number of acryloyl groups: 6), CN2304 (hyperbranched structure, average number of acryloyl groups: 18), and Eternal Examples include Etercure 6361-100 (hyperbranched structure, average number of acryloyl groups: 8), 6362-100 (hyperbranched structure, average number of acryloyl groups: 12), 6363 (hyperbranched structure, average number of acryloyl groups: 16), and DR-E522 (hyperbranched structure, average number of acryloyl groups: 15), all manufactured by Materials.

[0140] The polymerizable compound (B6) having a dendrimer structure or a hyperbranched structure can be used alone or in combination of two or more kinds.

[0141] (Other polymerizable compounds (B7)) Examples of other polymerizable compounds (B7) include 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, trimethylolpropane EO or PO modified tri(meth)acrylate, isocyanuric acid. Examples of the methacrylic acid ester include EO- or PO-modified tri(meth)acrylate, ditrimethylolpropane tetra(meth)acrylate, pentaerythritol tetra(meth)acrylate, dipentaerythritol hexa(meth)acrylate, dipentaerythritol EO- or PO-modified hexa(meth)acrylate, tricyclodecanyl (meth)acrylate, and (meth)acrylic acid ester of methylolated melamine; styrene, vinyl acetate, ethylene glycol divinyl ether, pentaerythritol trivinyl ether, (meth)acrylamide, N-vinyl formamide, and acrylonitrile.

[0142] Other commercially available products of the polymerizable compound (B7) include, for example, KAYARAD NPGDA, PEG400DA, FM-400, HX-200, HX-620, R-551, R-712, R-604, R-684, GPOD-303, TMPTA, T-1420(T), RP-1040, DPEA-12, and D-310 manufactured by Nippon Kayaku Co., Ltd., and Aronix M-101A, M-102, M-111, M-113, M-120, M-140, M-208, and M-21 manufactured by Toagosei Co., Ltd. 1B, M-220, M-225, M-270, M-240, M-309, M-310, M-321, M-350, M-360, M-408, M-460, Viscoat #150, #155, #160, #192, #MTG, #200, #196, #195, #230, #260, #310, #700HV, #295 manufactured by Osaka Organic Chemical Industry Co., Ltd., OGSOL manufactured by Osaka Gas Chemical Co., Ltd. Examples of such esters include EA-0200, EA-0300, Miramer HR6060, 6100, and 6200 manufactured by Miwon Specialty Chemical Co., Ltd., and NK Ester A-HD-N, A-NPG, A-200, A-400, APG-200, APG-400, A-DCP, ABE-300, A-BPE-4, A-BPE-10, A-TMPT, A-TMPT-9EO, A-GLY-3E, A-GLY-9E, A-TMMT, ATM-35E, and AD-TMP manufactured by Shin-Nakamura Chemical Co., Ltd.

[0143] The other polymerizable compounds (B7) can be used alone or in combination of two or more kinds.

[0144] [Polymerization initiator (C)] The photosensitive composition of the present invention contains a polymerization initiator (C).

[0145] The polymerization initiator (C) is not particularly limited, and any known compound can be used. For example, a compound that generates radicals by the action of light or heat to initiate or promote a radical polymerization reaction can be used. The polymerization initiator that generates radicals by light (hereinafter, also simply referred to as a photopolymerization initiator) is preferably a compound that generates radicals by light rays in the ultraviolet to visible light range. The polymerization initiator that generates radicals by heat (hereinafter, also simply referred to as a thermal polymerization initiator) may be a compound that generates radicals by the action of heat and light.

[0146] Examples of the photopolymerization initiator include acetophenone-based compounds such as 4-phenoxydichloroacetophenone, 4-t-butyl-dichloroacetophenone, diethoxyacetophenone, 1-(4-isopropylphenyl)-2-hydroxy-2-methylpropan-1-one, 1-hydroxycyclohexyl phenyl 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; triazine compounds such as 2,4,6-trichloro-s-triazine, 2-phenyl-4,6-bis(trichloromethyl)-s-triazine, 2-(p-methoxyphenyl)-4,6-bis(trichloromethyl)-s-triazine, 2-(p-tolyl)-4,6-bis(trichloromethyl)-s-triazine, 2-piperonyl-4,6-bis(trichloromethyl)-s-triazine, 2,4-bis(trichloromethyl)-6-styryl-s-triazine, 2-(naphth-1-yl)-4,6-bis(trichloromethyl)-s-triazine, 2-(4-methoxy-naphth-1-yl)-4,6-bis(trichloromethyl)-s-triazine, 2,4-trichloromethyl-(piperonyl)-6-triazine, and 2,4-trichloromethyl-(4'-methoxystyryl)-6-triazine; Oxime compounds such as 1,2-octanedione, 1-[4-(phenylthio)phenyl-, 2-(O-benzoyloxime)], ethanol, 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]-, 1-(O-acetyloxime); Acylphosphine compounds such as bis(2,4,6-trimethylbenzoyl)phenylphosphine oxide and diphenyl-2,4,6-trimethylbenzoylphosphine oxide; Examples of the compound include quinone-based compounds such as 9,10-phenanthrenequinone, camphorquinone, and ethylanthraquinone; borate-based compounds; and carbazole-based compounds.

[0147] Commercially available products include acetophenone compounds such as Omnirad 907, 369E, 379EG, 127, 184, 1173, and 2959 manufactured by IGM Resins, acylphosphine compounds such as Omnirad 819 and TPO manufactured by IGM Resins, oxime compounds such as IRGACURE OXE-01, 02, 03, 04, and 05 manufactured by BASF Japan, ADEKA Arcles N-1919, NCI-730, 831E, and 930 manufactured by ADEKA, TRONLY TR-PBG-301, 304, 305, 309, 314, 345, 358, 380, 365, 610, 3054, and 3057 manufactured by Changzhou Strong New Materials Co., Ltd., and IGM Examples of such adhesives include Omnirad 1312, 1314, and 1316 manufactured by Resins, SPI-02, 03, 04, 05, 06, and 07 manufactured by Samyang Corporation, and DFI-020, 306, and EOX-01 manufactured by Daito Chemistrys. Further, compounds described in JP 2007-210991 A, JP 2009-179619 A, JP 2010-037223 A, JP 2010-215575 A, JP 2011-020998 A, WO 2015 / 036910, JP 2019-507108 A, JP 2019-528331 A, WO 2021 / 175855 A, JP 2022-5115524 A, and the like are also included.

[0148] Examples of the thermal polymerization initiator include benzopinacol, 1,2-dimethoxy-1,1,2,2-tetraphenylethane, 1,2-dimethoxy-1,1,2,2-tetraphenylethane, 1,2-diphenoxy-1,1,2,2-tetraphenylethane, 1,2-dimethoxy-1,1,2,2-tetra(4-methylphenyl)ethane, 1,2-diphenoxy-1,1,2,2-tetra(4-methoxyphenyl)ethane, and 1,2-bis(trimethylsiloxy)-1,1,2,2-tetraphenylethane. pinacol compounds such as 1,2-bis(triethylsiloxy)-1,1,2,2-tetraphenylethane, 1,2-bis(tert-butyldimethylsiloxy)-1,1,2,2-tetraphenylethane, 1-hydroxy-2-trimethylsiloxy-1,1,2,2-tetraphenylethane, 1-hydroxy-2-triethylsiloxy-1,1,2,2-tetraphenylethane, and 1-hydroxy-2-tert-butyldimethylsiloxy-1,1,2,2-tetraphenylethane; azo compounds such as 2,2'-azobis(4-methoxy-2,4-dimethylvaleronitrile), 2,2'-azobis(2,4-dimethylvaleronitrile), dimethyl-2,2'-azobis(2-methylpropionate), 2,2'-azobis(2-methylbutyronitrile), 1,1'-azobis(cyclohexane-1-carbonitrile), 2,2'-azobis[N-(2-propenyl)2-methylpropionamide], 1-[(1-cyano-1-methylethyl)azo]formamide, 2,2'-azobis(N-butyl-2-methylpropionamide), and 2,2'-azobis(N-cyclohexyl-2-methylpropionamide); Examples of the organic peroxides include methyl ethyl ketone peroxide, cyclohexanone peroxide, 3,3,5-trimethylcyclohexanone peroxide, methylcyclohexanone peroxide, acetylacetone peroxide, 1,1-bis(tert-butylperoxy)-3,3,5-trimethylcyclohexane, 1,1-bis(tert-butylperoxy)cyclohexane, 2,2-bis(tert-butylperoxy)butane, succinic peroxide, and benzoyl peroxide.

[0149] The polymerization initiator (C) can be used alone or in combination of two or more kinds.

[0150] The content of the polymerization initiator (C) is preferably from 0.1 to 20 mass %, and more preferably from 0.5 to 10 mass %, based on 100 mass % of the nonvolatile content of the photosensitive composition.

[0151] From the viewpoints of suppressing water stains and adhesion, the photosensitive composition of the present invention preferably contains, as the polymerization initiator (C), one or more compounds selected from the group consisting of a compound (C1) represented by the following general formula (3), a compound (C2) represented by the following general formula (4), and a compound (C3) represented by the following general formula (5):

[0152] General formula (3) [ka]

[0153] In the general formula (3), R1 is an alkyl group having 4 to 20 carbon atoms and having an alicyclic hydrocarbon group. R2 is 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. R3 is a hydrogen atom, a nitro group, a group having an ether bond, or a group having an aromatic ring.

[0154] General formula (4) [ka]

[0155] In general formula (4), R4 and R5 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.

[0156] General formula (5) [ka]

[0157] In general formula (5), R6 and R7 each independently represent a hydrogen atom or an alkyl group having 1 to 8 carbon atoms. R8 is a hydrogen atom or a monovalent substituent.

[0158] (Compound (C1) represented by general formula (3)) The compound (C1) represented by formula (3) will be described below.

[0159] In the general formula (3), R1 represents an alkyl group having 4 to 20 carbon atoms and having an alicyclic hydrocarbon group. Examples of the alicyclic hydrocarbon group include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, and a cyclooctyl group. Among the above, from the viewpoint of suppressing water stains, a cyclopentyl group and a cyclohexyl group are preferred, and a cyclohexyl group is more preferred.

[0160] In general formula (3), R2 represents 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. The alkyl group having 1 to 20 carbon atoms may be linear, branched, or cyclic, or may be a combination of these, and examples thereof include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a tert-butyl group, an amyl group, an isoamyl group, a hexyl group, a heptyl group, an octyl group, an isooctyl group, a 2-ethylhexyl group, a nonyl group, an isononyl group, a decyl group, an isodecyl group, an undecyl group, a dodecyl group, a hexadecyl group, a cyclopentyl group, a cyclopentylmethyl group, a cyclohexyl group, and a cyclohexylmethyl group. Examples of the aryl group having 6 to 30 carbon atoms include a phenyl group, a tolyl group, a xylyl group, an ethylphenyl group, a naphthyl group, and an anthryl group. Examples of the arylalkyl group having 7 to 30 carbon atoms include a benzyl group, an α-methylbenzyl group, an α,α-dimethylbenzyl group, and a phenylethyl group. Examples of the heterocyclic group having 2 to 20 carbon atoms include a pyridyl group, a pyrimidyl group, a furyl group, a tetrahydrofuryl group, a dioxolanyl group, an imidazolidyl group, an oxazolidyl group, a piperidyl group, and a morpholinyl group. Among the above, from the viewpoint of reactivity, a methyl group, an ethyl group, and a phenyl group are preferred, and a methyl group and an ethyl group are more preferred.

[0161] In general formula (3), R3 represents a hydrogen atom, a nitro group, a group having an ether bond, or a group having an aromatic ring. When R3 is a group having an aromatic ring, the cyclic portion may be a single ring or a condensed ring. It may also be a heterocyclic ring or may further include an alicyclic ring. In particular, it is preferable that R3 has a carbonyl group, and the rings are bonded to each other via the carbonyl group. Examples of the aromatic ring include a benzene ring, a furan ring, a thiophene ring, a naphthalene ring, a benzofuran ring, a benzothiophene ring, and an indole ring. Among the above, from the viewpoint of reactivity, R3 is preferably a hydrogen atom or a nitro group, and more preferably a hydrogen atom.

[0162] The method for producing the compound (C1) represented by the general formula (3) is not particularly limited, and a known method can be used, for example, the method described in JP-A-2012-526185.

[0163] Specific examples of the compound (C1) represented by formula (3) are shown below, but the present invention is not limited thereto.

[0164] [ka]

[0165] The compound (C1) represented by the general formula (3) can be used alone or in combination of two or more kinds.

[0166] The content of the compound (C1) represented by formula (3) is preferably from 1 to 100 mass %, and more preferably from 5 to 95 mass %, in 100 mass % of the polymerization initiator (C).

[0167] (Compound (C2) represented by general formula (4)) The compound (C2) represented by the general formula (4) will be described below.

[0168] In general formula (4), R4 and R5 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. The alkyl group having 1 to 20 carbon atoms may be linear, branched, or cyclic, or may be a combination of these, and examples thereof include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a tert-butyl group, an amyl group, an isoamyl group, a hexyl group, a heptyl group, an octyl group, an isooctyl group, a 2-ethylhexyl group, a nonyl group, an isononyl group, a decyl group, an isodecyl group, an undecyl group, a dodecyl group, a hexadecyl group, a cyclopentyl group, a cyclopentylmethyl group, a cyclohexyl group, and a cyclohexylmethyl group. Examples of the aryl group having 6 to 30 carbon atoms include a phenyl group, a tolyl group, a xylyl group, an ethylphenyl group, a naphthyl group, and an anthryl group. Examples of the arylalkyl group having 7 to 30 carbon atoms include a benzyl group, an α-methylbenzyl group, an α,α-dimethylbenzyl group, and a phenylethyl group. Examples of the heterocyclic group having 2 to 20 carbon atoms include a pyridyl group, a pyrimidyl group, a furyl group, a tetrahydrofuryl group, a dioxolanyl group, an imidazolidyl group, an oxazolidyl group, a piperidyl group, and a morpholinyl group. Among the above, from the viewpoint of suppressing water stains, R4 is preferably an alkyl group having 1 to 12 carbon atoms or an arylalkyl group having 7 to 15 carbon atoms, and more preferably an alkyl group having 3 to 8 carbon atoms. Among the above, from the viewpoint of reactivity, R5 is preferably a methyl group, an ethyl group, or a phenyl group, and more preferably a methyl group or an ethyl group.

[0169] The method for producing the compound (C2) represented by the general formula (4) is not particularly limited, and a known method can be used. For example, the method described in International Publication No. 2015 / 152153 can be used.

[0170] Specific examples of the compound (C2) represented by formula (4) are shown below, but the present invention is not limited thereto.

[0171] [ka]

[0172] The compound (C2) represented by the general formula (4) can be used alone or in combination of two or more kinds.

[0173] The content of the compound (C2) represented by formula (4) is preferably from 1 to 100 mass%, more preferably from 5 to 95 mass%, in 100 mass% of the polymerization initiator (C).

[0174] (Compound (C3) represented by general formula (5)) The compound (C3) represented by the general formula (5) will be described below.

[0175] In formula (5), R6 and R7 each independently represent a hydrogen atom or an alkyl group having 1 to 8 carbon atoms. The alkyl group having 1 to 8 carbon atoms may be linear, branched, or cyclic, or may be a combination of these, and examples thereof include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a tert-butyl group, a pentyl group, an isopentyl group, a hexyl group, a heptyl group, an octyl group, a 2-ethylhexyl group, a cyclopentyl group, a cyclopentylmethyl group, a cyclohexyl group, and a cyclohexylmethyl group. Among the above, R6 and R7 are preferably a linear alkyl group having 3 to 8 carbon atoms, and more preferably a linear alkyl group having 4 to 6 carbon atoms.

[0176] R8 represents a hydrogen atom or any monovalent substituent. Examples of the monovalent substituent include alkyl groups having 1 to 20 carbon atoms, such as methyl and ethyl groups; alkoxy groups having 1 to 20 carbon atoms, such as methoxy and ethoxy groups; halogen atoms, such as F, Cl, Br, and I; acyl groups having 1 to 20 carbon atoms; alkyl ester groups having 1 to 20 carbon atoms; alkoxycarbonyl groups having 1 to 20 carbon atoms; halogenated alkyl groups having 1 to 20 carbon atoms, aromatic ring groups having 4 to 20 carbon atoms; amino groups; aminoalkyl groups having 1 to 20 carbon atoms; hydroxyl groups; nitro groups; cyano groups; benzoyl groups which may have a substituent; and thenoyl groups which may have a substituent. Examples of the substituents that the benzoyl group or thenoyl group may have include alkyl groups having 1 to 10 carbon atoms, alkoxy groups having 1 to 10 carbon atoms, and alkoxycarbonyl groups having 1 to 10 carbon atoms. Among the above, from the viewpoint of radical generation efficiency, R8 is preferably a hydrogen atom or a nitro group, and more preferably a hydrogen atom.

[0177] The method for producing the compound (C3) represented by the general formula (5) is not particularly limited, and a known method can be used. For example, the methods described in JP-T-2019-507108 and JP-T-2019-528331 can be mentioned.

[0178] Specific examples of the compound (C3) represented by formula (5) are shown below, but the present invention is not limited thereto.

[0179] [ka]

[0180] The compound (C3) represented by the general formula (5) can be used alone or in combination of two or more kinds.

[0181] The content of the compound (C3) represented by formula (5) is preferably from 1 to 100 mass%, more preferably from 5 to 95 mass%, in 100 mass% of the polymerization initiator (C).

[0182] It is more preferable that the polymerization initiator (C) contains two or more compounds selected from the group consisting of a compound (C1) represented by general formula (3), a compound (C2) represented by general formula (4), and a compound (C3) represented by general formula (5).

[0183] [Leveling agent (D)] The photosensitive composition of the present invention contains a leveling agent (D).

[0184] The leveling agent (D) is not particularly limited, and any known compound can be used, such as a silicone-based leveling agent, a fluorine-based leveling agent, an acrylic-based leveling agent, or an acetylene diol-based leveling agent.

[0185] Examples of commercially available silicone leveling agents include BYK-300, 306, 310, 313, 315N, 320, 322, 323, 330, 331, 333, 342, 345, 346, 347, 348, 349, 370, 377, 378, 3455, UV3510, and 3570 manufactured by BYK-Chemie Co., Ltd., and FZ-7002, 2110, 2122, 2123, 2191, and 5609 manufactured by Dow Corning Toray Co., Ltd. Examples of such silicone rubbers 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, and KP-341 manufactured by Shin-Etsu Silicones Co., Ltd., and TegoGlide 432, 440, and 450, TegoWet 250, 260, 265, 270, and 280 manufactured by Evonik Corporation.

