Photosensitive composition, film, optical filter, solid state imaging device, image display device, and infrared sensor

Abstract

To provide a photosensitive composition capable of forming a film having excellent adhesion, an excellent pattern shape and excellent durability by low-temperature heating.SOLUTION: There is provided a photosensitive composition comprising an alkali-soluble resin (A), a polymerizable compound (B), a photopolymerization initiator (C) and a silane coupling agent (E), wherein the silane coupling agent (E) contains a compound (E1) having 2 to 3 alkoxysilyl groups. The photosensitive composition may comprise a heat polymerization initiator (D). In addition, the alkali-soluble resin (A) may include an alkali-soluble rein (A1) having a block isocyanate group-containing monomer unit (a1) and a hydroxyl group-containing monomer unit (a2).SELECTED DRAWING: Figure 1

Description

Technical Field

[0001] The present invention relates to a photosensitive composition used for forming an optical filter used in a solid-state imaging device, an image display device, and the like.

Background Art

[0002] Due to the widespread use of liquid crystal display devices, digital cameras, smartphones, infrared sensors, etc., the demand for optical filters used in these devices is increasing. And for the sake of lightweight, thinness, and power saving of these devices, the use of organic EL (Electro-Luminescence) display devices using OLED (Organic Light Emitting Diode) etc. that do not require a backlight, and the use of organic materials for the optoelectronic conversion film in image sensors are being studied.

[0003] As the image display device and the solid-state imaging device are miniaturized and the number of pixels is increased, the area per pixel tends to become smaller, and at the same time, higher definition of the pattern is also required. However, when forming a colored pattern by photolithography, the pigment may prevent the transmission of ultraviolet rays or may absorb ultraviolet rays, and it is difficult to obtain sufficient deep curing property of the film during exposure. Therefore, undercut is likely to occur in the developing process, and since a pixel pattern with an inverse tapered cross-sectional shape is formed, there is a problem of insufficient adhesion between the pattern and the substrate. In addition, there has been a problem of insufficient solvent resistance of the film due to deterioration of the deep curing property.

[0004] Therefore, as a study to improve the developing adhesion between the pixel pattern and the substrate, Patent Document 1 discloses a photosensitive composition for forming a colored layer with high adhesion, which includes a colorant, a photopolymerizable compound, a photopolymerization initiator, and an adhesion enhancer which is a silane compound having a group containing nitrogen and in which the number of hydrogens bonded to the nitrogen is 1 or less.

[0005] In addition, since the heat resistance of the organic light-emitting layer used in an organic EL display device or the like is generally low, it is preferable to perform the heating step at a low temperature, for example, 150°C or lower, for the photosensitive composition for forming an optical filter used in the organic EL display device. Therefore, as a study on manufacturing an optical filter at a low temperature, attempts have been made to sufficiently cure it in the exposure step using a highly sensitive polymerization initiator. For example, Patent Document 2 discloses a colored photosensitive composition containing a colorant, a polymerizable compound, and a photopolymerization initiator, wherein the absorbance of a solution obtained by dissolving 0.001% by mass of the photopolymerization initiator in acetonitrile at a wavelength of 340 nm is 0.45 or more. Patent Document 3 discloses a photosensitive colored resin composition containing a coloring material, a (meth)acrylate copolymer-based dispersant, an alkali-soluble resin, a photopolymerizable compound, a photoinitiator, and a solvent, wherein the photoinitiator contains an oxime ester compound having a specific structure.

[0006] In addition, Patent Document 4 discloses a colored composition capable of forming a cured film in which color mixing with other colors is suppressed even when an image is formed by a low-temperature process, the colored composition containing a red colorant, a resin having a repeating unit containing a blocked isocyanate group, a polymerizable compound, and a photopolymerization initiator. Patent Document 5 discloses a colored composition capable of obtaining a cured film excellent in storage stability, low-temperature curability, and solvent resistance, the colored composition containing a colorant, a polymer, and a polymerizable compound, wherein at least one selected from the group consisting of the colorant, the polymer, and the polymerizable compound has a specific structure, and at least one selected from the group consisting of the colorant, the polymer, and the polymerizable compound has a hydroxyl group.

[0007] Furthermore, in recent years, development of mobile terminals such as foldable smartphones in which the image display portion can be folded has been carried out, and the optical filters used in these are required to be not damaged even when repeatedly folded.

Prior Art Documents

Patent Documents

[0008]

Patent Document 1

[0009] However, the compositions described in Patent Documents 1 to 5 tend to increase the width of the pattern to be formed compared to the opening width of the photomask. While having a line width of the pattern close to the opening width of the photomask, it was not possible to ensure adhesion and to satisfy the pattern shape and various resistances at a certain level in the cured product after heating at a lower temperature than before.

[0010] An object of the present invention is to provide a photosensitive composition capable of forming a film having an adhesion while having a line width of a pattern close to the opening width of a photomask, and further having a pattern shape and various resistances (high temperature and high humidity resistance, solvent resistance, bending resistance) after heating at a lower temperature than before. [Means for Solving the Problems]

[0011] The present invention is a photosensitive composition containing an alkali-soluble resin (A), a polymerizable compound (B), a photopolymerization initiator (C), and a silane coupling agent (E), The silane coupling agent (E) contains a compound (E1) having 2 to 3 alkoxysilyl groups, and relates to the photosensitive composition. [Effects of the Invention]

[0012] According to the present invention described above, it is possible to provide a photosensitive composition capable of forming a film having a line width of a pattern nearly equivalent to the opening width of a photomask and having adhesiveness, pattern shape at low-temperature heating, and various resistances (high-temperature and high-humidity resistance, solvent resistance, bending resistance). Further, the present invention can provide a film, an optical filter, a solid-state imaging device, an image display device, and an infrared sensor.

Brief Description of the Drawings

[0013]

Figure 1

Embodiments for Carrying Out the Invention

[0014] Hereinafter, embodiments for carrying out the photosensitive composition of the present invention will be described in detail. Note that the present invention is not limited to the following embodiments and can be implemented with modifications within the range capable of solving the problems.

[0015] In this specification, “(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, unless otherwise specified. Also, “C.I.” means Color Index (C.I.; published by The Society of Dyers and Colourists). The polymerizable unsaturated group is an ethylenically unsaturated double bond such as a vinyl group, a (meth)allyl group, a (meth)acryloyl group, or a (meth)acryloyloxy group. Regarding the molecular weight of the compounds in the present invention, for low-molecular compounds whose molecular weight can be specified, it is the value calculated by calculation (formula weight) or the molecular weight measured by ESI-MS (electrospray ionization mass spectrometry). For compounds with a molecular weight distribution, it is the weight-average molecular weight in terms of polystyrene measured by gel permeation chromatography using tetrahydrofuran as a solvent. In the present invention, a monomer is a compound that forms a resin by polymerization. A monomer is in an unreacted state, and a monomer unit is a state in which the monomer forms a resin after polymerization. In the present invention, low-temperature heating refers to performing the heat treatment carried out after development at a temperature of 100°C or lower.