[0186] Examples of commercially available fluorine-based leveling agents include Surflon S-242, 243, 420, 611, 651, and 386 manufactured by AGC Seimi Chemical Co., Ltd.; Megafac F-253, 477, 551, 552, 555, 558, 560, 570, 575, and 576, R-40-LM, R-41, RS-72-K, and DS-21 manufactured by DIC Corporation; FC-4430 and 4432 manufactured by Sumitomo 3M Limited; EF-PP31N09, EF-PP33G1, and EF-PP32C1 manufactured by Mitsubishi Materials Electronic Chemicals Co., Ltd.; and Futergent 602A manufactured by Neos Corporation.

[0187] Commercially available acrylic leveling agents include, for example, BYK-350, 352, 354, 355, 358, 380, 381, 392, and 394 manufactured by BYK-Chemie Co., Ltd., and Polyflow 57, 77, and 95 manufactured by Kyoeisha Chemical Co., Ltd.

[0188] Commercially available acetylene diol leveling agents include, for example, Surfynol 420, 440, 465, 485, SE, DF110D, DE85, and Olfine E1004 and 1010 manufactured by Nissin Chemical Industry Co., Ltd.

[0189] The leveling agent (D) can be used alone or in combination of two or more kinds.

[0190] The content of the leveling agent (D) is preferably from 0.01 to 2.0 mass %, and more preferably from 0.05 to 1.0 mass %, based on 100 mass % of the nonvolatile content of the photosensitive composition.

[0191] (Copolymer (D1) having monomer unit (d1) represented by general formula (1) and monomer unit (d2) represented by general formula (2)) The photosensitive composition of the present invention contains, as a leveling agent (D), a copolymer (D1) having a monomer unit (d1) represented by general formula (1) and a monomer unit (d2) represented by general formula (2).

[0192] General formula (1) [ka]

[0193] In general formula (1), R1's are each independently an alkyl group having 1 to 6 carbon atoms, or a group represented by -OSi(R5)3 (R5's are each independently an alkyl group having 1 to 3 carbon atoms). Each R2 is independently an alkyl group having 1 to 6 carbon atoms. R3 is an alkyl group having 1 to 6 carbon atoms. R4 is a hydrogen atom or a methyl group. L1 is a divalent organic group or a single bond. n is an integer from 1 to 70.

[0194] General formula (2) [ka]

[0195] In the general formula (2), R6 is a hydrogen atom or an alkyl group having 1 to 18 carbon atoms. R7 is a hydrogen atom or a methyl group. m is an integer from 1 to 4. o is an integer from 2 to 200.

[0196] [Monomer unit (d1) represented by general formula (1)] The monomer unit (d1) represented by the general formula (1) is a monomer unit formed from a monomer represented by the general formula (1).

[0197] In general formula (1), R1's are each independently an alkyl group having 1 to 6 carbon atoms, or a group represented by -OSi(R5)3 (R5's are each independently an alkyl group having 1 to 3 carbon atoms). The alkyl group having 1 to 6 carbon atoms may be any of linear, branched, or combinations thereof, and examples thereof include methyl, ethyl, butyl, n-propyl, n-butyl, n-pentyl, n-hexyl, isopropyl, isobutyl, etc. Among these, R1 is preferably a methyl group or a trimethylsiloxy group from the viewpoint of suppressing drying unevenness and water stains.

[0198] In general formula (1), R2's are each independently an alkyl group having 1 to 6 carbon atoms. The alkyl group having 1 to 6 carbon atoms may be any of linear, branched, and combinations thereof, and examples thereof include a methyl group, an ethyl group, a butyl group, a n-propyl group, a n-butyl group, a n-pentyl group, a n-hexyl group, an isopropyl group, an isobutyl group, etc. Among these, R2 is preferably a methyl group.

[0199] In the general formula (1), R3 is an alkyl group having 1 to 6 carbon atoms. The alkyl group having 1 to 6 carbon atoms may be any of linear, branched, or combinations thereof, and examples thereof include a methyl group, an ethyl group, a butyl group, a n-propyl group, a n-butyl group, a n-pentyl group, a n-hexyl group, an isopropyl group, an isobutyl group, etc. Among these, R3 is preferably an alkyl group having 1 to 4 carbon atoms.

[0200] In general formula (1), R4 is a hydrogen atom or a methyl group.

[0201] In the general formula (1), L1 is a divalent organic group or a single bond. Among these, L1 is preferably a divalent organic group, more preferably an alkylene group having 1 to 50 carbon atoms or an alkyleneoxy group having 1 to 50 carbon atoms. The alkylene group having 1 to 50 carbon atoms may be any of linear, branched, and combinations thereof, and examples thereof include a methylene group, an ethylene group, an n-propyl group, an n-butylene group, an n-pentylene group, an n-hexylene group, an n-heptylene group, an n-octylene group, an isopropylene group, a 2-methylpropylene group, a 2-methylhexylene group, a tetramethylethylene group, etc. Among these, a methylene group, an ethylene group, an n-propylene group, and an isopropylene group are preferred. Examples of the alkyleneoxy group having 1 to 50 carbon atoms include a methyleneoxy group, an ethyleneoxy group, a propyleneoxy group, an oxytrimethylene group, a butyleneoxy group, an oxytetramethylene group, a pentyleneoxy group, and a heptyleneoxy group.

[0202] A part of -CH2- in the alkylene group having 1 to 50 carbon atoms or the alkyleneoxy group having 1 to 50 carbon atoms may be substituted with a carbonyl group, a phenylene group, an amide bond or a urethane bond, and further, a hydroxyl group or the like may be substituted on the carbon atom.

[0203] In the general formula (1), n ​​is an integer of 1 to 70. From the viewpoint of suppressing uneven drying and suppressing water stains, n is preferably an integer of 1 to 50, and more preferably an integer of 1 to 30.

[0204] Examples of the monomer represented by the general formula (1) include 3-(methacryloyloxy)propyltris(trimethylsiloxy)silane, α-(3-methacryloyloxy)propylpolydimethylsiloxane, etc. Commercially available products include Silaplane FM-0711, FM-0721, FM-0725, and FM-0701T manufactured by JNC Corporation, and X-22-174ASX, X-22-174BX, X-22-2426, and X-22-2404 manufactured by Shin-Etsu Chemical Co., Ltd.

[0205] The monomer represented by the general formula (1) can be used alone or in combination of two or more kinds.

[0206] The content of the monomer unit (d1) represented by general formula (1) is preferably 20 to 95 mass%, and more preferably 30 to 85 mass%, based on 100 mass% of the copolymer (D1), from the viewpoint of suppressing uneven drying and suppressing water stains.

[0207] [Monomer unit (d2) represented by general formula (2)] The monomer unit (d2) represented by the general formula (2) is a monomer unit formed from a monomer represented by the general formula (2).

[0208] In the general formula (2), R6 is a hydrogen atom or an alkyl group having 1 to 18 carbon atoms. The alkyl group having 1 to 18 carbon atoms may be any of linear, branched, cyclic, and combinations thereof, and examples thereof 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, and octadecyl groups. Among these, R6 is preferably a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and more preferably a hydrogen atom.

[0209] In general formula (2), R9 is a hydrogen atom or a methyl group.

[0210] In the general formula (2), m is an integer of 1 to 4. From the viewpoint of suppressing uneven drying and suppressing water stains, m is preferably 3 or 4.

[0211] In the general formula (2), o is an integer of 2 to 200. From the viewpoint of suppressing uneven drying and suppressing water stains, o is preferably an integer of 3 to 50.

[0212] Examples of the monomer represented by the general formula (2) include polyethylene glycol mono(meth)acrylate, polypropylene glycol mono(meth)acrylate, polytrimethylene glycol mono(meth)acrylate, polytetramethylene glycol mono(meth)acrylate, poly(ethylene glycol·propylene glycol) mono(meth)acrylate, polyethylene glycol·polypropylene glycol mono(meth)acrylate, poly(ethylene glycol·tetramethylene glycol) mono(meth)acrylate, polyethylene glycol·polytetramethylene glycol mono(meth)acrylate, poly(propylene glycol·tetramethylene glycol) mono(meth)acrylate, polypropylene glycol·polytetramethylene glycol mono(meth)acrylate, poly(propylene glycol·1,2-butylene glycol) mono(meth)acrylate, polypropylene glycol·poly1,2-butylene glycol mono(meth)acrylate, poly(ethylene glycol·1,2-butylene glycol) mono(meth)acrylate, Poly(ethylene glycol·poly 1,2-butylene glycol) mono(meth)acrylate, Poly(tetramethylene glycol·1,2-butylene glycol) mono(meth)acrylate, Polytetraethylene glycol·poly 1,2-butylene glycol mono(meth)acrylate, Poly 1,2-butylene glycol mono(meth)acrylate, Poly(ethylene glycol·trimethylene glycol) mono(meth)acrylate, Polyethylene glycol·polytrimethylene glycol mono(meth)acrylate, poly(propylene glycol·trimethylene glycol) mono(meth)acrylate, poly(1,2-butylene glycol·trimethylene glycol) mono(meth)acrylate, poly 1,2-butylene glycol·polytrimethylene glycol mono(meth)acrylate, poly(1,2-butylene glycol·tetramethylene glycol) mono(meth)acrylate, poly 1,2-butylene glycol·polytetramethylene glycol mono(meth)acrylate, etc.In addition, the above "poly(ethylene glycol-propylene glycol)" means a random copolymer of ethylene glycol and propylene glycol, and "polyethylene glycol-polyethylene glycol" means a block copolymer of ethylene glycol and propylene glycol. Commercially available products include NK Ester M-20G, M-40G, M-90G, M-130G, M-230G, AM-90G, AM-130G, and AM-230G manufactured by Shin-Nakamura Chemical Co., Ltd., and Blenmar PE-90, PE-200, PE-350, PP-500, PP-800, PP-1000, 50PEP-300, 55PET-800, 10PPB-500B, AE-200, AE-400, and AP-400 manufactured by NOF Corporation.

[0213] The monomer represented by formula (2) can be used alone or in combination of two or more kinds.

[0214] The content of the monomer unit (d2) represented by general formula (2) is preferably 5 to 80 mass%, and more preferably 15 to 70 mass%, relative to 100 mass% of the copolymer (D1), from the viewpoint of suppressing uneven drying and suppressing water stains.

[0215] The copolymer (D1) may be a copolymer having a monomer unit (d1) represented by general formula (1) and a monomer unit (d2) represented by general formula (2), and the copolymer structure is not particularly limited. For example, a random copolymer, a block copolymer, or a graft copolymer may be mentioned. Among these, a block copolymer is preferable from the viewpoint of suppressing uneven drying and suppressing water stains. When the copolymer (D1) is a block copolymer having a monomer unit (d1) represented by general formula (1) and a monomer unit (d2) represented by general formula (2), the number and arrangement of each block are not particularly limited. For example, when the part consisting of the monomer unit (d1) represented by general formula (1) is block A, and the part consisting of the monomer unit (d2) represented by general formula (2) is block B, the copolymer (D1) may have an arrangement such as an AB block copolymer, an ABA block copolymer, or a BAB block copolymer.

[0216] The method for producing the block copolymer is not particularly limited, and any known method can be used, such as living polymerization methods such as living radical polymerization and living anionic polymerization. Living radical polymerization is described, for example, in JP-A-9-62002 and JP-A-2002-31713, and in P. Lutz, P. Masson et al., Polym. Bull. 12, 79 (1984), BC Anderson, GD Andrews et al., Macromolecules, 14, 1601 (1981), K. Hatada, K. Ute, et al. al, Polym. J. 17, 977 (1985), 18, 1037 (1986), Koichi Migite, Koichi Hatada, Polymer Processing, 36, 366 (1987), Toshinobu Higashimura, Mitsuo Sawamoto, Polymer Research Papers, 46, 189 (1989), M. Kuroki, T. Aida, J. Am. Chem. Soc, 109, 4737 (1987), Takuzo Aida, Shohei Inoue, Organic Synthesis Chemistry, 43, 300 (1985), DY Sogoh, WRHertler et al, Macromolecules, 20, 1473 (1987), etc. Among these, reversible addition-fragmentation chain transfer polymerization (hereinafter, RAFT), atom transfer radical polymerization (hereinafter, ATRP), living radical polymerization using an iodine compound, and living radical polymerization using an organotellurium compound (hereinafter, TERP) are preferred. Specifically, the copolymer (D1) of the present invention can be synthesized by, for example, the methods described in WO 2021 / 131726, WO 2022 / 050062, WO 2022 / 244586, etc.

[0217] [Other monomer units (d3)] The copolymer (D1) may have a monomer unit (d3) other than the monomer unit (d1) represented by general formula (1) and the monomer unit (d2) represented by general formula (2) (hereinafter also referred to as other monomer unit (d3)).

[0218] The monomer forming the other monomer unit (d3) (hereinafter also referred to as the other monomer) is not particularly limited, and examples thereof include a monomer represented by general formula (1) and a monomer copolymerizable with the monomer represented by general formula (2).

[0219] Examples of other monomers include methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, isopropyl (meth)acrylate, n-butyl (meth)acrylate, isobutyl (meth)acrylate, tert-butyl (meth)acrylate, n-pentyl (meth)acrylate, n-hexyl (meth)acrylate, n-heptyl (meth)acrylate, n-octyl (meth)acrylate, 2-ethylhexyl acrylate, decyl (meth)acrylate, and dodecyl (meth)acrylate. Acrylate, stearyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 2-hydroxybutyl (meth)acrylate, 2,3-dihydroxypropyl (meth)acrylate, benzyl (meth)acrylate, 2-phenoxymethyl (meth)acrylate, 2-phenoxyethyl (meth)acrylate, 2-hydroxy-3-phenoxypropyl (meth)acrylate, cyclohexyl (meth)acrylate, methylcyclohexyl (meth)acrylate acrylate, 4-tert-butylcyclohexyl (meth)acrylate, 1,4-cyclohexanedimethanol mono (meth)acrylate, isobornyl (meth)acrylate, dicyclopentanyl (meth)acrylate, dicyclopentenyloxyethyl (meth)acrylate, dicyclopentenyl (meth)acrylate, 1-adamantyl (meth)acrylate, 2-adamantyl (meth)acrylate, 2-methyl-2-adamantyl (meth)acrylate, 3-hydroxy-1-adamantyl (meth)acrylate acrylate, 2-isopropyl-2-adamantyl (meth)acrylate, dimethyl adamantyl (meth)acrylate, methyl vinyl ether, ethyl vinyl ether, n-propyl vinyl ether, isopropyl vinyl ether, n-butyl vinyl ether, isobutyl vinyl ether, 2-hydroxyethyl allyl ether, 4-hydroxybutyl allyl ether, glycerol monoallyl ether, styrene, α-methylstyrene, p-methylstyrene, p-methoxystyrene, N,N-dimethylacrylamide, N,Examples of the maleimide include N-diethylacrylamide, N-isopropylacrylamide, acroylmorpholine, methylmaleimide, ethylmaleimide, propylmaleimide, and butylmaleimide.

[0220] The other monomers can be used alone or in combination of two or more kinds.

[0221] The copolymer (D1) may also have a thermal crosslinkable group and / or a polymerizable unsaturated group. Examples of the thermal crosslinkable group include an epoxy group, an oxetanyl group, and a blocked isocyanate group. The polymerizable unsaturated group can be introduced by, for example, synthesizing the copolymer (D1) using a monomer represented by general formula (1), a monomer represented by general formula (2), and other monomers having a hydroxyl group, and then reacting the copolymer (D1) with a compound having a functional group and a polymerizable unsaturated group that reacts with the hydroxyl group. Examples of the compound having the functional group and the polymerizable unsaturated group include 2-(meth)acryloylethyl isocyanate, 2-(meth)acryloyloxyethyl isocyanate, and 1,1-bis[methacryloyloxy]ethyl isocyanate.

[0222] From the viewpoint of the environment, it is preferable that the copolymer (D1) of the present invention is substantially free of fluorine atoms. Here, "substantially free of fluorine atoms" means that the content of fluorine atoms is 3% by mass or less, preferably 1% by mass or less, and more preferably 0.1% by mass or less, based on 100% by mass of the copolymer (D1).

[0223] The weight average molecular weight of the copolymer (D1) is preferably from 5,000 to 40,000.

[0224] The number average molecular weight of the copolymer (D1) is preferably from 2,000 to 20,000.

[0225] The average molecular weight distribution (weight average molecular weight / number average molecular weight) of the copolymer (D1) is preferably from 1.0 to 3.0.

[0226] The copolymer (D1) can be used alone or in combination of two or more kinds.

[0227] The content of the copolymer (D1) is preferably from 0.005 to 2.0 mass %, and more preferably from 0.01 to 1.0 mass %, based on 100 mass % of the nonvolatile content of the photosensitive composition.

[0228] (Leveling agent (D2) other than copolymer (D1)) The photosensitive composition of the present invention may contain a leveling agent (D2) other than the copolymer (D1) (hereinafter, also simply referred to as other leveling agent (D2)). Examples of the other leveling agent (D2) include the leveling agents described above. From the viewpoint of suppressing defects such as pinholes, the other leveling agent (D2) is preferably a silicone-based leveling agent or an acrylic-based leveling agent.

[0229] [Organic solvent (E)] The photosensitive composition of the present invention contains an organic solvent (E).

[0230] The organic solvent (E) is not particularly limited, and known compounds can be used. For example, 1,2,3-trichloropropane, 1-methoxy-2-propanol, ethyl lactate, 1,3-butanediol, 1,3-butylene glycol, 1,3-butylene glycol diacetate, 1,4-dioxane, 2-heptanone, 2-methyl-1,3-propanediol, 3,5,5-trimethyl-2-cyclohexen-1-one, 3,3,5-trimethylcyclohexanone, 3-ethoxyethyl propionate, 3-methyl-1,3-butanediol, 3-methoxy-3-methyl-1-butanol, 3-methoxy-3-methyl butyl acetate, 3-methoxybutanol, 3-methoxybutyl acetate, 4-heptanone, m-xylene, m-diethylbenzene, m-dichlorobenzene, N,N-dimethylacetamide, N,N-dimethylformamide, n-butyl alcohol, n-butylbenzene, n-propyl acetate, N-methylpyrrolidone, o-xylene, toluene, o-chlorotoluene, benzene, o-diethylbenzene, o-dichlorobenzene, p-chlorotoluene, p-diethylbenzene, sec-butylbenzene, tert-butyl Benzene, γ-butyrolactone, isobutyl alcohol, isophorone, ethylene glycol diethyl ether, ethylene glycol dibutyl ether, ethylene glycol monoisopropyl ether, ethylene glycol monoethyl ether, ethylene glycol monoethyl ether acetate, ethylene glycol monotertiary butyl ether, ethylene glycol monobutyl ether, ethylene glycol monobutyl ether acetate, ethylene glycol monopropyl ether, ethylene glycol monohexyl ether, ethylene glycol monomethyl ether, ethylene glycol monomethyl ether acetate, diisobutyl ketone, diethylene glycol diethyl ether, diethylene glycol dimethyl ether, diethylene glycol monoisopropyl ether, diethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether, diethylene glycol monobutyl ether acetate, diethylene glycol monomethyl ether, cyclohexanol, cyclohexanol acetate, cyclohexanone,Dipropylene glycol dimethyl ether, dipropylene glycol methyl ether acetate, dipropylene glycol monoethyl ether, dipropylene glycol monobutyl ether, dipropylene glycol monopropyl ether, dipropylene glycol monomethyl ether, diacetone alcohol, triacetin, tripropylene glycol monobutyl ether, tripropylene glycol monomethyl ether, propylene glycol diacetate, propylene glycol phenyl ether, propylene glycol monoethyl ether, propylene glycol monoethyl ether acetate, propylene glycol monobutyl ether, propylene glycol monopropyl ether, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether propionate, benzyl alcohol, methyl isobutyl ketone, methylcyclohexanol, n-amyl acetate, n-butyl acetate, isoamyl acetate, isobutyl acetate, propyl acetate, dibasic acid esters, etc.,

[0231] From the viewpoint of environmental considerations, the photosensitive composition of the present invention preferably does not substantially contain organic solvents that are aromatic hydrocarbons (toluene, xylene, benzene, chlorobenzene, etc.) "Substantially not contained" means that the content of such organic solvents in the photosensitive composition is 50 ppm by mass or less, preferably 30 ppm by mass or less, and more preferably 10 ppm by mass or less.

[0232] The organic solvent (E) can be used alone or in combination of two or more kinds.

[0233] The content of the organic solvent (E) is preferably such that the nonvolatile content of the photosensitive composition is 5 to 60% by mass.

[0234] (Organic solvents with a boiling point of 100°C or higher and less than 150°C (E1)) The photosensitive composition of the present invention contains an organic solvent (E1) having a boiling point of 100°C or higher and lower than 150°C as the organic solvent (E).

[0235] Specific examples of the organic solvent (E1) include 1-methoxy-2-propanol (boiling point 120°C), propylene glycol monomethyl ether (boiling point 121°C), ethylene glycol monomethyl ether (boiling point 125°C), butyl acetate (boiling point 126°C), cyclopentanone (boiling point 130°C), propylene glycol monoethyl ether (boiling point 132°C), ethylene glycol monoethyl ether (boiling point 135°C), amyl acetate (boiling point 142°C), methyl 3-methoxypropionate (boiling point 142°C), methyl lactate (boiling point 144°C), and propylene glycol monomethyl ether acetate (boiling point 145°C). However, the present invention is not limited to these.

[0236] The organic solvent (E1) more preferably contains one or more selected from the group consisting of propylene glycol monomethyl ether, butyl acetate, cyclopentanone, methyl lactate, and propylene glycol monomethyl ether acetate.

[0237] The organic solvent (E1) can be used alone or in combination of two or more kinds.

[0238] The content of the organic solvent (E1) is preferably 60 to 99.5 mass % in 100 mass % of the organic solvent (E).

[0239] (Organic solvents with a boiling point of 150°C or higher and less than 230°C (E2)) The photosensitive composition of the present invention contains, as the organic solvent (E), an organic solvent (E2) having a boiling point of 150°C or higher and lower than 230°C.

[0240] Specifically, the organic solvent (E2) is ethyl lactate (boiling point 155°C), cyclohexanone (boiling point 156°C), 3-methoxy-1-butanol (boiling point 161°C), diethylene glycol dimethyl ether (boiling point 162°C), diacetone alcohol (boiling point 167°C), diisobutyl ketone (boiling point 168°C), 3-ethoxyethyl propionate (boiling point 170°C), 3-methoxybutyl acetate (boiling point 171°C), dipropylene glycol dimethyl ether (boiling point 175°C), propylene glycol (boiling point 188°C), diethylene glycol diethyl ether (boiling point 188°C), dipropylene glycol Examples of the ethanol include ethanol monomethyl ether (boiling point 188°C), 3-methoxy-3-methyl-1-butyl acetate (boiling point 188°C), propylene glycol diacetate (boiling point 190°C), ethylene glycol monobutyl ether acetate (boiling point 192°C), diethylene glycol monomethyl ether (boiling point 194°C), ethylene glycol (boiling point 198°C), dipropylene glycol methyl-n-propyl ether (boiling point 203°C), dipropylene glycol methyl ether acetate (boiling point 213°C), and diethylene glycol monoethyl ether acetate (boiling point 216°C). However, the present invention is not limited to these.

[0241] The organic solvent (E2) preferably contains at least one selected from the group consisting of ethyl lactate, cyclohexanone, 3-methoxy-1-butanol, ethyl 3-ethoxypropionate, propylene glycol diacetate, ethylene glycol monobutyl ether acetate, and diethylene glycol monomethyl ether.

[0242] The organic solvent (E2) can be used alone or in combination of two or more kinds.

[0243] The content of the organic solvent (E2) is preferably from 0.5 to 40 mass %, and more preferably from 1 to 30 mass %, in 100 mass % of the organic solvent (E).

[0244] From the viewpoint of suppressing drying unevenness, it is preferable to use two or more organic solvents (E2), and it is more preferable to use an organic solvent having a boiling point of 150° C. or more and less than 180° C. in combination with an organic solvent having a boiling point of 180° C. or more and less than 230° C. in combination. The content of the organic solvent having a boiling point of 180° C. or more and less than 230° C. is preferably 0.5 to 10 mass % in 100 mass % of the organic solvent (E).

[0245] (Organic solvents (E3) other than organic solvents (E1) and (E2)) The photosensitive composition of the present invention can contain an organic solvent (E3) other than the organic solvents (E1) and (E2) (also simply referred to as organic solvent (E3)) within the range not impairing the effects of the present invention.

[0246] [Dye (F)] The photosensitive composition of the present invention further comprises a dye (F).

[0247] The dye (F) is more hydrophilic than the pigment and is more likely to cause water spots, so the effects of the present invention can be easily achieved.

[0248] The dye (F) is not particularly limited, and known compounds can be used. Examples include acid dyes, direct dyes, basic dyes, salt-forming dyes, oil-soluble dyes, disperse dyes, reactive dyes, mordant dyes, vat dyes, and sulfur dyes. In addition, derivatives of these dyes and lake pigments obtained by converting dyes into lakes can also be used.

[0249] The acid dye preferably has an acid group such as a sulfo group or a carboxyl group. In addition, a salt-forming compound which is a salt of an acid dye and a nitrogen-containing compound such as a quaternary ammonium salt compound, a tertiary amine compound, a secondary amine compound, or a primary amine compound is preferred. In addition, a salt-forming compound which is a salt of a resin component having these functional groups and an acid dye is also preferred. In addition, the salt-forming compound is easily modified into a sulfonamide compound to obtain a photosensitive composition having excellent resistance (light resistance, solvent resistance). In addition, a salt-forming compound of an acid dye and a compound having an onium salt group is also preferable because it has excellent resistance (light resistance, solvent resistance). The compound having an onium salt group is preferably a resin having a cationic group.

[0250] Although the basic dye can be used as it is, a salt-forming compound that forms a salt with an organic acid, perchloric acid or a metal salt thereof is preferred. The salt-forming compound of the basic dye is preferred because it has excellent resistance (light resistance, solvent resistance) and affinity with pigments. In addition, the anion component acting as a counter ion in the salt-forming compound of the basic dye is preferably an organic sulfonic acid, an organic sulfuric acid, a fluorine group-containing phosphorus anion compound, a fluorine group-containing boron anion compound, a cyano group-containing nitrogen anion compound, an anion compound having a conjugate base of an organic acid having a halogenated hydrocarbon group, or a salt-forming compound formed with an acid dye. The resistance of the salt-forming compound is further improved when the salt-forming compound contains a polymerizable unsaturated group or a thermally crosslinkable group in the molecule.

[0251] The chemical structure of the dye (F) may be, for example, an azo dye, a disazo dye, an azomethine dye (such as indoaniline dye, indophenol dye), a dipyrromethene dye, a quinone dye (such as benzoquinone dye, naphthoquinone dye, anthraquinone dye, anthrapyridone dye), a carbonium dye (such as diphenylmethane dye, triphenylmethane dye, xanthene dye, acridine dye), a quinoneimine dye (such as oxazine dye, thiazine dye), an azine dye, Examples of the dye structure include those derived from dyes selected from polymethine dyes (oxonol dyes, merocyanine dyes, arylidene dyes, styryl dyes, cyanine dyes, squarylium dyes, croconium dyes, etc.), quinophthalone dyes, phthalocyanine dyes, naphthalocyanine dyes, subphthalocyanine dyes, perinone dyes, indigo dyes, thioindigo dyes, quinoline dyes, nitro dyes, nitroso dyes, rhodamine dyes, and metal complex dyes thereof.

[0252] Among these, from the viewpoint of color properties such as hue, color separation, and color unevenness, a dye structure derived from a dye selected from azo dyes, xanthene dyes, cyanine dyes, triphenylmethane dyes, anthraquinone dyes, dipyrromethene dyes, squarylium dyes, quinophthalone dyes, phthalocyanine dyes, naphthalocyanine dyes, and subphthalocyanine dyes is preferred, and a dye structure derived from a dye selected from xanthene dyes, cyanine dyes, triphenylmethane dyes, anthraquinone dyes, dipyrromethene dyes, and phthalocyanine dyes is more preferred.

[0253] The dye (F) can be used alone or in combination of two or more kinds.

[0254] The content of the dye (F) is preferably from 0.5 to 60 mass %, and more preferably from 1 to 50 mass %, based on 100 mass % of the nonvolatile content of the photosensitive composition.

[0255] Pigment The photosensitive composition of the present invention can contain a pigment (G).

[0256] The pigment (G) is not particularly limited, and a known compound can be used. For example, a chromatic pigment, a white pigment, a black pigment, and a near infrared absorbing pigment can be mentioned. The pigment (G) may be colorless. In the present invention, the solubility of the pigment (G) in 100 g of propylene glycol monomethyl ether acetate at 25° C. is preferably less than 2 g, more preferably less than 1 g, and particularly preferably 0.5 g or less.

[0257] When the photosensitive composition of the present invention is used for a color filter, the pigment (G) is preferably a chromatic pigment. The chromatic pigment may be used alone or in combination of two or more. When the photosensitive composition of the present invention is used for a near-infrared cut filter, the pigment (G) is preferably a near-infrared absorbing pigment. The near-infrared absorbing pigment may be used alone or in combination of two or more. When used for a near-infrared transmission filter, it is preferable to use a black pigment or two or more chromatic pigments in combination to produce black. Furthermore, a near-infrared absorbing pigment may be used in combination.

[0258] (chromatic pigments) The chromatic pigment is not particularly limited, and any known chromatic pigment can be used, for example, a compound classified as a pigment in the Color Index.

[0259] Chromatic 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, 63:1,63:2,64,64:1,68,69,81,81:1,81:2,81:3,81:4,83,88,90:1,101,101:1,104,108,108:1,109,112,113,114,122,123,144,146,147,149,151,166,168,169,170,172,173,174,175,176,177,178,179,1 81,184,185,187,188,190,193,194,200,202,206,207,208,209,210,214,216,220,221,224,230,231,232,233,235,236,237,238,239,242,243,245,247,249,250,251,253,254,255,256,257,258,259,260, Nos. 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, JP 2014-134712 A, and the pigments described in Japanese Patent No. 6368844.

[0260] Examples of orange pigments include CI Pigment Orange 36, 38, 43, 64, 71, and 73.

[0261] CI 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, 1 No. 27,128,129,138,139,147,150,151,152, 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 JP-A-2012-226110.

[0262] Further, examples of yellow pigments include metal azo pigments containing one or more anions selected from the group consisting of azo compounds represented by the following general formula (9) and mono-, di-, tri-, and tetraanions of azo compounds having a tautomeric 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 following general formula (10):

[0263] General formula (9) [ka]

[0264] In general formula (9), R1's each independently represent -OH, -NH2, -NH-CN, an acylamino group, an alkylamino group, or an arylamino group, and R2's each independently represent -OH or -NH2.

[0265] General formula (10) [ka]

[0266] In general formula (10), each R3 independently represents a hydrogen atom or an alkyl group.

[0267] Examples of the metal azo pigment include those described in JP-A-2014-12838, JP-A-2017-171912, JP-A-2017-171913, JP-A-2017-171914, JP-A-2017-171915, and JP-A-2022-61494.

[0268] Examples of green pigments include CI 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, 64, 65, and 66.

[0269] Examples of blue pigments include CI 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, 80, 87, and 88.

[0270] Examples of purple pigments include CI 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, and 50.

[0271] The chromatic pigments can be used alone or in combination of two or more kinds. For example, in the case of black, in addition to using the black pigment described later, two or more chromatic pigments selected from the group consisting of red pigments, yellow pigments, green pigments, blue pigments, and purple pigments can be used (combined) to obtain the color. Examples of the combination include the following modes. (1) Contains yellow and purple pigments. (2) Contains red, yellow, and purple pigments. (3) Contains red, yellow, and blue pigments. (4) Contains red, yellow, and green pigments. (5) Contains yellow pigment, blue pigment, and purple pigment. (6) Contains red pigment, yellow pigment, blue pigment, and purple pigment. (7) Contains yellow pigment, blue pigment, green pigment, and purple pigment.

[0272] An example of the above embodiment (1) is an embodiment in which the yellow pigment contains one or more selected from CI Pigment Yellow 139, 185, 231, and 233, and the purple pigment contains CI Pigment Violet 23. An example of the above embodiment (2) is an embodiment in which the red pigment is one or more selected from CI Pigment Red 177, 254, 291, 295, and 296; the yellow pigment is one or more selected from CI Pigment Yellow 139, 185, 231, and 233; and the purple pigment is CI Pigment Violet 23. An example of the above embodiment (3) is an embodiment containing one or more red pigments selected from CI Pigment Red 177, 254, 291, 295, and 296, one or more yellow pigments selected from CI Pigment Yellow 139, 185, 231, and 233, and one or more blue pigments selected from CI Pigment Blue 15:3, 15:4, and 15:6. An example of the above embodiment (4) is an embodiment containing one or more red pigments selected from CI Pigment Red 177, 254, 291, 295, and 296, one or more yellow pigments selected from CI Pigment Yellow 139, 185, 231, and 233, and one or more green pigments selected from CI Pigment Green 7, 36, 58, 59, and 63. An example of the above embodiment (5) is an embodiment in which the yellow pigment contains one or more selected from CI Pigment Yellow 139, 185, 231, and 233; the blue pigment contains one or more selected from CI Pigment Blue 15:3, 15:4, and 15:6; and the purple pigment contains CI Pigment Violet 23. An example of the above embodiment (6) is an embodiment in which the red pigment contains one or more selected from CI Pigment Red 177, 254, 291, 295, and 296; the yellow pigment contains one or more selected from CI Pigment Yellow 139, 185, 231, and 233; the blue pigment contains one or more selected from CI Pigment Blue 15:3, 15:4, and 15:6; and the purple pigment contains CI Pigment Violet 23. An example of the above embodiment (7) is an embodiment in which the yellow pigment contains one or more selected from CI Pigment Yellow 139, 185, 231, and 233; the blue pigment contains one or more selected from CI Pigment Blue 15:3, 15:4, and 15:6; the green pigment contains one or more selected from CI Pigment Green 7, 36, 58, 59, and 63; and the purple pigment contains CI Pigment Violet 23.

[0273] Table 1 shows the preferred mass ratio (mass %) of each chromatic pigment in each embodiment relative to the total pigment.

[0274] [Table 1]

[0275] The above combinations of chromatic pigments (1) to (7) are preferred when the photosensitive composition of the present invention is used for a near-infrared transmission filter.

[0276] (White pigment) The white pigment is not particularly limited, and any known white pigment can be used. Examples of the white pigment include titanium oxide, magnesium oxide, zirconium oxide, aluminum oxide, antimony oxide, barium sulfate, calcium carbonate, silica, zinc oxide, mica, talc, kaolin, clay, strontium titanate, barium tungstate, zinc phosphate, aluminum hydroxide, aluminum silicate, hollow resin particles, and compounds described in JP2011-075786A, WO2013 / 061621A, JP2015-047520A, and JP2015-164881A. Further, examples of compounds classified as pigments in the Color Index include CI Pigment White 1, 2, 3, 4, 5, 6, 6:1, 7, 8, 10, 11, 12, 13, 14, 15, 16, 17, 18, 18:1, 19, 20, 21, 22, 23, 24, 25, 26, 27, 28, 30, 32, and 33.

[0277] (Black pigment) The black pigment is not particularly limited, and known black pigments can be used, such as carbon black, titanium black, acetylene black, lamp black, graphite, aniline black, cyanine black, perylene black, and compounds described in JP-A-1-170601, JP-A-2-34664, JP-A-2007-302836, JP-T-2010-534726, and JP-T-2012-515233. Further, examples of compounds classified as pigments in the Color Index include CI Pigment Black 1, 6, 7, 12, 20, and 31.

[0278] (Near infrared absorbing pigment) The near-infrared absorbing pigment is a compound having a maximum absorption in the wavelength range of 700 to 2,000 nm, and may be either an organic pigment (also called a near-infrared absorbing organic pigment) or an inorganic pigment (also called a near-infrared absorbing inorganic pigment). In addition, a near-infrared absorbing organic pigment and a near-infrared absorbing inorganic pigment may be used in combination.

[0279] The near infrared absorbing organic pigment is not particularly limited, and known near infrared absorbing organic pigments can be used. For example, cyanine compounds, phthalocyanine compounds, naphthalocyanine compounds, indigo compounds, immonium compounds, anthraquinone compounds, pyrrolopyrrole compounds, squarylium compounds, croconium compounds, porphyrin compounds, etc. can be mentioned. Among these, from the viewpoint of near infrared absorbing property and heat resistance, naphthalocyanine compounds, pyrrolopyrrole compounds, squarylium compounds, and indigo compounds are preferred, and naphthalocyanine compounds, squarylium compounds, and indigo compounds are more preferred.