[0016] <Photosensitive composition> A photosensitive composition according to an embodiment of the present invention is a photosensitive composition containing an alkali-soluble resin (A), a polymerizable compound (B), a photopolymerization initiator (C), and a silane coupling agent (E), The silane coupling agent (E) is characterized by containing a compound (E1) having 2 to 3 alkoxysilyl groups. The alkoxysilyl group in the present invention refers to a hydrolyzable group in which 2 or 3 alkoxy groups are bonded to a silicon atom, and the compound (E1) having 2 to 3 alkoxysilyl groups refers to a compound having 2 to 3 of the hydrolyzable groups.

[0017] Although the mechanism by which the photosensitive composition having the above configuration can solve the problems of the present invention is not clear, it is speculated as follows.

[0018] The silane coupling agent (E) is hydrolyzed in the developing process, and the generated silanol groups form hydrogen bonds with the functional groups on the substrate surface or the functional groups of other components contained in the photosensitive composition, thereby presumably improving the adhesion between the substrate and the composition. Then, in the heating process, a siloxane bond is formed by a dehydration condensation reaction. It is presumed that this makes the film stronger. In addition, since the compound (E1) having 2 to 3 alkoxysilyl groups has a plurality of alkoxysilyl groups with a low reaction temperature, a cross-linked structure is formed by a self-condensation reaction between silanol groups generated by partial hydrolysis or a reaction with functional groups of other components contained in the photosensitive composition, and it is presumed that a strong film is formed. Further, since the condensate of the compound (E1) having 2 to 3 alkoxysilyl groups has flexibility, it is presumed that a film having adhesion, a pattern shape at low-temperature heating, and various resistances (high-temperature and high-humidity resistance, solvent resistance, bending resistance) can be formed while having a line width of a pattern close to the opening width of the photomask.

[0019] Hereinafter, the components contained in or that can be contained in the photosensitive composition of one embodiment will be described in detail.

[0020] [Silane coupling agent (E)] The photosensitive composition of the present invention contains a silane coupling agent (E).

[0021] The silane coupling agent (E) is a compound having a hydrolyzable group. The hydrolyzable group is a group directly bonded to a silicon atom and generating a siloxane bond by at least one of a hydrolysis reaction and a condensation reaction. Examples of the hydrolyzable group include a halogen atom, an alkoxy group, an acyloxy group, etc. Among these, an alkoxy group is preferable. 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, a ureido group, etc.

[0022] (Compound (E1) having 2 to 3 alkoxysilyl groups) The photosensitive composition of the present invention contains a compound (E1) having 2 to 3 alkoxysilyl groups as a silane coupling agent (E) from the viewpoint of forming a film having adhesion, a pattern shape at low-temperature heating, and resistance while having a line width of a pattern close to the opening width of a photomask.

[0023] Examples of the compound (E1) having 2 to 3 alkoxysilyl groups include 1,8-bis(trimethoxysilyl)octane, N,N-bis(trimethoxysilyl), tris(trimethoxysilylpropyl)isocyanurate, a compound having a fluorene structure and 2 alkoxysilyl groups, a chain hydrocarbon group-containing compound having an alkoxysilyl group, and a compound represented by the following general formula (2). Among these, the compound represented by the following general formula (2) is preferable.

[0024] General formula (2)

Chemical formula

[0025] In general formula (2), each R independently represents an alkyl group. L represents a divalent linking group, and n represents an integer of 1 to 10.

[0026] In general formula (2), each R independently represents an alkyl group. The alkyl group may be linear or branched, and is preferably a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms, more preferably an unsubstituted alkyl group having 1 to 6 carbon atoms. Among them, a methyl group or an ethyl group is preferable from the viewpoint of reactivity at low-temperature heating.

[0027] In general formula (2), L represents a divalent linking group. Examples of the divalent linking group include those composed of an alkylene group, an arylene group, an amino group, or a combination of these groups. The alkylene group may be linear or branched, and a substituted or unsubstituted alkylene group having 1 to 10 carbon atoms is preferred. The arylene group is preferably a substituted or unsubstituted arylene group having 6 to 12 carbon atoms. From the viewpoint of the pattern shape, L is preferably an alkylene group or an amino group, and more preferably an alkylene group.

[0028] In general formula (2), n represents an integer from 1 to 10. From the viewpoints of adhesion, pattern shape at low-temperature heating, and resistance, n is preferably from 1 to 3, and more preferably from 1 to 2.

[0029] Commercially available products of the compound (E1) having 2 to 3 alkoxysilyl groups include, for example, KBM-3066, KBM-3086, KBM-9659, X-12-5263HP, etc. manufactured by Shin-Etsu Silicone Co., Ltd.

[0030] The weight average molecular weight of the compound (E1) having 2 to 3 alkoxysilyl groups is preferably 300 or more and less than 1000.

[0031] The content of the compound (E1) having 2 to 3 alkoxysilyl groups is preferably 0.5 to 10% by mass, and more preferably 0.5 to 5% by mass, in 100% by mass of the non-volatile content of the photosensitive composition.

[0032] (Compound (E2) other than the compound (E1) having 2 to 3 alkoxysilyl groups) The photosensitive composition of the present invention can also use in combination a compound (E1) having 2 to 3 alkoxysilyl groups and a compound (E2) other than the compound (E1) having 2 to 3 alkoxysilyl groups (hereinafter, also simply referred to as other compound (E2)).

[0033] Other compound (E2) includes, for example, 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, hydrochloride of N-(vinylbenzyl)-2-aminoethyl-3-aminopropyltrimethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, 3-methacryloxypropylmethyldimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropylmethyldiethoxysilane, 3-methacryloxypropyltriethoxysilane, 3-acryloxypropyltrimethoxysilane, 3-isocyanatopropyltriethoxysilane, tris-(trimethoxysilylpropyl)isocyanurate, 3-mercaptopropylmethyldimethoxysilane, 3-mercaptopropyltrimethoxysilane, p-styryltrimethoxysilane, 3-ureidopropyltrialkoxysilane, etc.

[0034] Commercially available products of silane coupling agents include, for example, KBM-302, KBM-402, KBM-403, KBE-402, KBE-403, KBM-4803, KBM-602, KBM-603, KBM-903, KBE-9103P, KBM-573, KBM-6803, KBM-1003, KBE-1003, KBM-502, KBM-503, KBE-502, KBE-503, KBM-5803, KBE-9007N, KBM-802, KBM-803, KBM-1043, KBE-585A, X-12-1048, X-12-1050, etc. manufactured by Shin-Etsu Silicone Co., Ltd.

[0035] In addition, other compound (E2) may be of polymer type. The polymer type includes polysiloxane type and organic polymer type.