[0280] Cyanine compounds are disclosed in WO 2006 / 006573, WO 2010 / 073857, JP 2013-241598, JP 2016-113501, JP 2016-113504, etc.; phthalocyanine compounds are disclosed in JP 4-23868, JP 06-192584, JP 2000-63691, WO 2014 / 208514, JP 2022-022070, etc. , JP 2022-110262 A, etc.; naphthalocyanine compounds are described in JP 11-152414 A, JP 2000-86919 A, JP 2009-29955 A, WO 2018 / 186490 A, JP 2022-123689 A, JP 2022-091099 A, etc.; indigo compounds are described in JP 2013-230412 A, etc.; immonium compounds are described in JP 2005-336150 A, JP Anthraquinone compounds are described in JP-A-62-903 and JP-A-1-172458, etc. Pyrrolopyrrole compounds are described in JP-A-2009-263614, JP-A-2010-90313, JP-A-2011-068731, and WO 2021 / 039205; squarylium compounds are described in JP-A-2011-132361 and JP-A-2016 -142891, WO 2017 / 135359, WO 2018 / 225837, JP 2019-001987, WO 2020 / 054718, WO 2020 / 189459, etc.; croconium compounds are described in WO 2019 / 021767; porphyrin compounds are described in JP 2006-209059, WO 2022 / 131191, etc.

[0281] The near infrared absorbing inorganic pigment is not particularly limited, and any known near infrared absorbing inorganic pigment can be used, such as indium tin oxide, antimony tin oxide, zinc oxide, aluminum-doped zinc oxide, fluorine-doped tin dioxide, niobium-doped titanium dioxide, cesium tungsten oxide, lanthanum boride, copper, nickel, silver, gold, or other metal oxide particles or metal particles.

[0282] The pigment (G) can be used alone or in combination of two or more kinds.

[0283] The content of the pigment (G) is preferably from 0.5 to 60 mass %, and more preferably from 1 to 50 mass %, based on 100 mass % of the nonvolatile content of the photosensitive composition.

[0284] The pigment (G) is preferably used in a finely divided state. The method of finely dividing is not particularly limited, and examples thereof include wet grinding, dry grinding, and solution precipitation. Among these, salt milling treatment by a kneader method, which is a type of wet grinding, is preferred. The average primary particle diameter of the finely divided pigment determined by TEM (transmission electron microscope) is preferably 5 to 90 nm. From the viewpoint of dispersibility, the average primary particle diameter is more preferably 10 to 70 nm.

[0285] In the salt milling treatment, a resin may be added as necessary. By adding a resin, the pigment (G) is coated with the resin, and the stability, light resistance, etc. are improved. The type of the resin is not particularly limited, and examples thereof include 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 the resin added is preferably 2 to 200 parts by mass relative to 100 parts by mass of the pigment (G).

[0286] [Pigment derivatives (H)] The photosensitive composition of the present invention may contain a pigment derivative (H), which allows the pigment (G) to be stably dispersed.

[0287] The pigment derivative (H) is not particularly limited, and known compounds can be used. For example, compounds having a structure in which a part of the pigment is substituted with an acidic group, a basic group, a neutral group, etc. can be mentioned. For example, compounds having acidic substituents such as sulfo groups, carboxyl groups, and phosphoric acid groups, and amine salts thereof, compounds having basic substituents such as sulfonamide groups or tertiary amino groups at the terminals, and compounds having neutral substituents such as phenyl groups and phthalimidoalkyl groups can be mentioned. Examples of pigments include diketopyrrolopyrrole compounds, phthalocyanine compounds, anthraquinone compounds, quinacridone compounds, dioxazine compounds, perinone compounds, perylene compounds, thiazine indigo compounds, triazine compounds, benzimidazolone compounds, benzoisoindole compounds, isoindoline compounds, isoindolinone compounds, quinophthalone compounds, naphthol compounds, squarylium compounds, threne compounds, and naphthalocyanine compounds.

[0288] For example, pyrrolopyrrole pigment derivatives are disclosed in JP 2001-220520 A, WO 2009 / 081930 A, WO 2011 / 052617 A, WO 2012 / 102399 A, JP 2017-156397 A, and WO 2018 / 101189 A; phthalocyanine pigment derivatives are disclosed in JP 2007-226161 A, WO 2016 / 163351 A, JP 2017-165820 A, and Japanese Patent No. 5753266 A; and anthraquinone pigment derivatives are disclosed in JP 63-26 4674, JP-A-09-272812, JP-A-10-245501, JP-A-10-265697, JP-A-2007-079094, WO 2009 / 025325; quinacridone pigment derivatives include JP-A-48-54128, JP-A-03-9961, and JP-A-2000-273383; dioxazine pigment derivatives include JP-A-2011-162662; thiazine indigo pigment derivatives include JP-A-2007-314785; triazine pigment derivatives include , JP-A-61-246261, JP-A-11-199796, JP-A-2003-165922, JP-A-2003-168208, JP-A-2004-217842, JP-A-2007-314681, as benzoisoindole pigment derivatives, JP-A-2009-57478, as quinophthalone pigment derivatives, JP-A-2003-167112, JP-A-2006-291194, JP-A-2008-31281, JP-A-2012-226110, as naphthol pigment derivatives, Examples of squarylium pigment derivatives include those described in JP-A-2012-208329 and JP-A-2014-5439; examples of azo pigment derivatives include those described in JP-A-2001-172520 and JP-A-2012-172092; examples of acidic substituents include those described in JP-A-2004-307854; and examples of basic substituents include those described in JP-A-2002-201377, JP-A-2003-171594, JP-A-2005-181383, JP-A-2005-213404, and the like.In these documents, the term "derivative," "dye derivative," "dispersant," "dispersing aid," "pigment dispersant," or simply "compound" may be used, but these terms are synonymous with the pigment derivative (H).

[0289] The pigment derivative (H) is preferably added during the micronization of the pigment (G) or during the dispersion treatment of the pigment (G).The average primary particle size of the pigment derivative (H) is preferably 5 to 200 nm.

[0290] The pigment derivative (H) can be used alone or in combination of two or more kinds.

[0291] The content of the pigment derivative (H) is preferably from 1 to 50 parts by mass, and more preferably from 2 to 40 parts by mass, based on 100 parts by mass of the pigment (G).

[0292] [Dispersion resin (I)] The photosensitive composition of the present invention may contain a dispersing resin (I). This allows the pigment (G) to be stably dispersed. In this specification, the dispersing resin (I) is not included in the alkali-soluble resin (A).

[0293] The dispersing resin (I) is preferably a resin having an adsorptive group having a high affinity for the pigment (G). The adsorptive group preferably has at least one type of basic group and acidic group.

[0294] Examples of the basic group include a primary amino group, a secondary amino group, a tertiary amino group, a quaternary ammonium base, and a group containing a nitrogen atom such as a nitrogen-containing heterocycle.

[0295] Examples of the acidic group include a carboxyl group, a phosphoric acid group, and a sulfonic acid group.

[0296] Examples of the resin type of the dispersion resin (I) include urethane resins, polycarboxylates such as polyacrylates, unsaturated polyamides, polycarboxylic acids, polycarboxylate (partial) amine salts, polycarboxylate ammonium salts, polycarboxylate alkylamine salts, polysiloxanes, long-chain polyaminoamide phosphates, hydroxyl-containing polycarboxylates, and modified products thereof, amides and salts thereof formed by the reaction of poly(lower alkylene imines) 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 alcohols, and polyvinylpyrrolidone, polyesters, modified polyacrylates, ethylene oxide / propylene oxide adducts, and phosphates.

[0297] Examples of the structure of the dispersing resin (I) include a random structure, a block structure, a graft structure, a comb structure, and a star structure. Among these, from the viewpoint of dispersion stability, the block structure, the graft structure, and the comb structure are preferred.

[0298] From the viewpoint of resistance, the dispersing resin (I) preferably has a thermally crosslinkable group and / or a polymerizable unsaturated group. Examples of the thermally crosslinkable group include a cyclic ether group, a blocked isocyanate group, an acetoacetoxy group, an alkoxysilyl group, and a tertiary alkyl group.

[0299] Examples of the dispersing resin (I) include the resins described in paragraphs 0122 to 0155 of WO 2013 / 175978, the resins described in paragraphs 0317 to 0321 of JP 2019-78878 A, the resins described in paragraphs 0083 of WO 2018 / 139534, the resins described in paragraphs 0167 to 0191 of WO 2019 / 163505, the resins described in paragraphs 0299 ​​to 0310 of WO 2021 / 131927, the resins described in paragraphs 0080 to 0085 of WO 2022 / 102367, and the resins described in paragraphs 0099 to 0109 of WO 2022 / 172607.

[0300] Commercially available dispersion resins (I) 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, 2150, 2155, 2163, 2164, Anti-Terra-U203, 204, and BYK-P1 manufactured by BYK-Chemie Japan Co., Ltd. 04, P104S, 220S, Lactimon, Lactimon-WS, Bykumen, etc., SOLSPERSE-3000, 9000, 13000, 13240, 13650, 13940, 16000, 17000, 18000, 20000, 21000, 24000, 26000, 27000, 28000, 31845, 32000, 32500, 32550, 33500, 32600, 34750, 35100, 36600, 38500, 41000, 41090, 53095, 55000, 56000, 7 EFKA-6500 manufactured by BASF Japan, EFKA-46, 47, 48, 452, 4008, 4009, 4010, 4015, 4020, 4047, 4050, 4055, 4060, 4080, 4400, 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 manufactured by Ajinomoto Fine-Techno Co., Ltd., Aji-Super - PA111, PB711, PB821, PB822, PB824, and the like, resins described in JP2008-029901A, JP2009-155406A, JP2010-185934A, JP2011-157416A, WO2008 / 007776, JP2008-029901A, JP2009-155406A, JP2010-185934A, JP2011-157416A, JP2009-251481A, JP2007-23195A, JP1996-143651A, and the like.

[0301] The dispersing resin (I) can be used alone or in combination of two or more kinds.

[0302] From the viewpoint of dispersion stability, the content of the dispersing resin (I) is preferably from 3 to 200 parts by mass, and more preferably from 5 to 150 parts by mass, relative to 100 parts by mass of the pigment (G).

[0303] [Sensitizer (J)] The photosensitive composition of the present invention can contain a sensitizer (J).

[0304] Examples of the sensitizer (J) include polymethine dyes such as chalcone compounds, unsaturated ketones typified by dibenzalacetone, 1,2-diketone compounds typified by benzil and camphorquinone, benzoyl compounds, fluorene compounds, naphthoquinone compounds, anthraquinone compounds, xanthene compounds, thioxanthene compounds, xanthone compounds, thioxanthone compounds, coumarin compounds, ketocoumarin compounds, cyanine compounds, merocyanine compounds, and oxonol compounds, acridine compounds, azine compounds, thiazine compounds, oxazine compounds, indoline compounds, azulene compounds, and azulenium compounds. , squarylium compounds, porphyrin compounds, tetraphenylporphyrin compounds, triarylmethane compounds, tetrabenzoporphyrin compounds, tetrapyrazinoporphyrazine compounds, phthalocyanine compounds, tetraazaporphyrazine compounds, tetraquinoxalylporphyrazine compounds, naphthalocyanine compounds, subphthalocyanine compounds, pyrylium compounds, thiopyrylium compounds, tetraphylline compounds, annulene compounds, spiropyran compounds, spirooxazine compounds, thiospiropyran compounds, metal arene complexes, organic ruthenium complexes, or benzophenone compounds. Among these, thioxanthone compounds and benzophenone compounds are preferred.

[0305] The sensitizer (J) can be used alone or in combination of two or more kinds.

[0306] The content of the sensitizer (J) is preferably from 10 to 400 parts by mass, and more preferably from 20 to 300 parts by mass, based on 100 parts by mass of the polymerization initiator (C).

[0307] [Thermal crosslinkable compound (K)] The photosensitive composition of the present invention may contain a thermally crosslinkable compound (K).

[0308] The thermal crosslinking compound (K) is not particularly limited as long as it is a compound having a thermal crosslinking group, and a known compound can be used. For example, a compound having an epoxy group, a compound having a blocked isocyanate group, a compound having an oxetanyl group, a compound having a methylol group, a compound having a phenol group, a compound having an alkoxyalkyl group, etc. can be mentioned.

[0309] (Epoxy compounds) Examples of epoxy compounds include polycondensates of bisphenols (bisphenol A, bisphenol F, bisphenol S, biphenol, bisphenol AD, etc.), phenols (phenol, alkyl-substituted phenol, aromatic-substituted phenol, naphthol, alkyl-substituted naphthol, dihydroxybenzene, alkyl-substituted dihydroxybenzene, dihydroxynaphthalene, etc.) and various aldehydes (formaldehyde, acetaldehyde, alkyl aldehyde, benzaldehyde, alkyl-substituted benzaldehyde, hydroxybenzaldehyde, naphthaldehyde, glutaraldehyde, phthalaldehyde, crotonaldehyde, cinnamaldehyde, etc.), polycondensates of phenols and various diene compounds (dicyclopentadiene, terpenes, vinylcyclohexene, norbornadiene, vinylnorbornene, tetrahydroindene, divinylbenzene ... Examples of the epoxy resins include polymers of phenols and ketones (acetone, methyl ethyl ketone, methyl isobutyl ketone, acetophenone, benzophenone, etc.), polycondensates of phenols and aromatic dimethanols (benzene dimethanol, α,α,α',α'-benzene dimethanol, biphenyl dimethanol, α,α,α',α'-biphenyl dimethanol, etc.), polycondensates of phenols and aromatic dichloromethyls (α,α'-dichloroxylene, bischloromethylbiphenyl, etc.), polycondensates of bisphenols and various aldehydes, glycidyl ether epoxy resins obtained by glycidylating alcohols, alicyclic epoxy resins, heterocyclic epoxy resins, aliphatic epoxy resins, glycidyl amine epoxy resins, and glycidyl ester epoxy resins.

[0310] Examples of the epoxy compound include 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-5,5-spiro-3,4-epoxy)cyclohexane-metadioxane, bis(3,4-epoxycyclohexylmethyl-3,4-epoxy ... bis(3,4-epoxycyclohexylmethyl)adipate, 3,4-epoxy-6-methylcyclohexylcarboxylate, methylene bis(3,4-epoxycyclohexane), dicyclopentadiene diepoxide, ethylene bis(3,4-epoxycyclohexanecarboxylate), dioctyl epoxyhexahydrophthalate, di-2-ethylhexyl epoxyhexahydrophthalate, 1-epoxyethyl-3,4-epoxycyclohexane, 1,2-epoxy-2-epoxyethylcyclohexane, butanetetracarboxylate tetra(3,4-epoxycyclohexylmethyl) modified ε-caprolactone, 2,2-bis(hydroxymethyl)-1-butanol 1,2-epoxy-4-(2-oxiranyl)cyclohexane adduct, and the like.

[0311] Commercially available epoxy compounds include, for example, Epicoat 807, 815, 825, 827, 828, 190P, and 191P manufactured by Yuka Shell Epoxy Co., Ltd., and TECHMORE manufactured by Mitsui Chemicals, Inc. VG3101L, EPPN-201, 501H, 502H, EOCN-102S, 103S, 104S, 1020 manufactured by Nippon Kayaku Co., Ltd., Epicoat 1004, 1256, JER1032H60, 157S65, 157S70, 152, 154 manufactured by Japan Epoxy Resins Co., Ltd., Celloxide 2021, EHPE-3150, Epolead GT401 manufactured by Daicel Chemical Industries, Denacol EX-211, 212, 252, 313, 314, 321, 411, 421, 512, 521, 611, 612, 614, 614B, 622, 711, 721 manufactured by Nagase ChemteX Corporation, TEPIC-L, H, S manufactured by Nissan Chemical Industries, and EPICLON manufactured by 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, and HP-9500.

[0312] The epoxy compound is preferably a compound having 2 to 50 epoxy groups in the molecule.

[0313] The epoxy equivalent of the epoxy compound is preferably 50 to 400 g / eq, more preferably 100 to 200 g / eq. The epoxy equivalent is defined as the mass of an epoxy compound containing one equivalent of an epoxy group.

[0314] The epoxy compounds can be used alone or in combination of two or more kinds.

[0315] The content of the epoxy compound is preferably from 0.5 to 20 mass %, and more preferably from 1 to 15 mass %, based on 100 mass % of the nonvolatile content of the photosensitive composition.

[0316] (Oxetane Compounds) The oxetane compound is a known compound having an oxetane group. Examples of the oxetane compound include monofunctional oxetane compounds, bifunctional oxetane compounds, and trifunctional or higher oxetane compounds.

[0317] Examples of monofunctional oxetane compounds include (3-ethyloxetan-3-yl)methyl acrylate, (3-ethyloxetan-3-yl)methyl methacrylate, 3-ethyl-3-hydroxymethyloxetane, 3-ethyl-3-(2-ethylhexyloxymethyl)oxetane, 3-ethyl-3-(phenoxymethyl)oxetane, 3-ethyl-3-(2-methacryloxymethyl)oxetane, and 3-ethyl-3-{[3-(triethoxysilyl)propoxy]methyl}oxetane.

[0318] Examples of commercially available products include OXE-10,30 manufactured by Osaka Organic Chemical Industry Co., Ltd. and OXT-101,212 manufactured by Toagosei Co., Ltd.

[0319] Examples of the bifunctional oxetane compound include 4,4'-bis[(3-ethyl-3-oxetanyl)methoxymethyl]biphenyl), 1,4-bis[(3-ethyl-3-oxetanyl)methoxymethyl]benzene, 1,4-bis{[(3-ethyl-3-oxetanyl)methoxy]methyl}benzene, di[1-ethyl(3-oxetanyl)]methyl ether, di[1-ethyl(3-oxetanyl)]methyl ether 3-ethyl-3-hydroxymethyl oxetane, 3- Ethyl-3-(2-ethylhexyloxymethyl)oxetane, 3-ethyl-3-(2-phenoxymethyl)oxetane, 3,7-bis(3-oxetanyl)-5-oxa-nonane, 1,2-bis[(3-ethyl-3-oxetanylmethoxy)methyl]ethane, 1,3-bis[(3-ethyl-3-oxetanylmethoxy)methyl]propane, ethyleneglycol bis(3-ethyl-3-oxetanylmethyl)ether, dicyclopentenyl bis(3-ethyl- 3-oxetanylmethyl) ether, triethylene glycol bis(3-ethyl-3-oxetanylmethyl) ether, tetraethylene glycol bis(3-ethyl-3-oxetanylmethyl) ether, 1,4-bis(3-ethyl-3-oxetanylmethoxy)butane, 1,6-bis(3-ethyl-3-oxetanylmethoxy)hexane, polyethylene glycol bis(3-ethyl-3-oxetanylmethyl) ether, ethylene oxide (EO)-modified bisphenol A bis(3-ethyl-3-oxetanylmethyl) ether, propylene oxide (PO)-modified bisphenol A bis(3-ethyl-3-oxetanylmethyl) ether, EO-modified hydrogenated bisphenol A bis(3-ethyl-3-oxetanylmethyl) ether, PO-modified hydrogenated bisphenol A bis(3-ethyl-3-oxetanylmethyl) ether, EO-modified bisphenol F(3-ethyl-3-oxetanylmethyl) ether, and the like.

[0320] Examples of commercially available products include OXBP and OXTP manufactured by Ube Industries, and OXT-121 and 221 manufactured by Toagosei.

[0321] Examples of the trifunctional or higher oxetane compounds include pentaerythritol tris(3-ethyl-3-oxetanylmethyl)ether, pentaerythritol tetrakis(3-ethyl-3-oxetanylmethyl)ether, dipentaerythritol hexa(3-ethyl-3-oxetanylmethyl)ether, dipentaerythritol pentakis(3-ethyl-3-oxetanylmethyl)ether, dipentaerythritol tetrakis(3-ethyl-3-oxetanylmethyl)ether, and caprolactone-modified dipentaerythritol. Examples of such polymers include erythritol hexa(3-ethyl-3-oxetanylmethyl) ether, caprolactone-modified dipentaerythritol pentakis(3-ethyl-3-oxetanylmethyl) ether, ditrimethylolpropane tetrakis(3-ethyl-3-oxetanylmethyl) ether, resins containing an oxetane group (e.g., the oxetane-modified phenol novolac resin described in Japanese Patent No. 3783462), and polymers obtained by radical polymerization of (meth)acrylic monomers such as the above-mentioned OXE-30.

[0322] The oxetane compounds can be used alone or in combination of two or more kinds.

[0323] The content of the oxetane compound is preferably from 0.5 to 20 mass %, and more preferably from 1 to 15 mass %, based on 100 mass % of the nonvolatile content of the photosensitive composition.

[0324] (Melamine compounds) The melamine compound is a compound having a melamine ring structure, and is preferably a compound having a methylol group.

[0325] Examples of commercially available products include Nikalac MW-30HM, MW-390, MW-100LM, MX-750LM, MW-30M, MW-30, MW-22, MS-21, MS-11, MW-24X, MS-001, MX-002, MX-730, MX-750, MX-708, MX-706, MX-042, MX-45, MX-500, MX-520, MX-43, MX-417, and MX-410 manufactured by Sanwa Chemical Co., Ltd., and Cymel 232, 235, 236, 238, 285, 300, 301, 303, 350, and 370 manufactured by Nippon Cytec Industries Co., Ltd.

[0326] The melamine compounds can be used alone or in combination of two or more kinds.

[0327] The content of the melamine compound is preferably from 0.01 to 10 mass %, and more preferably from 0.1 to 5 mass %, based on 100 mass % of the nonvolatile content of the photosensitive composition.

[0328] (Blocked isocyanate compound) A blocked isocyanate compound is a compound obtained by reacting a compound having two or more isocyanate groups in the molecule with a blocking agent.

[0329] Examples of compounds having two or more isocyanate groups in the molecule include compounds having an aliphatic structure, such as butane-1,4-diisocyanate, hexamethylene diisocyanate, isopropylene 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(isocyanatemethyl)cyclohexane, methylcyclohexane diisocyanate, norbornane diisocyanate, and bis(isocyanatemethyl)cyclohexane; Examples of the aromatic compounds include 1,5-naphthylene diisocyanate, 4,4'-diphenylmethane diisocyanate, 4,4'-diphenyldimethylmethane diisocyanate, 4,4'-dibenzyl isocyanate, dialkyl diphenylmethane diisocyanate, tetraalkyl diphenylmethane diisocyanate, 1,3-phenylene diisocyanate, 1,4-phenylene diisocyanate, 2,4-toluene diisocyanate, 2,6-toluene diisocyanate, xylylene diisocyanate, m-tetramethyl xylylene diisocyanate, 4,4-diphenylmethane diisocyanate, tolylene diisocyanate, bischloromethyl diphenylmethane diisocyanate, 2,6-diisocyanate-benzyl chloride, and bis(isocyanate methyl)benzene. Further, biuret, isocyanurate, adduct and allophanate forms of these compounds are also included.

[0330] Examples of the blocking agent include the above-mentioned compounds. Among these, at least one selected from the group consisting of oxime compounds, lactam compounds, phenol compounds, alcohol compounds, amine compounds, active methylene compounds, pyrazole compounds, mercaptan compounds, imidazole compounds, and imide compounds is preferred.

[0331] Examples of commercially available products include Duranate SBN-70D, SBB-70P, SBF-70E, TPA-B80E, 17B-60P, MF-B60B, E402-B80B, and MF-K60B manufactured by Asahi Kasei Corporation; Takenate B-882, B-830, B-815N, and B-846 manufactured by Mitsui Chemicals, Inc.; Coronate BI-301, 2507, and 2554 manufactured by Tosoh Corporation; and BI7960, BI7961, BI7982, BI7991, BI7992, BI7950, BI7951, and BI7990 manufactured by Baxenden.

[0332] The blocked isocyanate compounds can be used alone or in combination of two or more kinds.

[0333] The content of the blocked isocyanate compound is preferably from 0.1 to 20 mass %, and more preferably from 0.5 to 15 mass %, based on 100 mass % of the nonvolatile content of the photosensitive composition.

[0334] The thermally crosslinkable compound (K) can be used alone or in combination of two or more kinds.

[0335] [Thermal crosslinking accelerator] The photosensitive composition of the present invention can be used in combination with a thermal crosslinking accelerator to aid in the curing of the thermal crosslinking compound (K). Examples of the thermal crosslinking accelerator include amine compounds, acid anhydrides, active esters, carboxylic acid compounds, and sulfonic acid compounds. Examples of the curing agent include amine compounds (e.g., dicyandiamide, benzyldimethylamine, 4-(dimethylamino)-N,N-dimethylbenzylamine, 4-methoxy-N,N-dimethylbenzylamine, 4-methyl-N,N-dimethylbenzylamine, etc.), quaternary ammonium salt compounds (e.g., triethylbenzylammonium chloride, etc.), blocked isocyanate compounds (e.g., dimethylamine, etc.), imidazole derivatives, bicyclic amidine compounds and their salts (e.g., imidazole, 2-methylimidazole, 2-ethylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, 4-phenylimidazole, 1-cyanoethyl-2-phenylimidazole, 1-(2-cyanoethyl)-2-ethyl-4-methylimidazole, etc.), phosphorus compounds (e.g., triphenylphosphine, etc.), S-triazine derivatives (e.g., 2,4-diamino-6-methacryloyloxyethyl-S-triazine, 2-vinyl-2,4-diamino-S-triazine, 2-vinyl-4,6-diamino-S-triazine·isocyanuric acid adduct, 2,4-diamino-6-methacryloyloxyethyl-S-triazine·isocyanuric acid adduct, etc.).

[0336] The thermal crosslinking accelerators can be used alone or in combination of two or more kinds.

[0337] The content of the thermal crosslinking accelerator is preferably 0.01 to 15 parts by mass relative to 100 parts by mass of the thermal crosslinkable compound (K).

[0338] [Thiol-based chain transfer agent (L)] The photosensitive composition of the present invention may contain a thiol chain transfer agent (L).

[0339] Examples of the thiol-based chain transfer agent (L) include monofunctional thiol compounds such as thiophenol, 2-mercaptobenzothiazole, 2-mercaptobenzimidazole, 2-mercaptobenzoxazole, 2-mercapto-5-methoxybenzothiazole, 2-mercapto-5-benzimidazole, butanethiol, octanethiol, 1-dodecanethiol, methyl 3-mercaptopropionate, ethyl 3-mercaptopropionate, octyl 3-mercaptopropionate, and 2-ethylhexyl 3-mercaptopropionate; Monofunctional thiol compounds having a hydroxyl group or an acidic group, 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 tetrakis thioglycolate, pentaerythritol tetrakis(3-mercaptopropionate), trimercaptopropionic acid tris(2-hydroxyethyl)isocyanate, 1,4-dimethylmercaptobenzene, 2,4,6-trimercapto-s-triazine, and 2-(N,N-dibutylamino)-4,6-dimercapto-s-triazine.

[0340] The thiol chain transfer agent (L) can be used alone or in combination of two or more kinds.

[0341] The content of the thiol chain transfer agent (L) is preferably from 0.5 to 10% by mass in 100% by mass of the nonvolatile content of the photosensitive composition.

[0342] [Silane coupling agent (M)] From the viewpoint of adhesion, the photosensitive composition of the present invention preferably contains a silane coupling agent (M), which is presumed to react with functional groups on the substrate surface or functional groups of other components contained in the photosensitive composition, improving adhesion.

[0343] The silane coupling agent (M) is a compound having a hydrolyzable group and other functional groups. The hydrolyzable group is a group that is directly bonded to a silicon atom and generates a siloxane bond by at least one of hydrolysis and condensation reactions. Examples of the hydrolyzable group include a halogen atom, an alkoxy group, and an acyloxy group. Among these, an alkoxy group is preferred. From the viewpoint of reactivity, the alkoxy group is preferably a methoxy group or an ethoxy group. Examples of the other functional groups include an epoxy group, an amino group, a vinyl group, a (meth)acryloyl group, an isocyanate group, an isocyanurate group, a mercapto group, an oxetanyl group, a styryl group, and a ureido group. In this specification, the silane coupling agent (M) is not included in the polymerizable compound (B).

[0344] Examples of the silane coupling agent (M) include 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. hydrochloride, vinyltrimethoxysilane, vinyltriethoxysilane, 3-methacryloxypropylmethyldimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropylmethyldiethoxysilane, 3-methacryloxypropyltriethoxysilane, 3-acryloxypropyltrimethoxysilane, 3-isocyanatepropyltriethoxysilane, tris-(trimethoxysilylpropyl)isocyanurate, 3-mercaptopropylmethyldimethoxysilane, 3-mercaptopropyltrimethoxysilane, p-styryltrimethoxysilane, 3-ureidopropyltrialkoxysilane, and the like.

[0345] Commercially available silane coupling agents (M) 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, and 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, X-12-1048, X-12-50, etc.

[0346] The silane coupling agent (M) may be a polymer type, such as a polysiloxane type or an organic polymer type.

[0347] The polysiloxane type is a compound in which the hydrolyzable group and the other functional groups are bonded to a polymer having a polysiloxane skeleton in the main chain. 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.

[0348] The organic polymer type is a silane coupling agent (M) in which the hydrolyzable group and the other functional groups are bonded to an organic polymer whose main chain is an organic structure. Commercially available organic polymer type products include X-12-9815, X-12-9845, X-12-1154, X-12-972F, and X-12-1159L manufactured by Shin-Etsu Silicone Co., Ltd.

[0349] The silane coupling agents (M) can be used alone or in combination of two or more kinds.

[0350] The content of the silane coupling agent (M) is preferably from 0.05 to 10% by mass in 100% by mass of the nonvolatile content of the photosensitive composition.

[0351] (Compound (M1) represented by general formula (11)) The silane coupling agent (M) preferably contains a compound (M1) represented by the following general formula (11). The compound (M1) represented by the general formula (11) has a urethane bond, and therefore forms hydrogen bonds between the urethane bonds and with functional groups of other components contained in the photosensitive composition, forming a strong film. In addition, it is presumed that the urethane bond has flexibility, resulting in a strong yet flexible film.

[0352] General formula (11) [ka]

[0353] In general formula (11), R1 each independently represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, R2 represents an alkylene group having 1 to 8 carbon atoms, Q represents a group represented by any one of the following general formulae (Q-1) to (Q-4), and n represents an integer of 1 to 10.

[0354] [ka]

[0355] In the general formula (Q-1), R3 represents an alkylene group having 1 to 8 carbon atoms. In the general formulae (Q-1) to (Q-4), R4 each independently represents a hydrogen atom or a methyl group. * represents a bond to an oxygen atom.

[0356] In the general formula (11), all of the three R1s are preferably a methyl group.

[0357] In the general formula (11), Q is preferably any of the general formulae (Q-1) to (Q-3).

[0358] The molecular weight (formula weight) or weight average molecular weight of the compound (M1) represented by the general formula (11) is preferably from 100 to 3,000, more preferably from 150 to 1,500.

[0359] The acid value of the compound (M1) represented by the general formula (11) is preferably 10 mgKOH / g or less.

[0360] The compound (M1) represented by the general formula (11) can be used alone or in combination of two or more kinds.

[0361] The content of the compound (M1) represented by the general formula (11) is preferably from 0.05 to 10% by mass in 100% by mass of the nonvolatile content of the photosensitive composition.

[0362] [Ultraviolet absorber (N)] The photosensitive composition of the present invention may contain an ultraviolet absorber (N).

[0363] The ultraviolet absorber (N) is not particularly limited, and a known compound can be used. For example, a benzophenone compound, a benzotriazole compound, a triazine compound, a conjugated diene compound, a methyldibenzoyl compound, a coumarin compound, an acrylnitrile compound, a benzothiazole compound, a salicylate compound, etc. can be mentioned.

[0364] Examples of the benzophenone compound include 2,4-dihydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-methoxybenzophenone-5-sulfonic acid trihydrate, 2-hydroxy-4-octyloxybenzophenone, 4-benzyloxy-2-hydroxybenzophenone, 2,2'-dihydroxy-4,4'-dimethoxybenzophenone, 2,2',4,4'-tetrahydroxybenzophenone, diethylaminohydroxybenzoyl hexyl benzoate, 4,4'-bis(dimethylamino)benzophenone, 4,4'-bis(diethylamino)benzophenone, and 2-aminobenzophenone. Examples of commercially available products include Uvinal A, 3049, 3050, and UVA-935LH manufactured by BASF Japan, and Adeka STAB 1413 manufactured by ADEKA. Among these, 2,2',4,4'-tetrahydroxybenzophenone and 4,4'-bis(diethylamino)benzophenone are preferred.

[0365] Benzotriazole compounds include, for example, 2-(5-tert-butyl-2-hydroxyphenyl)benzotriazole, ester compounds of benzenepropanoic acid and 3-(2H-benzotriazol-2-yl)-5-(1,1-dimethylethyl)-4-hydroxy (C7-9 side chain and straight chain alkyl), 2-[5-chloro-(2H)-benzotriazol-2-yl]-4-methyl-6-(tert-butyl)phenol, and 2-(2H-benzotriazol-2-yl)-4,6-bis(1-methyl-1-phenylethyl)phenol. , 2-(2H-benzotriazol-2-yl)-6-(1-methyl-1-phenylethyl)-4-(1,1,3,3-tetramethylbutyl)phenol, 2-(2H-benzotriazol-2-yl)-4-(1,1,3,3-tetramethylbutyl)phenol, 2,2'-methylenebis[6-(2H-benzotriazol-2-yl)-4-(1,1,3,3-tetramethylbutyl)phenol], 2-[2-hydroxy-5-[2-(methacryloyloxy)ethyl]phenyl]-2H-benzotriazole, etc. Commercially available products include, for example, Tinuvin PS, 99-2, 326, 384-2, 900, 928, 970, 1130, UVA-903KT manufactured by BASF Japan, and Adeka STAB LA-31RG, LA-31G, etc. manufactured by ADEKA Corporation.

[0366] Examples of the triazine compound include a reaction product of 2-(4,6-bis(2,4-dimethylphenyl)-1,3,5-triazin-2-yl)-5-hydroxyphenyl with [(C10-C16 (mainly C12-C13) alkyloxy)methyl]oxirane, 2,4-bis[2-hydroxy-4-butoxyphenyl]-6-(2,4-dibutoxyphenyl)-1,3,5-triazine, 2-[4-[(2-hydroxy-3-(2-ethyl)hexyl)oxy]-2-hydroxyphenyl]-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine, 2,4- Examples of the bis-[{4-(4-ethylhexyloxy)-4-hydroxy}-phenyl]-6-(4-methoxyphenyl)-1,3,5-triazine, 2-(4,6-diphenyl-1,3,5-triazin-2-yl)-5-[2-(2-ethylhexanoyloxy)ethoxy]-phenol, 2-(2-hydroxy-4-[1-octyloxycarbonylethoxy]phenyl)-4,6-bis(4-phenylphenyl)-1,3,5-triazine, 2-(4,6-diphenyl-1,3,5-triazin-2-yl)-5-[(hexyl)oxy]-phenol, etc. Examples of commercially available products include Tinuvin 400, 405, 406, 477, and 479 manufactured by BASF Japan, and Adeka STAB LA-46 and LA-F70 manufactured by ADEKA.

[0367] An example of the conjugated diene compound is UV503 manufactured by Daito Chemical Co., Ltd.

[0368] Examples of the methyldibenzoyl compound include 1,3-diphenyl-1,3-propanedione, 1-(4-tert-butylphenyl)-3-(4-methoxyphenyl)-1,3-propanedione, and 1,3-bis(4-methoxyphenyl)-1,3-propanedione.

[0369] Examples of the coumarin compound include 4-hydroxycoumarin and 7-hydroxycoumarin.

[0370] The ultraviolet absorbents (N) can be used alone or in combination of two or more kinds.

[0371] The content of the ultraviolet absorber (N) is preferably from 0.1 to 5% by mass in 100% by mass of the nonvolatile content of the photosensitive composition.

[0372] [Polymerization inhibitor (O)] The photosensitive composition of the present invention may contain a polymerization inhibitor (O).

[0373] Examples of the polymerization inhibitor (O) include alkyl catechol compounds such as catechol, resorcinol, 1,4-hydroquinone, 2-methyl catechol, 3-methyl catechol, 4-methyl catechol, 2-ethyl catechol, 3-ethyl catechol, 4-ethyl catechol, 2-propyl catechol, 3-propyl catechol, 4-propyl catechol, 2-n-butyl catechol, 3-n-butyl catechol, 4-n-butyl catechol, 2-t-butyl catechol, 3-t-butyl catechol, 4-t-butyl catechol, and 3,5-di-t-butyl catechol; 2-methyl resorcinol, 4-methyl resorcinol, 2-ethyl resorcinol, 4-ethyl resorcinol, 2-propyl resorcinol, 4-propyl resorcinol, and 2-n- alkyl resorcinol compounds such as butylresorcinol, 4-n-butylresorcinol, 2-t-butylresorcinol, and 4-t-butylresorcinol; alkylhydroquinone compounds such as methylhydroquinone, ethylhydroquinone, propylhydroquinone, tert-butylhydroquinone, and 2,5-di-t-butylhydroquinone; phosphine compounds such as tributylphosphine, trioctylphosphine, tricyclohexylphosphine, triphenylphosphine, and tribenzylphosphine; phosphine oxide compounds such as trioctylphosphine oxide and triphenylphosphine oxide; phosphite compounds such as triphenylphosphite and trisnonylphenylphosphite; pyrogallol; and phloroglucine.