[0036] The polysiloxane type is a silane coupling agent in which a hydrolyzable group and the other functional groups are bonded to a polymer having a polysiloxane skeleton in the main chain. Commercially available products of the polysiloxane type include KR-513, KR-516, KR-517, X-41-1805, X-41-1810, etc. manufactured by Shin-Etsu Silicone Co., Ltd.

[0037] The organic polymer type is a silane coupling agent in which a hydrolyzable group and the other functional groups are bonded to an organic polymer having an organic structure in the main chain. Commercially available products of the organic polymer type include X-12-9815, X-12-9845, X-12-1154, X-12-972F, X-12-1159L, etc. manufactured by Shin-Etsu Silicone Co., Ltd.

[0038] The silane coupling agent (E) can be used alone or in combination of two or more.

[0039] The content of the silane coupling agent (E) is preferably 0.5% by mass or more and 10% by mass or less in 100% by mass of the non-volatile content of the photosensitive composition.

[0040] [Alkali-soluble resin (A)] The photosensitive composition of the present invention contains an alkali-soluble resin (A). The alkali-soluble resin (A) is preferably a chain random polymer. Note that the chain includes a branched chain.

[0041] The alkali-soluble resin (A) is not particularly limited as long as it can be dissolved in an alkali developer described later, and known resins can be used. For example, (meth)acrylic resin, styrene resin, styrene / (meth)acrylic resin, epoxy resin, urethane resin, polycarbonate resin, polyester resin, polyether resin, polyimide resin, polyamideimide resin, cyclic olefin resin, etc. can be mentioned.

[0042] The weight average molecular weight of the alkali-soluble resin (A) is preferably 2,000 or more and 200,000 or less.

[0043] The acid value of the alkali-soluble resin (A) is preferably 30 mgKOH / g or more and 200 mgKOH / g or less, more preferably 40 mgKOH / g or more and 180 mgKOH / g or less.

[0044] The alkali-soluble resin (A) can be used alone or in combination of two or more.

[0045] In 100% by mass of the non-volatile content of the photosensitive composition, the alkali-soluble resin (A) is preferably 1% by mass or more and 95% by mass or less, more preferably 5% by mass or more and 80% by mass.

[0046] An alkali-soluble resin (A1) having a blocked isocyanate group-containing monomer unit (a1) and a hydroxyl group-containing monomer unit (a2) The photosensitive composition of the present invention contains, as the alkali-soluble resin (A), an alkali-soluble resin (A1) having a blocked isocyanate group-containing monomer unit (a1) and a hydroxyl group-containing monomer unit (a2).

[0047] The alkali-soluble resin (A1) is a resin having a blocked isocyanate group-containing monomer unit (a1) and a hydroxyl group-containing monomer unit (a2). The alkali-soluble resin (A1) can be obtained, for example, by copolymerizing a monomer forming the blocked isocyanate group-containing monomer unit (a1) and a monomer forming the hydroxyl group-containing monomer unit (a2).

[0048] [Blocked isocyanate group-containing monomer unit (a1)] The blocked isocyanate group-containing monomer is a monomer in which the isocyanate group of the isocyanate group-containing monomer is protected with a compound that desorbs by heat (hereinafter also referred to as a blocking agent). The desorption temperature of the blocking agent is preferably 60°C or more and 160°C or less, more preferably 70°C or more and 130°C or less, and particularly preferably 80°C or more and 100°C or less.

[0049] Isocyanate group-containing monomers include, for example, 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, methacryloyl isocyanate, and the like. Also, an equimolar reaction product of 2-hydroxyalkyl (meth)acrylate and a diisocyanate compound can be used. Among these, 2-isocyanatoethyl (meth)acrylate and 2-isocyanatopropyl (meth)acrylate are preferred.

[0050] Blocking agents 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, and the like.

[0051] Examples of oxime compounds include formaldehyde oxime, acetaldehyde oxime, acetone oxime, methyl ethyl ketone oxime, methyl isobutyl ketone oxime, cyclohexanone oxime, benzophenone oxime, and the like, and methyl ethyl ketone oxime is preferred. Examples of lactam compounds include ε-caprolactam, δ-valerolactam, γ-butyrolactam, β-propiolactam, and the like. Examples of phenol 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, and the like, and 3,5-xylenol, methyl 2-hydroxybenzoate, and methyl 4-hydroxybenzoate are preferred. Alcohol compounds include, for example, methanol, ethanol, propanol, butanol, ethylene glycol, methyl cellosolve, butyl cellosolve, methyl carbitol, benzyl alcohol, phenyl cellosolve, and furfuryl alcohol. Amine compounds include, for example, diphenylamine, phenylnaphthylamine, aniline, carbazole, etc. Active methylene compounds include, for example, dimethyl malonate, diethyl malonate, methyl acetoacetate, ethyl acetoacetate, acetylacetone, etc., and diethyl malonate is preferred. Pyrazole compounds include, for example, pyrazole, methylpyrazole, 3,5-dimethylpyrazole, etc., and 3,5-dimethylpyrazole is preferred. Mercaptan compounds include, for example, butyl mercaptan, thiophenol, tert-dodecyl mercaptan, etc. Imidazole compounds include, for example, imidazole, 2-methylimidazole, 2-ethylimidazole, 1,2-dimethylimidazole, 2-ethyl-4-methylimidazole, 1-benzyl-2-phenylimidazole, etc. Imide compounds include, for example, succinimide, maleimide, maleic imide, phthalimide, etc. Urea compounds include, for example, urea, thiourea, ethylene urea, etc. Imine compounds include, for example, ethylene imine, polyethylene imine, etc. Bisulfite compounds include, for example, sodium bisulfite, potassium bisulfite, etc. These blocking agents can be used alone or in combination of two or more.

[0052] The blocking agent is preferably 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. More preferably, it is at least one selected from the group consisting of oxime compounds, phenol compounds, active methylene compounds, and pyrazole compounds. From the perspective of resistance to low-temperature heating, active methylene compounds are particularly preferred. The elimination temperature of the active methylene compound or the temperature of the transesterification reaction is as low as 80 to 110 °C, and the reaction proceeds sufficiently even with low-temperature heating, improving the resistance.

[0053] Examples of the blocked isocyanate group-containing monomer include the following compounds. However, the present invention is not limited thereto.

[0054] [Chemical formula]

[0055] Examples of commercially available products of the blocked isocyanate group-containing monomer include Kurenz MOI-DEM (desorption temperature of the blocking agent: 85 to 95 °C), MOI-BP (desorption temperature of the blocking agent: 105 to 115 °C), MOI-BM (desorption temperature of the blocking agent: 125 to 135 °C), etc. manufactured by Showa Denko KK.

[0056] The content of the blocked isocyanate group-containing monomer unit (a1) is preferably 1 mol% or more and 50 mol% or less, more preferably 3 mol% or more and 40 mol% or less, based on all the monomer units of the alkali-soluble resin (A1).