[0374] The polymerization inhibitor (O) can be used alone or in combination of two or more kinds.

[0375] The content of the polymerization inhibitor (O) is preferably from 0.01 to 0.4% by mass in 100% by mass of the nonvolatile content of the photosensitive composition.

[0376] [Antioxidants (P)] The photosensitive composition of the present invention may contain an antioxidant (P). The antioxidant (P) prevents the polymerization initiator (C) and the thermally crosslinkable compound (K) in the photosensitive composition from being oxidized and yellowed by heat during the heating process or ITO annealing.

[0377] Examples of the antioxidant (P) include hindered phenol-based, hindered amine-based, phosphorus-based, sulfur-based, and hydroxylamine-based compounds, etc. Among these, hindered phenol-based antioxidants, hindered amine-based antioxidants, phosphorus-based antioxidants, and sulfur-based antioxidants are preferred.

[0378] Examples of the hindered phenol antioxidant include 1,3,5-tris(3,5-di-t-butyl-4-hydroxybenzyl)-1,3,5-triazine-2,4,6(1H,3H,5H)-trione, 1,1,3-tris-(2'-methyl-4'-hydroxy-5'-t-butylphenyl)-butane, 4,4'-butylidene-bis-(2-t-butyl-5-methylphenol), 3-(3,5-di-t-butyl-4-hydroxyphenyl)stearyl propionate, pentaerythritol tetrakis[3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate, 3,9-bis[2-[3-(3-t-butyl-4-hydroxy-5-methylphenyl)propionyloxy]-1,1-dimethylethyl]-2,4,8,10-tetraoxaspiro[5.5]Undecane, 1,3,5-tris(3,5-di-t-butyl-4-hydroxyphenylmethyl)-2,4,6-trimethylbenzene, 1,3,5-tris(3-hydroxy-4-t-butyl-2,6-dimethylbenzyl)-1,3,5-triazine-2,4,6(1H,3H,5H)-trione, 2,2'-methylenebis(6-t-butyl-4-ethylphenol), 2,2'-thiodiethylbis-(3,5-di -t-butyl-4-hydroxyphenyl)-propionate, N,N-hexamethylenebis(3,5-di-t-butyl-4-hydroxy-hydrocinnamamide), i-octyl-3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate, 4,6-bis(dodecylthiomethyl)-o-cresol, calcium salt of 3,5-di-t-butyl-4-hydroxybenzylphosphonic acid monoethyl ester, 4 ,6-bis(octylthiomethyl)-o-cresol, bis[3-(3-methyl-4-hydroxy-5-t-butylphenyl)propionic acid]ethylene bisoxybisethylene, 1,6-hexanediol bis[3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate, 2,4-bis-(n-octylthio)-6-(4-hydroxy-3,5-di-t-butylanilino)-1,3,5-triazine, Examples of such phenols include 2,2'-thio-bis-(6-t-butyl-4-methylphenol), 2,5-di-t-amyl-hydroquinone, 2,6-di-t-butyl-4-nonylphenol, 2,2'-isobutylidene-bis-(4,6-dimethyl-phenol), 2,2'-methylene-bis-(6-(1-methyl-cyclohexyl)-p-cresol), and 2,4-dimethyl-6-(1-methyl-cyclohexyl)-phenol.

[0379] Examples of commercially available products include ADK STAB AO-20, AO-30, AO-40, AO-50, AO-60, AO-80, and AO-330 manufactured by ADEKA CORPORATION, KEMINOX 101, 179, 76, and 9425 manufactured by Chemipro Corporation, IRGANOX 1010, 1035, 1076, 1098, 1135, 1330, 1726, 1425WL, 1520L, 245, 259, 3114, 5057, and 565 manufactured by BASF Japan Ltd., and Cyanox CY-1790 and CY-2777 manufactured by Sun Chemical Company.

[0380] Examples of the hindered amine antioxidant include tetrakis(1,2,2,6,6-pentamethyl-4-piperidyl)-1,2,3,4-butane tetracarboxylate, tetrakis(2,2,6,6-tetramethyl-4-piperidyl)1,2,3,4-butane tetracarboxylate, bis(1,2,2,6,6-pentamethyl-4-piperidyl)sebacate, bis(2,2,6,6-tetramethyl-4-piperidyl)sebacate, bis(1-undecanoxy-2,2,6,6-tetramethylpiperidin-4-yl)carbonate, and 1,2,2,6,6-pentamethyl-4-piperidyl tetramethyl-4-piperidyl methacrylate, 2,2,6,6-tetramethyl-4-piperidyl methacrylate, polycondensation product of dimethyl succinate and 1-(2-hydroxyethyl)-4-hydroxy-2,2,6,6-tetramethylpiperidine, poly[[6-[(1,1,3,3-tetramethylbutyl)amino]-s-triazine-2,4-diyl]-[(2,2,6,6-tetramethyl-4-piperidyl)imino]-hexamethylene-[(2,2,6,6-tetramethyl-4-piperidyl)imino]], 4-hydroxy-2,2,6,6-tetramethyl-1- Ester of piperidineethanol with 3,5,5-trimethylhexanoic acid, N,N'-4,7-tetrakis[4,6-bis{N-butyl-N-(1,2,2,6,6-pentamethyl-4-piperidyl)amino}-1,3,5-triazin-2-yl]-4,7-diazadecane-1,10-diamine, decanedioic acid bis(2,2,6,6-tetramethyl-1-(octyloxy)-4-piperidinyl)ester, reaction products of 1,1-dimethylethyl hydroperoxide with octane, bis(1,2,2,6,6-pentamethyl-4-pyridyl)[[3,5-bi 1,2,2,6,6-pentamethyl-4-pyridyl sebacate, poly[[6-morpholino-s-triazine-2,4-diyl]-[(2,2,6,6-tetramethyl-4-piperidyl)imino]-hexamethylene-[(2,2,6,6-tetramethyl-4-piperidyl)imino]], 2,2,6,6-tetramethyl-4-piperidyl-C12-21 and C18 unsaturated fatty acid esters, N,N'-bis(2,2,6,6-tetramethyl-4-piperidyl)-1,6-Hexamethylenediamine, 2-methyl-2-(2,2,6,6-tetramethyl-4-piperidyl)amino-N-(2,2,6,6-tetramethyl-4-piperidyl)propionamide, etc.

[0381] Examples of commercially available products include ADK STAB LA-52, LA-57, LA-63P, LA-68, LA-72, LA-77Y, LA-77G, LA-81, LA-82, LA-87, LA-402F, and LA-502XP manufactured by ADEKA CORPORATION, KAMISTAB 29, 62, 77, and 94 manufactured by Chemipro Chemicals Co., Ltd., Tinuvin 111FDL, 123, 144, 249, 292, and 5100 manufactured by BASF Japan Ltd., and Cyasorb UV-3346, UV-3529, and UV-3853 manufactured by Sun Chemical Co., Ltd.

[0382] Examples of phosphorus-based antioxidants include di(2,6-di-t-butyl-4-methylphenyl)pentaerythritol diphosphite, distearyl pentaerythritol diphosphite, 2,2'-methylenebis(4,6-di-t-butylphenyl)2-ethylhexyl phosphite, tris(2,4-di-t-butylphenyl)phosphite, tris(nonylphenyl)phosphite, tetra(C12-C15 alkyl)-4,4'-isopropylidene diphenyl diphosphite, diphenyl mono (2-ethylhexyl)phosphite, diphenyl isodecyl phosphite, tris(isodecyl)phosphite, triphenyl phosphite, tetrakis(2,4-di-t-butylphenyl)-4,4-biphenyl diphosphonite, tris(tridecyl)phosphite, phenyl isooctyl phosphite, phenyl isodecyl phosphite, phenyl di(tridecyl)phosphite, diphenyl isooctyl phosphite, diphenyl tridecyl phosphite, 4,4'-isopropylide diphenol alkyl phosphite, trisnonylphenyl phosphite, trisdinonylphenyl phosphite, tris(biphenyl) phosphite, di(2,4-di-t-butylphenyl)pentaerythritol diphosphite, di(nonylphenyl)pentaerythritol diphosphite, phenyl bisphenol A pentaerythritol diphosphite, tetratridecyl 4,4'-butylidenebis(3-methyl-6-t-butylphenol) diphosphite, hexatridecyl Examples of such phosphite include 1,1,3-tris(2-methyl-4-hydroxy-5-t-butylphenyl)butane triphosphite, 3,5-di-t-butyl-4-hydroxybenzyl phosphite diethyl ester, sodium bis(4-t-butylphenyl)phosphite, sodium-2,2-methylene-bis(4,6-di-t-butylphenyl)-phosphite, 1,3-bis(diphenoxyphosphonyloxy)-benzene, and ethyl bis(2,4-di-t-butyl-6-methylphenyl)phosphite.

[0383] Examples of commercially available products include Adeka STAB PEP-36, PEP-8, HP-10, 2112, 1178, 1500, C, 135A, 3010, and TPP manufactured by ADEKA CORPORATION, IRGAFOS168 manufactured by BASF Japan Ltd., and HostanoxP-EPQ manufactured by Clariant Chemicals.

[0384] Examples of sulfur-based antioxidants include 2,2-bis{[3-(dodecylthio)-1-oxopropoxy]methyl}propane-1,3-diylbis[3-(dodecylthio)propionate], ditridecyl 3,3'-thiobispropionate, 2,2-thio-diethylenebis[3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate], 2,4-bis[(octylthio)methyl]-o-cresol, and 2,4-bis[(laurylthio)methyl]-o-cresol.

[0385] Examples of commercially available products include Adeka STAB AO-412S and AO-503 manufactured by ADEKA CORPORATION, and KEMINOXPLS manufactured by Chemipro Chemicals.

[0386] The antioxidants (P) can be used alone or in combination of two or more.

[0387] The content of the antioxidant (P) is preferably from 0.5 to 5.0% by mass based on 100% by mass of the nonvolatile content of the photosensitive composition.

[0388] [Storage stabilizer (Q)] The photosensitive composition of the present invention may contain a storage stabilizer (Q), which stabilizes the viscosity of the photosensitive composition over time.

[0389] Examples of the storage stabilizer (Q) include quaternary ammonium chlorides such as benzyltrimethyl chloride and diethylhydroxyamine, organic acids such as lactic acid and oxalic acid and their methyl ethers, organic phosphines such as t-butylpyrocatechol, tetraethylphosphine and tetraphenylphosphine, and phosphites.

[0390] The storage stabilizer (Q) can be used alone or in combination of two or more kinds.

[0391] The content of the storage stabilizer (Q) is preferably from 0.05 to 5% by mass based on 100% by mass of the nonvolatile content of the photosensitive composition.

[0392] [Specific metal element content] The photosensitive composition of the present invention preferably has a total content of Li, Na, K, Mg, Ca, Fe, and Cr (hereinafter also referred to as specific metal elements) of 500 mass ppm or less.

[0393] When the total amount of the specific metal elements in the photosensitive composition is within the above range, the composition has excellent dispersion stability even after storage over time. The content of the specific metal elements can be measured by inductively coupled plasma emission spectrometry (ICP).

[0394] [Water content] The photosensitive composition of the present invention preferably has a water content of 2.0% by mass or less.

[0395] A photosensitive composition having a water content within the above range has excellent dispersion stability and sensitivity even after storage over time. The water content can be measured by a known method such as the Karl Fischer method.

[0396] [Method of producing photosensitive composition] The photosensitive composition of the present invention can be prepared by mixing the above-mentioned components. In preparing the composition, the components may be mixed at once, or each component may be dissolved or dispersed in the polymerizable compound (B) or the organic solvent (E) and then mixed successively. When using a component with low solubility, such as a pigment (G), it is preferable to first carry out a dispersion treatment. For example, a dispersion is produced by adding a pigment (G), a dispersing resin (I), an organic solvent (E), etc., and carrying out a dispersion treatment. Then, an alkali-soluble resin (A), a polymerizable compound (B), a polymerization initiator (C), a leveling agent (D), etc. are blended and mixed with the dispersion to produce the dispersion. The timing of blending each material is arbitrary. The dispersion process can also be carried out multiple times.

[0397] Examples of dispersing machines for carrying out the dispersion treatment include a two-roll mill, a three-roll mill, a ball mill, a horizontal sand mill, a vertical sand mill, an annular bead mill, and an attritor.

[0398] The average dispersed particle size (secondary particle size) of the particles in the dispersion is preferably from 30 to 200 nm, more preferably from 40 to 200 nm.

[0399] The average dispersed particle size (secondary particle size) is measured, for example, using Nikkiso Microtrack UPA-EX150, which employs dynamic light scattering (FFT power spectrum method), with particle permeability set to absorption mode, particle shape set to non-spherical, and D50 particle size set to average size. The dilution solvent used for measurement is the organic solvent used for dispersion, and it is preferable to measure samples treated with ultrasonic waves immediately after sample preparation, as this tends to provide results with less variation.

[0400] The photosensitive composition is preferably subjected to removal of coarse particles of 5 μm or more, preferably coarse particles of 1 μm or more, more preferably coarse particles of 0.5 μm or more, and mixed dust by means of centrifugation, filtration with a sintered filter or membrane filter, etc. The photosensitive composition of the present invention preferably does not substantially contain particles of 0.5 μm or more, and more preferably does not contain particles of 0.3 μm or less.

[0401] <Membrane> The film of the present invention is formed by using the above-mentioned photosensitive composition. The film is preferably a patterned film, but can also be used as a flat film.

[0402] [Membrane manufacturing method] The method for producing the film is not particularly limited, and any known method can be used. For example, the film can be produced through a step of applying the photosensitive composition of the present invention onto a substrate and a step of drying the composition.

[0403] [Coating process] Examples of the substrate include substrates made of materials such as glass, resin, and silicone. The glass may be colorless and transparent, or colored glass such as blue glass may be used depending on the application. Examples of the resin include polyester-based resins such as polyester terephthalate, polyolefin-based 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. Also, an imaging element such as a CCD or a CMOS may be formed on the substrate. Also, an undercoat layer may be provided on the substrate as necessary to improve adhesion with the upper layer, prevent diffusion of substances, and flatten the surface.

[0404] The coating method is not particularly limited, and any known method can be used, such as a dropping method, a slit coating method, a spray method, a roll coating method, a spin coating method, a casting coating method, an inkjet method, flexographic printing, screen printing, gravure printing, and offset printing.

[0405] The thickness of the membrane can be appropriately adjusted depending on the purpose, and is preferably 0.05 to 20.0 μm, more preferably 0.3 to 10.0 μm.

[0406] [Drying process] The method for drying the film applied to the substrate is not particularly limited, and any known method can be used. For example, reduced pressure drying using a vacuum drying device, heat drying using a hot plate, an IR oven, a convection oven, or the like, and a combination of these methods can be used.

[0407] The drying temperature and time can be appropriately adjusted. The drying temperature is preferably about 50 to 130° C., and the drying time is preferably about 5 seconds to 5 minutes.

[0408] Next, a pattern is formed. The method for forming the pattern includes photolithography and dry etching, and photolithography is preferable. When the film is used as a flat film, the step of forming a pattern is not necessary, and the entire surface is exposed to light.

[0409] The method for forming the pattern will now be described in detail.

[0410] When forming a pattern by photolithography, the photosensitive composition of the present invention is applied onto a substrate, and the layer formed by drying is exposed to light in a pattern through a mask (exposure process), and the unexposed parts are removed with an alkaline developer (development process), and the pattern is then heat-treated (post-bake process).

[0411] [Exposure process] In the exposure process, the layer formed by coating and drying is exposed to a specific pattern through a mask using an exposure device such as a stepper. This allows the exposed portion to be cured. 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 with a specific wavelength, an optical filter can also be used. In addition, the exposure may be performed by continuous irradiation with light, or by repeating irradiation and pause of light in a short cycle (for example, on the order of milliseconds or less) (pulse exposure). In addition, a plurality of active energy rays may be used in combination, or exposure may be performed in a plurality of steps.

[0412] [Development process] Next, an alkaline development process is carried out, whereby the unexposed portions of the layer are dissolved in an alkaline developer, and only the hardened portions remain, yielding a patterned film. Examples of the alkaline developer 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, 1,8-diazabicyclo-[5.4.0]-7-undecene, etc. Two or more of these alkaline compounds can be used in combination. The alkaline developer may contain a surfactant and an organic solvent in addition to the alkaline compound and water. The concentration of the alkaline developer is preferably 0.001 to 10% by mass, more preferably 0.01 to 1% by mass. The pH of the alkaline developer is preferably 11 to 13, more preferably 11.5 to 12.5. When used at an appropriate pH, it suppresses roughening and peeling of the pattern and improves the remaining film rate after development. Examples of the developing method include a dipping method, a spraying method, a puddle method, etc. The developing temperature is preferably 15 to 40° C. After the alkaline development, it is preferable to wash with pure water.

[0413] [Post-bake process] After development, a heat treatment (post-baking) is performed, which improves the resistance of the film. The temperature is preferably 80 to 300° C., more preferably 100 to 260° C. The time is preferably about 2 minutes to 2 hours. When a material with low heat resistance is used for the substrate, when a substrate having an organic electroluminescence element as the light-emitting layer is used, or from the viewpoint of the environment, the temperature is preferably 180° C. or less.

[0414] <Optical filters> The optical filter of the present invention has the above-mentioned film. The optical filter is used, for example, in a color filter, a black matrix, a light-shielding filter, an anti-reflection filter, an infrared cut filter, an infrared transmission filter, a microlens, etc. The optical filter of the present invention can be manufactured by the same method as the above-mentioned film.

[0415] <Solid-state imaging element> The solid-state imaging device of the present invention has the above optical filter. The solid-state imaging device is not particularly limited as long as it includes the optical filter of the present invention and functions as a solid-state imaging device. For example, the following configurations can be mentioned.

[0416] The substrate has a plurality of photodiodes constituting a light receiving area of ​​a solid-state imaging device (CCD image sensor, CMOS image sensor, etc.) and a transfer electrode made of polysilicon or the like, a light shielding film with only the light receiving part of the photodiode open on the photodiode and the transfer electrode, a device protection film made of silicon nitride or the like formed on the light shielding film so as to cover the entire light shielding film and the light receiving part of the photodiode, and the optical filter (color filter) of the present invention on the device protection film. Furthermore, the device protection film may have a light collecting means (e.g., a microlens, etc., the same below) on the device protection film and below the optical filter (the side closer to the substrate), or a light collecting means on the optical filter. The filter may have a structure in which a cured film forming each color pixel is embedded in a space partitioned by partitions, for example, in a lattice shape. In this case, the partitions preferably have a low refractive index with respect to each color pixel. An imaging device including a solid-state imaging element of the present invention can be used for various purposes, such as digital cameras, electronic devices with imaging functions (such as mobile phones and smartphones), vehicle-mounted cameras, and surveillance cameras.