[0057] [Hydroxyl group-containing monomer unit (a2)] Examples of the hydroxyl group-containing monomer include 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 2-hydroxybutyl (meth)acrylate, 3-hydroxybutyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, 2,3-dihydroxypropyl (meth)acrylate, glycerol mono(meth)acrylate, cyclohexanedimethanol mono(meth)acrylate, 2-hydroxy-3-phenoxypropyl acrylate, 2-acryloyloxyethyl-2-hydroxyethyl phthalate, 4-hydroxyphenyl (meth)acrylate, 4-vinylphenol, 4-isopropenylphenol, and the like.

[0058] The content of the hydroxyl group-containing monomer unit (a2) is preferably 3 mol% or more and 60 mol% or less, more preferably 5 mol% or more and 50 mol% or less, based on all the monomer units of the alkali-soluble resin (A1).

[0059] Examples of the method for introducing the hydroxyl group-containing monomer unit (a2) into the alkali-soluble resin (A1) include a method of adding a monomer having a carboxyl group to the epoxy group contained in the alkali-soluble resin (A1), and a method of adding a monomer having an epoxy group to the carboxyl group contained in the alkali-soluble resin (A1).

[0060] The total content of the blocked isocyanate group-containing monomer unit (a1) and the hydroxyl group-containing monomer unit (a2) is preferably 10 mol% or more and 60 mol% or less, more preferably 20 mol% or more and 50 mol% or less, based on all the constituent units of the alkali-soluble resin (A1).

[0061] The molar ratio of the blocked isocyanate group-containing monomer unit (a1) to the hydroxyl group-containing monomer unit (a2) is preferably 10:90 to 50:50, more preferably 15:85 to 45:55.

[0062] The alkali-soluble resin (A1) may have monomer units other than the blocked isocyanate group-containing monomer unit (a1) and the hydroxyl group-containing monomer unit (a2). For example, an aliphatic condensed ring structure-containing monomer unit (a3), an acidic group-containing monomer unit (a4), an epoxy group-containing monomer unit (a5), a polymerizable unsaturated group-containing monomer unit (a6), and other monomer units (a7) can be mentioned. Among these, from the viewpoint of resistance to low-temperature heating, it is preferable to have an aliphatic condensed ring structure-containing monomer unit (a3).

[0063] [Aliphatic condensed ring structure-containing monomer unit (a3)] Examples of the aliphatic condensed ring structure-containing monomer include isobornyl (meth)acrylate, dicyclopentanyl (meth)acrylate, dicyclopentenyl (meth)acrylate, dicyclopentanyloxyethyl (meth)acrylate, dicyclopentenyl oxyethyl (meth)acrylate, adamantyl (meth)acrylate, and the like. Among these, dicyclopentanyl (meth)acrylate, dicyclopentenyl (meth)acrylate, and dicyclopentanyloxyethyl (meth)acrylate are preferable.

[0064] The content of the aliphatic condensed ring structure-containing monomer unit (a3) is preferably 1 mol% or more and 40 mol% or less, more preferably 5 mol% or more and 30 mol% or less, based on all the constituent units of the alkali-soluble resin (A1).

[0065] [Acidic group-containing monomer unit (a4)] Examples of the acidic group-containing monomer include (meth)acrylic acid, crotonic acid, propiolic acid, cinnamic acid, itaconic acid, itaconic anhydride, maleic acid, maleic acid monomethyl, maleic acid monoethyl, maleic acid monoisopropyl, maleic anhydride, fumaric acid, 2-methacryloyloxyethyl succinic acid, 2-acryloyloxyethyl phthalic acid, 2-acryloyloxyethyl hexylhydrophthalic acid, p-styrenesulfonic acid, vinylsulfonic acid, 2-acrylamido-2-methylpropanesulfonic acid, tert-butylacrylamidosulfonic acid, 2-(meth)acryloyloxyethyl acid phosphate, and the like.

[0066] From the viewpoint of developability, the content of the acidic group-containing monomer unit (a4) is preferably 1 mol% or more and 40 mol% or less, more preferably 5 mol% or more and 30 mol% or less, based on all the constituent units of the alkali-soluble resin (A1).

[0067] 〔Epoxy group-containing monomer unit (a5)〕 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, 3-(3,4-epoxycyclohexylmethyloxy)propyl (meth)acrylate, and the like.

[0068] 〔Polymerizable unsaturated group-containing monomer unit (a6)〕 Examples of the polymerizable unsaturated group-containing monomer unit (a6) include units introduced by the following methods (i) to (iii).

[0069] <Method (i)> This is method (i) in which the epoxy group-containing monomer described above is added to the acidic group of the resin having the acidic group-containing monomer unit (a4).

[0070] <Method (ii)> This is method (ii) in which the acidic group-containing monomer described above is added to the epoxy group of the resin having the epoxy group-containing monomer unit (a5).

[0071] Also preferred as the polymerizable unsaturated group-containing monomer unit (a6) is one obtained by reacting an acid anhydride with the hydroxyl group generated by the reactions of methods (i) and (ii).

[0072] Examples of the acid anhydride include tetrahydrophthalic anhydride, phthalic anhydride, hexahydrophthalic anhydride, succinic anhydride, maleic anhydride, and the like.

[0073] <Method (iii)> It is Method (iii) of reacting the isocyanate group of the isocyanate group-containing monomer with the hydroxyl group of the resin having the hydroxyl group-containing monomer unit (a2).

[0074] Examples of the isocyanate group-containing monomer include 2-(meth)acryloylethyl isocyanate, 2-(meth)acryloyloxyethyl isocyanate, 1,1-bis[methacryloyloxy]ethyl isocyanate, and the like.

[0075] 〔Other monomer unit (a7)〕 Examples of the other monomers include acrylic esters such as methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, isopropyl (meth)acrylate, n-butyl (meth)acrylate, isobutyl (meth)acrylate, tert-butyl (meth)acrylate, pentyl (meth)acrylate, hexyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, lauryl (meth)acrylate, cyclohexyl (meth)acrylate, benzyl (meth)acrylate, phenoxyethyl (meth)acrylate, phenoxydiethylene glycol (meth)acrylate, EO-modified (meth)acrylate of phenol, EO- or PO-modified (meth)acrylate of nonylphenol, EO- or PO-modified (meth)acrylate of p-cumylphenol, dimethylaminoethyl (meth)acrylate, diethylaminoethyl (meth)acrylate; Aromatic vinyl compounds such as styrene, α-methylstyrene, p-vinyltoluene, p-chlorostyrene, vinylnaphthalene; (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 fatty acids such as vinyl acetate or vinyl propionate; N-substituted maleimides such as phenylmaleimide, methylmaleimide, ethylmaleimide, 1,2-bismaleimidoethane, 1,6-bismaleimidohexane, 6,7-methylenedioxy-4-methyl-3-maleimidocoumarin, 4,4'-bismaleimidodiphenylmethane, bis(3-ethyl-5-methyl-4-maleimidophenyl)methane, N,N'-1,3-phenylenedimaleimide, N,N'-1,4-phenylenedimaleimide, N-(1-pyrenyl)maleimide, N-(2,4,6-trichlorophenyl)maleimide, N-(4-aminophenyl)maleimide, N-(4-nitrophenyl)maleimide, N-benzylmaleimide, N-bromomethyl-2,3-dichloromaleimide, N-succinimidyl-3-maleimidobenzoate, N-succinimidyl-3-maleimidopropionate, N-succinimidyl-4-maleimidobutyrate, N-succinimidyl-6-maleimidohexanoate, N-[4-(2-benzimidazolyl)phenyl]maleimide, 9-maleimidoacridine; Examples include dimethyl 2,2'-[oxybis(methylene)]bis-2-propenoate, 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, di(2-ethylhexyl) 2,2'-[oxybis(methylene)]bis-2-propenoate, etc. Other monomers can be used alone or in combination of two or more.

[0076] The weight average molecular weight of the alkali-soluble resin (A1) is preferably 5,000 or more and 40,000 or less, more preferably 6,000 or more and 40,000 or less.

[0077] The acid value of the alkali-soluble resin (A1) is preferably 30 mgKOH / g or more and 200 mgKOH / g or less, more preferably 40 mgKOH / g or more and 180 mgKOH / g or less.

[0078] The alkali-soluble resin (A1) can be used alone or in combination of two or more.

[0079] The content of the alkali-soluble resin (A1) is preferably 30% by mass or more and 100% by mass or less in 100% by mass of the alkali-soluble resin (A).

[0080] The content of the alkali-soluble resin (A1) is preferably 5 parts by mass or more and 600 parts by mass or less, more preferably 15 parts by mass or more and 400 parts by mass or less with respect to 100 parts by mass of the compound (E1) having 2 to 3 alkoxysilyl groups. It is presumed that this makes it easier for the compound (E1) having 2 to 3 alkoxysilyl groups and the alkali-soluble resin (A1) to react, improving the resistance at low-temperature heating. Furthermore, from the viewpoint of improving the resistance at low-temperature heating, the total content of the alkali-soluble resin (A1) and the compound (E1) having 2 to 3 alkoxysilyl groups is preferably 5% by mass or more and 50% by mass or less in 100% by mass of the non-volatile content of the photosensitive composition.

[0081] (Alkali-soluble resin (A2)) From the viewpoint of the pattern shape, it is also preferable that the photosensitive composition of the present invention contains an alkali-soluble resin (A2) other than the alkali-soluble resin (A1) as the alkali-soluble resin (A) (hereinafter, also simply referred to as the alkali-soluble resin (A2)).

[0082] [Polymerizable compound (B)] The photosensitive composition of the present invention contains a polymerizable compound (B).

[0083] The polymerizable compound (B) is a monomer or an oligomer having a polymerizable unsaturated group. In this specification, the polymerizable compound (B) is not contained in the alkali-soluble resin (A).

[0084] The content of the polymerizable compound (B) is preferably 1% by mass or more and 80% by mass or less, more preferably 5% by mass or more and 70% by mass or less, based on 100% by mass of the non-volatile content of the photosensitive composition.

[0085] (Urethane (meth) acrylate (B1) having a secondary or tertiary amine structure) From the viewpoints of adhesion and resistance to low-temperature heating, the photosensitive composition of the present invention preferably contains urethane (meth) acrylate (B1) having a secondary or tertiary amine structure as the polymerizable compound (B). The amine structure of the urethane (meth) acrylate (B1) having a secondary or tertiary amine structure does not include an amide structure, an imide structure, and a urethane structure in which a carbonyl group is directly bonded to a nitrogen atom. It is more preferable to contain a urethane (meth) acrylate having a secondary amine structure from the viewpoints of adhesion and resistance to low-temperature heating.

[0086] Since the urethane (meth)acrylate (B1) having a secondary or tertiary amine structure has a secondary or tertiary amine structure in the molecule, it is presumed that the hydrogen at the α-position of the amine structure is easily extracted to generate a carbon radical. Therefore, the generated peroxy radical extracts hydrogen from the urethane (meth)acrylate (B1) having a secondary or tertiary amine structure, and the newly generated carbon radical initiates polymerization. In addition, since the generated carbon radical can also capture oxygen, it has the effect of reducing the oxygen concentration. Due to these mechanisms, it is presumed that the polymerization inhibition by oxygen is suppressed and the polymerization proceeds sufficiently, so that sufficient adhesion and resistance can be obtained. Furthermore, the urethane (meth)acrylate (B1) having a secondary or tertiary amine structure forms a physical cross-linked structure by intermolecular hydrogen bonding between urethane bonds and between functional groups of the substrate together with a chemical cross-linked structure by polymerization. The molecular aggregation energy of the intermolecular hydrogen bond at the urethane bond part is larger than the aggregation energy of other organic structures such as ether bonds. Therefore, it is presumed that the film becomes flexible and strong due to the interaction between urethane bonds, and the resistance, particularly the bending resistance, is improved.

[0087] The number of (meth)acryloyl groups of the urethane (meth)acrylate (B1) having a secondary or tertiary amine structure is preferably 2 or more and 60 or less.

[0088] The urethane (meth)acrylate (B1) having a secondary or tertiary amine structure can be used alone or in combination of two or more.

[0089] The content of the urethane (meth)acrylate (B1) having a secondary or tertiary amine structure is preferably 0.1% by mass or more and 80% by mass or less, more preferably 0.5% by mass or more and 60% by mass or less in 100% by mass of the polymerizable compound (B).

[0090] The urethane (meth)acrylate (B1) having a secondary or tertiary amine structure can be produced by a urethane reaction of a Michael addition reaction product (precursor) of a (meth)acrylate compound (X) and an amine compound (Y) having a hydroxyl group with a polyisocyanate compound (Z).

[0091] (Meth)acrylate compound (X) includes, for example, ethylene glycol di(meth)acrylate, propylene glycol di(meth)acrylate, butanediol di(meth)acrylate, hexanediol di(meth)acrylate, glycerin tri(meth)acrylate, trimethylolpropane tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, ditrimethylolpropane tetra(meth)acrylate, dipentaerythritol hexa(meth)acrylate, diglycerin tri(meth)acrylate, diglycerin tetra(meth)acrylate, trimethylolpropane EO or PO modified tri(meth)acrylate, ditrimethylolpropane EO or PO modified tetra(meth)acrylate, pentaerythritol EO or PO modified tetra(meth)acrylate, dipentaerythritol EO or PO modified hexa(meth)acrylate, etc.

[0092] (Meth)acrylate compound (X) can be used alone or in combination of two or more.