[0417] <Image display device> The image display device of the present invention includes the above optical filter. Examples of the image display device include a liquid crystal display and an organic EL display. The form used for the image display device is not particularly limited as long as it functions as an image display device. For example, the configuration described in "Next Generation Liquid Crystal Display Technology" (by Tatsuo Uchida, published by Kogyo Chosakai Co., Ltd. in 1994) can be mentioned. The definition of image display devices and details of each image display device are described, for example, in "Electronic Display Devices" (written by Sasaki Akio, published by Kogyo Chosakai Co., Ltd. in 1990) and "Display Devices" (written by Ibuki Yoshiaki, published by Sangyo Tosho Co., Ltd. in 1989).

[0418] <Infrared sensor> The infrared sensor of the present invention has the above optical filter. The form of the infrared sensor used is not particularly limited as long as it is provided with the optical filter of the present invention and functions as an infrared sensor, and examples thereof include the following configurations.

[0419] A substrate has a plurality of photodiodes constituting a light receiving area of ​​a solid-state imaging element (CCD image sensor, CMOS image sensor, etc.) and a transfer electrode made of polysilicon or the like. A light shielding film with only the light receiving portion of the photodiodes open is provided on the photodiodes and the transfer electrodes. A device protection film is provided on this light shielding film, and the optical filter of the present invention is provided on this device protection film. Furthermore, the device protection film may have a light collecting means (e.g., a microlens, etc., the same applies below) below the optical filter (the side closer to the substrate) on the device protection film, or the light collecting means may be provided on the optical filter.

[0420] 1 is a schematic cross-sectional view showing an example of the configuration of an infrared sensor equipped with an optical filter of the present invention. The infrared sensor shown in FIG.

[0421] The imaging area provided on the solid-state imaging element 110 is configured by combining an infrared cut filter 111 and a color filter 112 .

[0422] 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).

[0423] The color filter 112 is a color filter having pixels formed therein that transmit and absorb light of specific wavelengths in the visible light region, and for example, a color filter having red (R), green (G), and blue (B) pixels formed therein is used.

[0424] Between the infrared transmission filter 113 and the solid-state imaging element 110, a resin film 114 that is capable of transmitting light of a wavelength that has passed through the infrared transmission filter 113 is disposed.

[0425] The infrared transmission filter 113 is a filter that has a visible light blocking property and transmits infrared rays of a specific wavelength. The infrared transmission filter 113 preferably blocks light with a wavelength of 400 to 830 nm and transmits light with a wavelength of 900 to 1,300 nm, for example.

[0426] A microlens 115 is disposed on the incident light h side of the color filter 112 and the infrared transmission filter 113. A planarization film 116 is formed so as to cover the microlens 115.

[0427] In the embodiment shown in FIG. 1, the resin film 114 is disposed, but instead of the resin film 114, an infrared transmission filter 113 may be formed.

[0428] This infrared sensor can simultaneously capture image information, making it possible to perform motion sensing that recognizes the object whose movement is to be detected. In addition, this infrared sensor can obtain distance information, making it possible to capture images that include 3D information. Furthermore, this infrared sensor can also be used as a biometric authentication sensor.

[0429] In addition to the above applications, the photosensitive composition of the present invention can also be used to form transparent spacers, colored spacers, and the like. EXAMPLES

[0430] The present invention will be described in more detail below with reference to examples. However, the present invention is not limited to these examples. In addition, "parts" means "parts by mass" and "%" means "% by mass". In addition, in the present invention, the non-volatile content or non-volatile content concentration refers to the mass residue after standing in an oven at 110°C for 3 hours.

[0431] Before describing the examples, each measurement method will be described.

[0432] (Average molecular weight of resin) The number average molecular weight (Mn) and weight average molecular weight (Mw) of the resin were measured by gel permeation chromatography (GPC) equipped with an RI detector. The instrument used was an HLC-8220GPC (manufactured by Tosoh Corporation), with two separation columns connected in series, and both packings were "TSK-GEL SUPER HZM-N" connected in series. The oven temperature was 40°C, a tetrahydrofuran (THF) solution was used as the eluent, and the flow rate was 0.35 ml / min. The sample was dissolved in a solvent consisting of 1% by mass of the above eluent, and 20 microliters were injected. The molecular weight is a polystyrene equivalent value.

[0433] (Acid value of resin) 80 ml of acetone and 10 ml of water were added to 0.5 to 1 g of the resin solution, and the solution was stirred to dissolve uniformly. The solution was titrated with an automatic titrator ("COM-555" manufactured by Hiranuma Sangyo Co., Ltd.) using a 0.1 mol / L KOH aqueous solution as the titrant to measure the acid value (mgKOH / g). The acid value per unit of non-volatile content of the resin was calculated from the acid value of the resin solution and the concentration of the non-volatile content of the resin solution.

[0434] (Amine value of resin) The amine value of the resin is the total amine value (mgKOH / g) measured according to the method of ASTM D 2074 and converted into non-volatile content.

[0435] <Production of alkali-soluble resin (A)> (Solution of alkali-soluble resin (A1-1) having monomer unit (a1) with homopolymer glass transition temperature of 0° C. or lower) 262.0 parts of propylene glycol monomethyl ether acetate (hereinafter, PGMAc) was placed in a reaction vessel equipped with a thermometer, a cooling tube, a nitrogen gas inlet tube, and a stirrer in a separable 4-neck flask, and heated to 120°C while injecting nitrogen gas into the vessel. At the same temperature, a mixture of 49.7 parts of 2-ethylhexyl acrylate (2-EHA), 99.4 parts of glycidyl methacrylate (GMA), 6.6 parts of dicyclopentanyl methacrylate (DCPMA), 19.0 parts of t-butylperoxy-2-ethylhexanoate as a polymerization initiator, and PGMAc was added dropwise from the dropping tube over 2.5 hours. After the dropwise addition was completed, the mixture was stirred at 120°C for another 2 hours to obtain a precursor. The atmosphere in the flask was then replaced with air, and 50.4 parts of acrylic acid (AA) as a modified compound, 0.6 parts of triphenylphosphine as a catalyst, and 0.2 parts of methylhydroquinone were added, and the mixture was reacted at 110°C for 10 hours. This caused the epoxy group of GMA to react with the carboxyl group of AA, generating hydroxyl groups by cleavage of the epoxy group of GMA and simultaneously introducing polymerizable unsaturated groups (GMA+AA). Next, 21.3 parts of tetrahydrophthalic anhydride (THPA) was added as a modifying compound and reacted at 110°C for 4 hours. This caused a part of the hydroxyl groups of GMA+AA to react with THPA (GMA+AA+THPA). After that, PGMAc was added so that the non-volatile content was 30 mass%, and an alkali-soluble resin (A1-1) solution having a monomer unit (a1) with a homopolymer glass transition temperature of 0°C or less was prepared. The acid value was 38 mgKOH / g and the weight average molecular weight was 12,000. The blending amounts in Table 2 are expressed in mol%.

[0436] (Alkali-soluble resin (A1-2) to (A1-7) solutions) Alkali-soluble resins (A1-2) to (A1-7) were synthesized by varying the type and amount of monomer and the amount of polymerization initiator so as to obtain the constituent molar ratios and weight average molecular weights shown in Table 2, and PGMAc was added to adjust the non-volatile content to 30 mass%.

[0437] [Table 2]

[0438] GMA+AA+SHA in Table 2 represents a polymerizable unsaturated group-containing monomer unit (a2) obtained by reacting some of the hydroxyl groups of GMA+AA with succinic anhydride (SHA).

[0439] (Alkali-soluble resin (A2-1) solution) 162.0 parts of PGMAc was placed in a reaction vessel equipped with a separable 4-neck flask equipped with a thermometer, a cooling tube, a nitrogen gas inlet tube, and a stirrer, and the vessel was heated to 120°C while injecting nitrogen gas into the vessel. At the same temperature, a mixture of 16.7 parts of styrene (St), 76.8 parts of glycidyl methacrylate (GMA), 66.1 parts of dicyclopentanyl methacrylate (DCPMA), 19.0 parts of t-butylperoxy-2-ethylhexanoate as a polymerization initiator, and PGMAc was added dropwise from the dropping tube over 2.5 hours. After the dropwise addition was completed, the mixture was stirred at 120°C for another 2 hours to obtain a precursor. The atmosphere in the flask was then replaced with air, and 38.9 parts of acrylic acid (AA) as a modified compound, 0.6 parts of triphenylphosphine as a catalyst, and 0.2 parts of methylhydroquinone were added, and the mixture was reacted at 110°C for 10 hours. This caused the epoxy group of GMA to react with the carboxyl group of AA, generating hydroxyl groups through the cleavage of the epoxy group of GMA and simultaneously introducing polymerizable unsaturated groups (GMA+AA). Next, 40 parts of succinic anhydride (SHA) was added as a modifying compound and reacted at 110°C for 4 hours. This caused a part of the hydroxyl groups of GMA+AA to react with succinic anhydride (GMA+AA+SHA). After that, PGMAc was added so that the non-volatile content was 30% by mass. The acid value was 95 mgKOH / g and the weight average molecular weight was 5,000. In Table 3, the blending amounts are shown in mol%.

[0440] Alkali-soluble resins (A2-2) and (A2-3) were synthesized by varying the type and amount of monomer and the amount of polymerization initiator so as to obtain the constituent molar ratios and weight average molecular weights shown in Table 3, and PGMAc was added to adjust the non-volatile content to 30 mass%.

[0441] [Table 3]

[0442] <Production of polymerizable compound (B)> (Polymerizable compound having a urethane bond (B3-1)) In a five-neck flask equipped with a stirrer, reflux condenser, nitrogen inlet tube, thermometer, and dropping tube, 400 parts of dipentaerythritol pentaacrylate and 0.5 parts of N,N-dimethylbenzylamine were charged, and the temperature was raised to 70°C. 66 parts of toluene diisocyanate was added dropwise from the dropping tube over 2 hours. After the dropwise addition, the mixture was reacted at a temperature of 50 to 70°C for 8 hours, and the IR showed a peak at 2,180 cm- 1 The disappearance of the isocyanate absorption was confirmed. Next, 35 parts of mercaptoacetic acid and 0.6 parts of 4-methoxyphenol were charged and reacted at a temperature of 50 to 60° C. for 6 hours to obtain a polymerizable compound (B3-1) having a urethane bond.

[0443] (Polymerizable compound having a urethane bond (B3-2)) In a five-neck flask equipped with a stirrer, a reflux condenser, a nitrogen inlet tube, a thermometer, and a dropping tube, 400 parts of dipentaerythritol pentaacrylate and 0.5 parts of N,N-dimethylbenzylamine were charged, and the temperature was raised to 70°C. 64 parts of hexamethylene diisocyanate was added dropwise from the dropping tube over 2 hours. After the dropwise addition, the mixture was reacted at a temperature of 50 to 70°C for 8 hours, and the IR was measured at 2,180 cm. -1 The disappearance of the isocyanate absorption was confirmed, and a polymerizable compound (B3-2) having a urethane bond was obtained.

[0444] <Production of Leveling Agent (D)> (Copolymer (D1-1) solution) In a nitrogen-substituted flask, 15.0 parts of 3-methacryloyloxypropyltris(trimethylsiloxy)silane and 79.0 parts of methyl ethyl ketone were charged, and the temperature was raised to 50°C while stirring under a nitrogen stream. Next, 4.2 parts of 2,2'-bipyridyl and 1.5 parts of cuprous chloride were charged, and the mixture was stirred at 50°C for 30 minutes. Then, 2.7 parts of ethyl 2-bromoisobutyrate were added, and the mixture was reacted at 50°C for 3 hours under a nitrogen stream to synthesize the A block portion, which is a polymer of 3-methacryloyloxypropyltris(trimethylsiloxy)silane. Next, 35.0 parts of polypropylene glycol monomethacrylate (average repeat number of propylene glycol: 4-6) was added to the reaction system containing the A block, which was a polymer of 3-methacryloyloxypropyltris(trimethylsiloxy)silane, and the reaction was carried out at 50°C for 18 hours to synthesize the B block, which was a polymer of polypropylene glycol monomethacrylate (average repeat number of propylene glycol: 4-6). Then, 30 parts of activated alumina was added and stirred. After filtration, the mixture was distilled under reduced pressure to obtain a copolymer (D1-1) having a block structure. Thereafter, PGMAc was added so that the non-volatile content became 1% by mass, to obtain a solution of a copolymer (D1-1) having a block structure. The weight average molecular weight was 10,300 and the number average molecular weight was 9,200.

[0445] (Copolymer (D1-2)~(D1-7) solution) Copolymers (D1-2) to (D1-7) were synthesized in the same manner as for copolymer (D1-1) by changing the type and amount of monomers so as to obtain the composition and structure shown in Table 4, and PGMAc was added to adjust the non-volatile content to 1 mass%.

[0446] [Table 4]

[0447] The components listed in Table 4 are as follows:

[0448] Chemical formula (12) [ka]

[0449] Chemical formula (13) [ka]

[0450] <Production of dye (F)> (Dye (F-1)) A four-necked separable flask equipped with a thermometer, a stirrer, a distillation tube, and a condenser was charged with 67.3 parts of methyl ethyl ketone and heated to 75°C under a nitrogen stream. Separately, 34.0 parts of methyl methacrylate, 28.0 parts of n-butyl methacrylate, 28.0 parts of 2-ethylhexyl methacrylate, 10.0 parts of dimethylaminoethyl methacrylate, 6.5 parts of 2,2'-azobis(2,4-dimethylvaleronitrile), and 25.1 parts of methyl ethyl ketone were homogenized, then charged into a dropping funnel, attached to a four-necked separable flask, and dropped over 2 hours. Two hours after the end of the dropwise addition, it was confirmed from the non-volatile content that the polymerization yield was 98% or more and the weight average molecular weight was 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 heated to 80° C. over 1 hour, and reacted for 2 hours to obtain Resin 1. Next, 30 parts of resin 1 in terms of non-volatile content was added to 2,000 parts of water, and the mixture was thoroughly stirred and mixed, and then 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 the solution was gradually dropped into the resin 1 solution. After the dropwise addition, the mixture was stirred at 60°C for 120 minutes to thoroughly react. To confirm the end point of the reaction, the reaction solution was dropped onto a filter paper, and the end point was determined to be when no bleeding occurred, and the salt-forming compound was obtained. After cooling to room temperature while stirring, suction filtration was performed, and the salt-forming compound remaining on the filter paper was dried by removing moisture in a dryer to obtain dye (F-1), which is a salt-forming compound of 32 parts of CI Acid Red 52 and resin 1. At this time, the content of the component derived from CI Acid Red 52 in dye (F-1) was 25% by mass.

[0451] (Dye (F-2)) Dye (F-2) was produced in the same manner as dye (F-1), except that CI Acid Red 52 was changed to CI Acid Red 289. At this time, the content of the component derived from CI Acid Red 289 in dye (F-2) was 25 mass%.

[0452] (Dye (F-3)) A reaction apparatus equipped with a gas inlet tube, a condenser, an agitator, and a thermometer was charged with 18.2 parts of methyl methacrylate, 14.8 parts of n-butyl methacrylate, 14.8 parts of 2-ethylhexyl methacrylate, 10.0 parts of methacrylic acid, 15.0 parts of 3-ethyl-3-methacryloxymethyloxetane, and 15.0 parts of tert-butyl methacrylate, and the mixture was stirred at 50°C for 1 hour while flowing nitrogen, and the system was replaced with nitrogen. Next, 2.1 parts of ethyl bromoisobutyrate, 1.9 parts of cuprous chloride, and 62.3 parts of propylene glycol monomethyl ether were charged, and the temperature was raised to 100°C under a nitrogen stream to initiate polymerization of the first block. After polymerization for 4 hours, the polymerization solution was sampled and the nonvolatile content was measured, and it was confirmed that the polymerization conversion rate was 98% or more based on the nonvolatile content. Next, 8.1 parts of propylene glycol monomethyl ether and 12.2 parts of dimethylaminoethyl methacrylate methyl chloride salt as the second block monomer were added to the reactor, and the reaction was continued by stirring while maintaining the temperature at 100°C under a nitrogen atmosphere. Two hours after adding the dimethylaminoethyl methacrylate methyl chloride salt, a sample of the polymerization solution was taken and the non-volatile content was measured. It was confirmed that the polymerization conversion rate of the second block was 98% or more based on the non-volatile content, and after cooling to 50°C, methanol was added to obtain resin 2. The weight average molecular weight was 7,700. Next, 30 parts of resin 2 in terms of non-volatile content were added to 2,000 parts of water, thoroughly stirred and mixed, and then heated to 60°C. Meanwhile, an aqueous solution was prepared by dissolving 10 parts of a compound represented by the following chemical formula (14) in 90 parts of water, and the solution was gradually dropped into the previous resin 2 solution. After dropping, the solution was stirred at 60°C for 120 minutes to thoroughly react. To confirm the end point of the reaction, the reaction solution was dropped onto a filter paper, and the end point was determined to be when no bleeding occurred, and the salt-forming compound was obtained. After cooling to room temperature while stirring, suction filtration was performed, and the salt-forming compound remaining on the filter paper was dried by removing moisture in a dryer to obtain dye (F-3), which is a salt-forming compound of 32 parts of the compound represented by chemical formula (14) and resin 2. At this time, the content of the component derived from the compound represented by chemical formula (14) in dye (F-3) was 25% by mass.

[0453] Chemical formula (14) [ka]

[0454] (Dye (F-4)) According to paragraphs 0102 to 0104 of JP2015-57487A, dye (F-4) of the following chemical formula (15) was synthesized. The numerical values ​​shown next to the repeating units are mass ratios.

[0455] Chemical formula (15) [ka]

[0456] (Dye (F-5)) According to Example 30 of JP-A-05-345861, a compound represented by the following chemical formula (16) was obtained: In the chemical formula (16), Et represents an ethyl group.

[0457] Chemical formula (16) [ka]

[0458] <Production of Pigment (G)> (Pigment (G-11)) According to the description in JP2014-12838A, a pigment (G-11) was obtained that contains anions of an azo compound represented by general formula (9) and an azo compound having a tautomeric structure thereof, and a compound represented by general formula (10), with a molar ratio of Ni and Zn metal ions of 65:35.