[0093] Amine compound (Y) having a hydroxyl group includes, for example, ethanolamine, butanolamine, diethylene glycol amine, o-aminophenol, m-aminophenol, p-aminophenol, 2-aminobenzyl alcohol, N-methylethanolamine, N-ethylethanolamine, N-propylethanolamine, N-isopropylethanolamine, N-butylethanolamine, N-isobutylethanolamine, N-methylbutanolamine, N-ethylbutanolamine, N-butyl-4-hydroxybutylamine, N-(2-hydroxyethyl)piperazine, etc.

[0094] Amine compound (Y) having a hydroxyl group can be used alone or in combination of two or more.

[0095] (Meta)acrylate compound (X) and amine compound (Y) having a hydroxyl group can be used in the Michael addition reaction by any method without particular limitation, and known methods can be employed. For example, methods described in WO2006 / 075754, JP-T-2008-545859, JP-A-2017-066347, JP-T-2018-517797, etc. can be mentioned.

[0096] The polyisocyanate compound (Z) includes, for example, polyisocyanate compounds having an aliphatic structure such as butane-1,4-diisocyanate, hexamethylene diisocyanate, isopropylenediisocyanate, methylene diisocyanate, 2,2,4-trimethylhexamethylene diisocyanate, etc.; 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(isocyanatomethyl)cyclohexane, methylcyclohexane diisocyanate, norbornane diisocyanate, bis(isocyanatomethyl)cyclohexane, etc.; Polyisocyanate compounds having an aromatic structure such as 1,5-naphthylene diisocyanate, 4,4'-diphenylmethane diisocyanate, 4,4'-diphenyldimethylmethane diisocyanate, 4,4'-dibenzyl isocyanate, dialkyldiphenylmethane diisocyanate, tetraalkyldiphenylmethane diisocyanate, 1,3-phenylene diisocyanate, 1,4-phenylene diisocyanate, 2,4-toluene diisocyanate, 2,6-toluene diisocyanate, xylylene diisocyanate, m-tetramethylxylylene diisocyanate, 4,4-diphenylmethane diisocyanate, tolylene diisocyanate, bis(chloromethyl)diphenylmethane diisocyanate, 2,6-diisocyanate-benzyl chloride, bis(isocyanatomethyl)benzene, etc. In addition, burette bodies, isocyanurate bodies, adduct bodies, allophanate bodies, etc. of these compounds can be mentioned.

[0097] The polyisocyanate compound (Z) can be used alone or in combination of two or more thereof.

[0098] The method for the urethane reaction between the precursor and the polyisocyanate compound (Z) is not particularly limited, and known methods can be used. For example, the methods described in JP-T-2018-517797 and the like can be mentioned.

[0099] Commercially available products of urethane (meth)acrylate (B1) having a secondary or tertiary amine structure include CN9906NS manufactured by Arkema and the like.

[0100] The urethane (meth)acrylate (B1) having a secondary or tertiary amine structure can be used alone or in combination of two or more thereof.

[0101] ((Meth)acrylate (B2) other than urethane (meth)acrylate (B1) having a secondary or tertiary amine structure) From the viewpoints of the pattern shape and resistance at low-temperature heating, the photosensitive composition of the present invention preferably contains a (meth)acrylate (B2) other than urethane (meth)acrylate (B1) having a secondary or tertiary amine structure (hereinafter, also simply referred to as other (meth)acrylate (B2)) as the polymerizable compound (B).

[0102] Examples of other (meth)acrylate (B2) include (meth)acrylate having a hydroxyl group, (meth)acrylate having an acidic group, lactone-modified (meth)acrylate, (meth)acrylate having a urethane bond, (meth)acrylate having an amine structure, (meth)acrylate having a dendrimer structure or a hyperbranched structure, and the like. The (meth)acrylate having a urethane bond and the (meth)acrylate having an amine structure are compounds other than urethane (meth)acrylate (B1) having a secondary and tertiary amine structure.

[0103] Other (meth)acrylate (B2) can be used alone or in combination of two or more thereof.

[0104] The content of other (meth)acrylates (B2) is preferably 20% by mass or more and 100% by mass or less in 100% by mass of the polymerizable compound (B).

[0105] [(Meth)acrylate having a hydroxyl group] Examples of the (meth)acrylate 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, isocyanuric acid EO or 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, dipentaerythritol caprolactone modified penta(meth)acrylate and other acrylic esters, epoxy (meth)acrylate obtained by reacting the epoxy group of an epoxy compound with the carboxyl group of (meth)acrylic acid, and the like. Among these, pentaerythritol tri(meth)acrylate and dipentaerythritol penta(meth)acrylate are preferred.

[0106] Commercially available products of (meth)acrylates having a salicylic acid group include, for example, 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 manufactured by Kyoeisha Chemical Co., Ltd., Epoxy Ester M-600A, 40EM, 70PA, 200PA, 80MFA, 3002M(N), 3002A(N), and 3000A, and OGSOL GA-5060P and GA-2800 manufactured by Osaka Gas Chemical Co., Ltd.

[0107] [(Meth)acrylate having an acidic group] Examples of (meth)acrylates having an acidic group include esterified products of polyhydric alcohols and free hydroxyl group-containing poly(meth)acrylates of (meth)acrylic acid with dicarboxylic acids; esterified products of polycarboxylic acids with monohydroxyalkyl (meth)acrylates, and the like.

[0108] Examples of the above polyhydric alcohols include ethylene glycol, propylene glycol, polyethylene glycol, polypropylene glycol, glycerin, trimethylolpropane, ditrimethylolpropane, pentaerythritol, dipentaerythritol, and the like.

[0109] Examples of the above dicarboxylic acids include malonic acid, succinic acid, maleic acid, glutaric acid, phthalic acid, itaconic acid, and the like.

[0110] Examples of the above polycarboxylic acids include trimellitic acid, pyromellitic acid, and the like. Examples of monohydroxyalkyl (meth)acrylates include 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 2-hydroxybutyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, pentaerythritol triacrylate, 2-hydroxy-3-acryloyloxypropyl methacrylate, and the like.

[0111] Commercially available (meth)acrylates having an acidic group include Aronix M-5300, M-5400, M-510, M-520, M-521 manufactured by Toagosei Co., Ltd., β-CEA manufactured by Daicel Ornex Co., Ltd., and the like.

[0112] 〔Lactone-modified (meth)acrylate〕 Lactone-modified (meth)acrylate is a (meth)acrylate having a structure modified with lactone in the molecule. Lactone-modified (meth)acrylate can be obtained by esterifying a polyhydric alcohol such as trimethylolethane, ditrimethylolethane, trimethylolpropane, ditrimethylolpropane, pentaerythritol, tripentaerythritol, glycerin, diglycerol, trimethol melamine, etc. with (meth)acrylic acid and ε-caprolactone or other lactone compounds.

[0113] Commercially available lactone-modified (meth)acrylates include, for example, KAYARAD DPCA-20, DPCA-30, DPCA-60, DPCA-120, etc. manufactured by Nippon Kayaku Co., Ltd.

[0114] 〔(Meth)acrylate having a urethane bond〕 (Meth)acrylates having a urethane bond include, for example, compounds obtained by reacting a (meth)acrylate having a hydroxyl group with a polyisocyanate, and compounds obtained by reacting a polyhydric alcohol with a polyfunctional isocyanate and then reacting with a (meth)acrylate having a hydroxyl group.

[0115] The (meth)acrylate having the above hydroxyl group includes, for example, 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 carboxy(meth)acrylate, a hydroxyl group-containing polyol polyacrylate, and the like.

[0116] The above polyisocyanate includes, for example, tolylene diisocyanate which is an aromatic diisocyanate, diphenylmethane diisocyanate, xylylene diisocyanate, trimethylene diisocyanate which is an aliphatic diisocyanate, tetramethylene diisocyanate, hexamethylene diisocyanate, isophorone diisocyanate which is an alicyclic diisocyanate, and burette bodies, isocyanurate bodies, trimethylolpropane adduct bodies thereof, and the like.

[0117] The (meth)acrylate having a urethane bond preferably further has an acidic group from the viewpoint of developability. Examples of the acidic group include a sulfonic acid group, a carboxyl group, a phosphoric acid group, and the like. Among them, a carboxyl group is preferable.

[0118] A method for introducing an acidic group into the (meth)acrylate having a urethane bond can be synthesized, for example, by first reacting the above hydroxyl group-containing (meth)acrylate with the above polyfunctional isocyanate, and then adding a mercapto compound having a carboxyl group to the product.

[0119] Examples of the mercapto compound having a carboxyl group include mercaptoacetic acid, 2-mercaptopropionic acid, 3-mercaptopropionic acid, o-mercaptobenzoic acid, 2-mercaptonicotinic acid, mercaptosuccinic acid, and the like.

[0120] Examples of commercially available (meth)acrylates having a urethane bond include AH-600, UA-306H, UA-306T, UA-306I, UA-510H, UF-8001G manufactured by Kyoeisha Chemical Co., Ltd., UA-1100H, U-6LPA, UA-33H, U-10HA, U-15HA manufactured by Shin-Nakamura Chemical Co., Ltd., EBECRYL1290, KRM8452 manufactured by Daicel Ornex Co., Ltd., and the like.

[0121] [(Meth)acrylate having an amine structure] The amine structure of the (meth)acrylate having an amine structure may be any of a primary amine, secondary amine, and tertiary amine structure, but a secondary or tertiary amine is preferred. However, the amine structure of the (meth)acrylate having an amine structure does not include an amide structure, imide structure, and urethane structure in which a carbonyl group is directly bonded to a nitrogen atom.

[0122] Examples of the (meth)acrylate having an amine structure include tris(acryloyloxyethyl)amine, tris(methacryloyloxyethyl)amine, tris(2-hydroxy-3-methacryloyloxypropyl)amine, and the like.

[0123] Examples of commercially available (meth)acrylates having an amine structure include EBECRYL80, 7100 manufactured by Daicel Ornex Co., Ltd., CN371NS, 372, 374, 383, 386 manufactured by Arkema Co., Ltd., Aronix MT-3041, 3042 manufactured by Toagosei Co., Ltd., and the like.

[0124] [(Meth)acrylate having a dendrimer structure or hyperbranched structure] (Meth)acrylates having a dendrimer structure have a chemical structure in which branching is regularly repeated from the chemical structure constituting the core (hereinafter also referred to as the core part) to the outside, and a (meth)acryloyl group is bonded to the terminal thereof, and have a spherical and highly controlled chemical structure and molecular weight. The hyperbranched structure has a chemical structure similar to the dendrimer structure.

[0125] Commercially available products of (meth)acrylates having a dendrimer structure or a hyperbranched structure include, for example, Biscoat #1000LT (dendrimer structure, average number of acryloyl groups 14), 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), Miramer 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) manufactured by SARTOMER Co., Ltd., Etercure6361-100 (hyperbranched structure, average number of acryloyl groups 8), Etercure6362-100 (hyperbranched structure, average number of acryloyl groups 12), Etercure6363 (hyperbranched structure, average number of acryloyl groups 16), EtercureDR-E522 (hyperbranched structure, average number of acryloyl groups 15) manufactured by Eternal Materials Co., Ltd., and the like.

[0126] Other (meth)acrylates (B2) other than those described above include, for example, methyl (meth)acrylate, ethyl (meth)acrylate, cyclohexyl (meth)acrylate, polyethylene glycol di(meth)acrylate, 1,6 - hexanediol di(meth)acrylate, triethylene glycol di(meth)acrylate, polypropylene glycol di(meth)acrylate, trimethylolpropane tri(meth)acrylate, phenoxytetraethylene glycol (meth)acrylate, phenoxyhexaethylene glycol (meth)acrylate, glycerol tri(meth)acrylate, trimethylolpropane PO - modified tri(meth)acrylate, trimethylolpropane EO - modified or PO - modified tri(meth)acrylate, isocyanuric acid EO - modified 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, (meth)acrylic acid esters of methylolated melamine, and various (meth)acrylic acid esters such as styrene, vinyl acetate, ethylene glycol divinyl ether, pentaerythritol trivinyl ether, (meth)acrylamide, N - vinylformamide, acrylonitrile, etc.

[0127] Commercially available products 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, D-310 manufactured by Nippon Kayaku Co., Ltd.; Aronix M-101A, M-102, M-111, M-113, M-120, M-140, M-208, M-211B, M-220, M-225, M-270, M-240, M-309, M-310, M-321, M-350, M-360, M-408, M-460, M-930 manufactured by Toagosei Co., Ltd.; Biscoat #150, #155, #160, #192, #MTG, #200, #196, #195, #230, #260, #310, #700HV, #295 manufactured by Osaka Organic Chemical Industry Co., Ltd.; OGSOL EA-0200, EA-0300 manufactured by Osaka Gas Chemical Co., Ltd.; Miramer HR6060, 6100, 6200 manufactured by Miwon Specialty Chemical Co., Ltd.; 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, AD-TMP manufactured by Shin-Nakamura Chemical Co., Ltd., etc.

[0128] Also included are (meth)acrylates having a hydroxyl group and an acidic group, (meth)acrylates having a hydroxyl group and a urethane bond, (meth)acrylates having an acidic group and a urethane bond, lactone-modified (meth)acrylates having a hydroxyl group, etc.

[0129] Examples of polyfunctional (meth)acrylates having a condensed ring structure include tricyclodecane dimethanol di(meth)acrylate, 1,3-adamantanediol di(meth)acrylate, 9,9-bis[4-(2-acryloyloxyethoxy)phenyl]fluorene, etc. The polyfunctional (meth)acrylate having a complex ring structure includes, for example, dioxyglycol di(meth)acrylate, di(meth)acrylate isocyanurate, tri(meth)acrylate isocyanurate, EO-modified or PO-modified di(meth)acrylate isocyanurate, EO-modified or PO-modified tri(meth)acrylate isocyanurate, and the like.