[0459] <Production of Dispersion Resin (I)> (Dispersion resin (I-1) solution) In a reaction vessel equipped with a gas inlet tube, a condenser, a stirring blade, and a thermometer, 4 parts of trimellitic anhydride, 2 parts of 3-mercapto-1,2-propanediol, 50 parts of PGMAc, and 0.1 parts of dimethylbenzylamine were charged. After replacing with nitrogen gas, the reaction vessel was heated to 120°C and reacted for 4 hours, and then reacted at 80°C for 2 hours. Furthermore, 30 parts of tertiary butyl acrylate, 20 parts of (3-ethyloxetan-3-yl)methyl methacrylate ("ETERNACOLL (registered trademark) OXMA" manufactured by Ube Industries, Ltd.), 5 parts of methacrylic acid, 40 parts of ethyl acrylate, and 10 parts of PGMAc were charged, and 0.2 parts of 2,2'-azobisisobutyronitrile were added in 15 portions every 30 minutes while maintaining the reaction vessel at 80°C. The nonvolatile content was measured 1 hour after the final addition, and it was confirmed that 95% or more had reacted. PGMAc was added so that the non-volatile content was 30% by mass, to obtain a dispersion resin (I-1) solution. The acid value was 55 mgKOH / g and the weight average molecular weight was 15,000.

[0460] (Dispersion resin (I-2) solution) A reaction vessel equipped with a gas inlet tube, a thermometer, a condenser, and a stirrer was charged with 10 parts of methacrylic acid, 100 parts of methyl methacrylate, 70 parts of iso-butyl methacrylate, 20 parts of benzyl methacrylate, and 50 parts of PGMAc, and substituted with nitrogen gas. The reaction vessel was heated to 50°C and stirred, and 12 parts of 3-mercapto-1,2-propanediol was added. The temperature was raised to 90°C, and a solution of 0.1 parts of 2,2'-azobisisobutyronitrile and 90 parts of PGMAc was added and reacted for 7 hours. It was confirmed that 95% had reacted by measuring the non-volatile content. 19 parts of pyromellitic anhydride, 50 parts of PGMAc, 50 parts of cyclohexanone, and 0.4 parts of 1,8-diazabicyclo-[5.4.0]-7-undecene as a catalyst were added, and the reaction was carried out at 100°C for 7 hours. The reaction was terminated after confirming that 98% or more of the acid anhydride had been half-esterified by measuring the acid value. After cooling, PGMAc was added so that the non-volatile content was 30% by mass, and a dispersion resin (I-2) solution was obtained. The acid value was 70 mgKOH / g and the weight average molecular weight was 8,500.

[0461] (Dispersion resin (I-3) solution) In a reaction vessel equipped with a gas inlet tube, a condenser, an agitator, and a thermometer, 40 parts of methyl methacrylate, 10 parts of n-butyl methacrylate, and 13.2 parts of tetramethylethylenediamine as a catalyst were charged, and the mixture was stirred at 50°C for 1 hour while flowing nitrogen, and the inside of the system was replaced with nitrogen. Next, 9.3 parts of ethyl bromoisobutyrate as an initiator, 5.6 parts of cuprous chloride as a catalyst, and 100 parts of PGMAc were charged, and the temperature was raised to 110°C under a nitrogen stream to start polymerization of the first block (B block). After polymerization for 4 hours, the polymerization solution was sampled and the nonvolatile content was measured, and it was confirmed that the polymerization conversion rate was 98% or more based on the nonvolatile content. Next, 50 parts of PGMAc, 40 parts of dimethylaminoethyl methacrylate as a second block (A block) monomer, and 10 parts of methacryloyloxyethylbenzyldimethylammonium chloride were charged into the reaction vessel, and the reaction was continued by stirring while maintaining 110°C under a nitrogen atmosphere. Two hours after the addition, the polymerization solution was sampled and the non-volatile content was measured, and it was confirmed that the polymerization conversion rate of the second block (A block) was 98% or more based on the non-volatile content. After cooling, PGMAc was added so that the non-volatile content became 30% by mass, and a dispersion resin (I-3) solution was obtained. The amine value was 169.8 mg KOH / g.

[0462] <Production of silane coupling agent (M)> (Compound (M1-1) represented by general formula (11)) In a 1 L separable flask equipped with a stirrer, reflux condenser, dropping funnel and thermometer, 116 parts of hydroxyethyl acrylate was charged and heated to 80°C. 205 parts of 3-isocyanatepropyltrimethoxysilane was added dropwise thereto and reacted with stirring at 80°C for 4 hours. After that, IR measurement confirmed that the absorption peak derived from the isocyanate group of the raw material had completely disappeared and instead an absorption peak derived from a urethane bond had been generated, and a compound whose main component is represented by the following chemical formula (17) was obtained. Note that as a secondary component, a dimer to decamer, which is a condensation product of chemical formula (17), was included.

[0463] Chemical formula (17) [ka]

[0464] <Preparation of Dispersion> (Dispersion 1) The following raw materials were mixed and stirred until uniform, and then dispersed for 3 hours using zirconia beads with a diameter of 0.5 mm in an Eiger mill (Eiger Japan Co., Ltd. "Mini Model M-250 MKII"), followed by filtration through a filter with a pore size of 1.0 μm to produce Dispersion 1. The non-volatile content was 22.0 mass%. Each raw material was recorded as a non-volatile content, and the organic solvent contained in each raw material was recorded as organic solvent (E). Pigment (G-1): 15.0 parts Pigment derivative (H-1): 1.0 part Dispersion resin (I-1): 3.0 parts Dispersion resin (I-2): 3.0 parts Organic solvent (E1-1): 78.0 parts

[0465] (Dispersion 2~11) Dispersions 2 to 11 were prepared in the same manner as Dispersion 1, except that the raw materials and amounts shown in Table 5 were changed.

[0466] [Table 5]

[0467] The components listed in Table 5 are as follows:

[0468] Pigment G-1: CI Pigment Blue 15:6 G-2: CI Pigment Violet 23 G-3: CI Pigment Green 58 G-4: CI Pigment Green 59 G-5: CI Pigment Green 63 G-6: CI Pigment Yellow 138 G-7: CI Pigment Yellow 139 G-8: CI Pigment Yellow 150 G-9: CI Pigment Red 254 G-10: CI Pigment Red 177

[0469] Each of the pigments (G-1) to (G-11) was pulverized by salt milling, thoroughly washed with ion-exchanged water so as to have the specific metal content described above, and thoroughly dried before use.

[0470] [Pigment derivatives (H)] [ka]

[0471] [Organic solvent (E)] (Organic solvent (E1-1)) E1-1:PGMAc

[0472] <Production of Photosensitive Composition> [Example 1] The following raw materials were mixed and stirred, and filtered through a filter with a pore size of 1.0 μm to obtain a photosensitive composition 1. The nonvolatile content was 17.0 mass%. Each raw material was recorded as the nonvolatile content, and the organic solvent contained in each raw material was recorded as organic solvent (E). Dispersion 1: 3.63 parts Alkali-soluble resin (A1-1): 4.00 parts Alkali-soluble resin (A2-1): 0.55 parts Lactone-modified polymerizable compound (B1-2): 2.50 parts Polymerizable compound having an acidic group (B2-1): 2.00 parts Polymerizable compound having a urethane bond (B3-1): 1.00 part Compound (C1-1) represented by formula (3): 0.30 parts Compound (C2-1) represented by general formula (4): 0.30 parts Compound (C3-1) represented by general formula (5): 0.30 parts Copolymer (D1-1): 0.02 part Organic solvent (E1-1): 61.00 parts Organic solvent (E2-3): 5.00 parts Organic solvent (E2-4): 15.00 parts Organic solvent (E2-5): 2.00 parts Dye (F-1): 1.80 parts Sensitizer (J): 0.20 parts Compound (M1-1) represented by general formula (11): 0.20 parts UV absorber (N): 0.20 parts

[0473] [Examples 2 to 57 and Comparative Examples 1 to 3] (Photosensitive composition 2-60) Photosensitive compositions 2 to 60 were prepared in the same manner as in Example 1 using the raw materials and amounts shown in Tables 6-1 to 6-6.

[0474] [Table 6-1]

[0475] [Table 6-2]

[0476] [Table 6-3]

[0477] [Table 6-4]

[0478] [Table 6-5]

[0479] [Table 6-6]

[0480] The respective raw materials listed in Tables 6-1 to 6-6 are as follows.

[0481] [Polymerizable compound (B)] (Lactone-modified polymerizable compound (B1)) B1-1: KAYARAD DPCA-20 (manufactured by Nippon Kayaku Co., Ltd.) B1-2: KAYARAD DPCA-30 (manufactured by Nippon Kayaku Co., Ltd.)

[0482] (Polymerizable compound (B2) having an acidic group) B2-1: Aronix M-520 (manufactured by Toagosei) B2-2: Aronix M-510 (manufactured by Toagosei)

[0483] [Polymerization initiator (C)] (Compound (C1) represented by general formula (3)) C1-1: Compound (C1-1) described above C1-2: Compound (C1-2) described above

[0484] (Compound (C2) represented by general formula (4)) C2-1: The compound (C2-1) described above C2-2: The compound (C2-2) described above

[0485] (Compound (C3) represented by general formula (5)) C3-1: The compound (C3-1) described above C3-2: The compound (C3-2) described above

[0486] (Compound (C4) other than the compounds represented by the general formulas (3) to (5)) C4-1: Omnirad 907 (IGM Resins)

[0487] [Leveling agent (D)] (Other leveling agents (D2)) D2-1: 1% PGMAc solution of BYK-330 (manufactured by BYK-Chemie) (not included in copolymer (D1)) D2-2: 1% PGMAc solution of a block copolymer (n:m = 50:50 (mol%)) having the following structure

[0488] [ka] D2-3: 1% PGMAc solution of the compound with the following structure (hydroxyl value 80 mg KOH / g)

[0489] [ka]

[0490] [Organic solvent (E)] (Organic solvent (E1)) E1-1: PGMAc (boiling point 145℃) E1-2: Propylene glycol monomethyl ether (boiling point 121°C) E1-3: Butyl acetate (boiling point 126°C) E1-4: Cyclopentanone (boiling point 130℃) E1-5: Methyl lactate (boiling point 144°C)

[0491] (Organic solvent (E2)) E2-1: Ethyl lactate (boiling point 155°C) E2-2: Cyclohexanone (boiling point 156℃) E2-3: 3-Methoxy-1-butanol (boiling point 156°C) E2-4: Ethyl 3-ethoxypropionate (boiling point 170°C) E2-5: Propylene glycol diacetate (boiling point 190°C) E2-6: Ethylene glycol monobutyl ether acetate (boiling point 192°C) E2-7: Diethylene glycol monomethyl ether (boiling point 194°C)

[0492] (Organic solvent (E3)) E3-1: 1,3-butylene glycol diacetate

[0493] [Sensitizer (J)] 2,4-Diethylthioxanthone

[0494] [Silane coupling agent (M)] M2-1: 3-glycidoxypropyltrimethoxysilane

[0495] [Ultraviolet absorber (N)] A 5:5 mixture of 2-[5-chloro-(2H)-benzotriazol-2-yl]-4-methyl-6-(tert-butyl)phenol and 2,2',4,4'-tetrahydroxybenzophenone by mass ratio.

[0496] <Evaluation of Photosensitive Composition> The following evaluations were carried out on the obtained photosensitive compositions 1 to 60. The evaluation results are shown in Table 7.

[0497] [Evaluation of uneven drying] The obtained photosensitive composition was applied to a glass substrate (Corning Eagle 2000) having a length of 100 mm, width of 100 mm, and thickness of 0.7 mm using a spin coater so that the dry film thickness was 2.0 μm, and dried under reduced pressure at 100 Pa for 60 seconds. Next, the glass substrate was placed on a cylindrical metal pin (diameter 1 cm, height 1 cm) placed on a hot plate so that the glass substrate side was in contact with the metal pin, and dried at 90° C. for 1 minute to obtain an evaluation substrate. The film thickness of the obtained evaluation substrate was measured using an optical film thickness meter (F50) manufactured by Filmetrics. The evaluation was performed by calculating the difference in film thickness between the thinnest part and the thickest part (hereinafter referred to as film thickness difference). The evaluation criteria are as follows, with 3 or more being practical. 5: Film thickness difference is 0.02 μm or less 4: The difference in thickness is greater than 0.02 μm and less than 0.03 μm 3: The difference in thickness is greater than 0.03 μm and less than 0.04 μm 2: The difference in thickness is greater than 0.04 μm and less than 0.05 μm 1: The thickness difference is greater than 0.05 μm

[0498] [Water stain evaluation] The obtained photosensitive composition was applied to a glass substrate (Corning Eagle 2000) measuring 100 mm in length, 100 mm in width, and 0.7 mm in thickness using a spin coater so that the dry film thickness would be 2.0 μm, and the substrate was dried under reduced pressure at 100 Pa for 60 seconds, and then dried on a hot plate at 90° C. for 1 minute. Next, the substrate was cooled to room temperature, and then exposed to an illuminance of 30 mW / cm using an ultra-high pressure mercury lamp through a photomask having a 100 μm-wide stripe pattern. 2 , exposure dose 50mJ / cm 2 Thereafter, the substrate was developed by immersing it in an aqueous developer containing 0.12 mass % of a nonionic surfactant and 0.04 mass % of potassium hydroxide at 23° C. for 40 seconds, and then washed with pure water. The pattern surface of the obtained evaluation board was observed using a Nikon ECLIPSE LV100POL Model optical microscope, and the degree of discoloration was evaluated. The evaluation criteria are as follows, with 3 or more being considered usable. 5: There were no water stains. 4: Water stains accounted for less than 10% of the total area. 3: Water stains were greater than 10% but less than 20% of the total area. 2: Water stains were more than 20% but less than 30% of the total area. 1: Water stains accounted for 30% or more of the total area.

[0499] [Adhesion evaluation] The obtained photosensitive composition was applied to a glass substrate (Corning Eagle 2000) measuring 100 mm in length, 100 mm in width, and 0.7 mm in thickness using a spin coater so that the dry film thickness would be 2.0 μm, and the substrate was dried under reduced pressure at 100 Pa for 60 seconds, and then dried on a hot plate at 90° C. for 1 minute. Next, the substrate was cooled to room temperature, and then exposed to an ultra-high pressure mercury lamp through a photomask with a stripe pattern with 5 μm width intervals, with an illumination intensity of 30 mW / cm. 2 , 50mJ / cm 2The substrate was then spray-developed using an aqueous developer containing 0.12% of a nonionic surfactant and 0.04% of potassium hydroxide at 23°C, washed with ion-exchanged water, air-dried, and heated at 230°C for 30 minutes in a clean oven to obtain a substrate for evaluation. The spray development was carried out for the shortest time possible for forming a pattern without leaving any residual development for each photosensitive composition coating, and this was determined as the appropriate development time. Among the patterns on the evaluation substrate, the fine line patterns with a width of 5 to 25 μm were observed with an optical microscope to confirm the remaining fine line patterns. The evaluation criteria are as follows, with 3 or more being considered practical. 5: Fine lines of 10 μm or less remain. 4: Fine lines of 15 μm or more remain. Fine lines of 10 μm or less do not remain. 3: Fine lines of 20 μm or more remain. Fine lines of 15 μm or less do not remain. 2: 25 μm fine lines remain. No fine lines of 20 μm or less remain. 1: No fine lines remain.

[0500] [Table 7] [Explanation of symbols]

[0501] 100 Infrared Sensor 110 Solid-state image sensor 111 Infrared cut filter 112 Color Filter 113 Infrared transmission filter 114 Resin Film 115 Micro Lens 116 Flat membrane

Claims

1. A photosensitive composition comprising an alkali-soluble resin (A), a polymerizable compound (B), a polymerization initiator (C), a leveling agent (D), and an organic solvent (E), The leveling agent (D) contains a copolymer (D1) having a monomer unit (d1) represented by the following general formula (1) and a monomer unit (d2) represented by the following general formula (2), The photosensitive composition, wherein the organic solvent (E) comprises an organic solvent (E1) having a boiling point of 100° C. or more and less than 150° C., and an organic solvent (E2) having a boiling point of 150° C. or more and less than 230° C. General formula (1) 【Chemistry 1】 (In general formula (1), R １ are each independently an alkyl group having 1 to 6 carbon atoms, or —OSi(R ５ ) ３ A group represented by (R ５ are each independently an alkyl group having 1 to 3 carbon atoms. R ２ are each independently an alkyl group having 1 to 6 carbon atoms. R ３ is an alkyl group having 1 to 6 carbon atoms. R ４ is a hydrogen atom or a methyl group. L １ is a divalent organic group or a single bond. n is an integer from 1 to 70. General formula (2) 【Chemistry 2】 (In general formula (2), R ６ is a hydrogen atom or an alkyl group having 1 to 18 carbon atoms. R ７ is a hydrogen atom or a methyl group. m is an integer from 1 to 4. o is an integer from 2 to 200.

2. 2. The photosensitive composition according to claim 1, wherein the content of the organic solvent (E2) is 0.5 to 40 mass % based on 100 mass % of the organic solvent (E).

3. 2. The photosensitive composition according to claim 1, wherein the alkali-soluble resin (A) comprises an alkali-soluble resin (A1) having a monomer unit (a1) whose homopolymer has a glass transition temperature of 0° C. or lower.

4. 2. The photosensitive composition according to claim 1, wherein the polymerizable compound (B) comprises at least one selected from the group consisting of a lactone-modified polymerizable compound (B1), a polymerizable compound having an acidic group (B2), and a polymerizable compound having a urethane bond (B3).

5. The photosensitive composition according to claim 1, wherein the polymerization initiator (C) comprises at least one selected from the group consisting of a compound (C1) represented by the following general formula (3), a compound (C2) represented by the following general formula (4), and a compound (C3) represented by the following general formula (5): General formula (3) 【Chemistry 3】 (In general formula (3), R １ is an alkyl group having 4 to 20 carbon atoms and having an alicyclic hydrocarbon group. R ２ is 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. R ３ is a hydrogen atom, a nitro group, a group having an ether bond, or a group having an aromatic ring. General formula (4) 【Chemistry 4】 (In general formula (4), R ４ and R ５ are each independently 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. General formula (5) 【Chemistry 5】 (In general formula (5), R 6 and R ７ are each independently a hydrogen atom or an alkyl group having 1 to 8 carbon atoms. R ８ is a hydrogen atom or a monovalent substituent.

6. 2. The photosensitive composition according to claim 1, wherein the copolymer (D1) is a block copolymer having an A block containing a monomer unit (d1) represented by general formula (1) and a B block containing a monomer unit (d2) represented by general formula (2).

7. The photosensitive composition of claim 1 , further comprising a dye (F).

8. A film formed from the photosensitive composition according to any one of claims 1 to 7.

9. An optical filter comprising the film according to claim 8.

10. A solid-state imaging device comprising the optical filter according to claim 9.

11. An image display device comprising the optical filter according to claim 9.

12. An infrared sensor comprising the optical filter according to claim 9.

Images