[0130] [Photopolymerization initiator (C)] The photosensitive composition of the present invention contains a photopolymerization initiator (C).

[0131] The photopolymerization initiator (C) can be used alone or in combination of two or more.

[0132] The content of the photopolymerization initiator (C) is preferably 0.1% by mass or more and 20% by mass or less, more preferably 0.5% by mass or more and 10% by mass or less in 100% by mass of the nonvolatile content of the photosensitive composition.

[0133] Examples of the photopolymerization initiator (C) include acetophenone-based compounds such as 4-phenoxydichloroacetophenone, 4-t-butyldichloroacetophenone, 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, 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-(naphthalen-1-yl)-4,6-bis(trichloromethyl)-s-triazine, 2-(4-methoxynaphthalen-1-yl)-4,6-bis(trichloromethyl)-s-triazine, 2,4-trichloromethyl-(piperonyl)-6-triazine, 2,4-trichloromethyl-(4'-methoxystyryl)-6-triazine; Oxime ester 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-acetoxime); Acylphosphine compounds such as bis(2,4,6-trimethylbenzoyl)phenylphosphine oxide, diphenyl-2,4,6-trimethylbenzoylphosphine oxide; Quinone compounds such as 9,10-phenanthrenequinone, camphorquinone, ethylanthraquinone; borate compounds; carbazole compounds and the like.

[0134] In commercial products, as acetophenone-based compounds, Omnirad 907, 369E, 379EG, 127, 184, 1173, 2959 manufactured by IGM Resins; as acylphosphine-based compounds, Omnirad 819, TPO manufactured by IGM Resins; as oxime ester-based compounds, IRGACURE OXE-01, 02, 03, 04, 05 manufactured by BASF Japan, Adeka Arcles N-1919, NCI-730, 831E, 930 manufactured by ADEKA, TRONLY TR-PBG-301, 304, 305, 309, 314, 345, 358, 380, 365, 610, 3054, 3057 manufactured by Changzhou Qiangli New Materials Co., Ltd., Omnirad 1312, 1314, 1316 manufactured by IGM Resins, SPI-02, 03, 04, 05, 06, 07 manufactured by Samyang Corporation, DFI-020, 306, EOX-01 manufactured by Daito Chemicals, etc. are included. In addition, compounds described in JP-A No. 2007-210991, JP-A No. 2009-179619, JP-A No. 2010-037223, JP-A No. 2010-215575, JP-A No. 2011-020998, WO2015 / 036910, JP-T No. 2019-507108, JP-T No. 2019-528331, WO2021 / 175855, etc. are also included.

[0135] (Oxime ester-based compound (C1)) From the viewpoint of resistance to low-temperature heating, the photosensitive composition of the present invention preferably contains an oxime ester-based compound (C1) as the polymerization initiator (C).

[0136] Hereinafter, specific examples of the oxime ester-based compound (C1) are shown. Note that the present invention is not limited thereto.

[0137] (Oxime ester-based compound having a carbazole structure) [Chemical formula]

[0138] (Oxime ester-based compound having a carbazole structure) [Chemical formula]

[0139] (Oxime ester compounds having a diphenyl sulfide structure) [Chemical formula]

[0140] (Oxime ester compounds having a fluorene structure) [Chemical formula]

[0141] (Oxime ester compounds having a phenothiazine structure) [Chemical formula]

[0142] (Oxime ester compounds having an indole structure) [Chemical formula]

[0143] Among the oxime ester compounds (C1), from the viewpoint of resistance to low-temperature heating, the extinction coefficient of light with a wavelength of 365 nm in propylene glycol monomethyl ether acetate is 5.0 × 10 3 Compounds of L / mol·cm or more are preferred.

[0144] (Compounds (C2) other than the oxime ester compounds (C1)) In the photosensitive composition of the present invention, as the photopolymerization initiator (C), an oxime ester compound (C1) and a compound (C2) other than the oxime ester compound (C1) (hereinafter, also simply referred to as the other compound (C2)) can be used in combination.

[0145] The other compound (C2) is not particularly limited, and known compounds can be used. Among them, compounds having a fluorene structure are preferable, and it is more preferable to include compounds represented by the following general formula (1).

[0146] General formula (1)

Chemical formula

[0147] In general formula (1), R1 and R2 each independently represent a hydrogen atom or an alkyl group having 1 to 8 carbon atoms. R3 represents a hydrogen atom or a monovalent substituent.

[0148] In general formula (1), R1 and R2 each independently represent a hydrogen atom or an alkyl group having 1 to 8 carbon atoms. Examples of the alkyl group having 1 to 8 carbon atoms include linear, branched, cyclic, or those in which they are combined. For example, methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, t-butyl group, pentyl group, isopentyl group, hexyl group, heptyl group, octyl group, 2-ethylhexyl group, cyclopentyl group, cyclopentylmethyl group, cyclohexyl group, cyclohexylmethyl group, cyclohexylmethyl group, etc. Among them, a linear alkyl group having 3 to 8 carbon atoms is preferable, and a linear alkyl group having 4 to 6 carbon atoms is more preferable.

[0149] In general formula (1), R3 represents a hydrogen atom or an arbitrary monovalent substituent. Examples of the monovalent substituent include alkyl groups having 1 to 20 carbon atoms such as methyl group and ethyl group; alkoxy groups having 1 to 20 carbon atoms such as methoxy group and ethoxy group; 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 substituents; tenoyl groups which may have substituents, and the like. Examples of the substituent that the benzoyl group or tenoyl group may have include alkyl groups having 1 to 10 carbon atoms, alkoxy groups having 1 to 10 carbon atoms, alkoxycarbonyl groups having 1 to 10 carbon atoms, and the like. Among them, from the viewpoint of radical generation efficiency, a hydrogen atom and a nitro group are preferable, and a hydrogen atom is more preferable.

[0150] Examples of the method for producing the compound represented by the general formula (1) include the methods described in JP-T-2019-507108, JP-T-2019-528331, and the like.

[0151] Specific examples of the compound represented by the general formula (1) are shown below. Note that the present invention is not limited thereto.

[0152] [Chemical formula]

[0153] The other compound (C2) can be used alone or in combination of two or more.

[0154] [Thermal polymerization initiator (D)] The photosensitive composition of the present invention preferably contains a thermal polymerization initiator (D).

[0155] The thermal polymerization initiator (D) is a polymerization initiator that generates radicals by heat.

[0156] The thermal polymerization initiator (D) is, for example, pinacol compounds such as 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, 1,2-bis(trimethylsiloxy)-1,1,2,2-tetraphenylethane, 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, 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), 2,2'-azobis(N-cyclohexyl-2-methylpropionamide); organic peroxides such as 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, benzoyl peroxide, etc. can be mentioned.

[0157] The thermal polymerization initiator (D) can be used alone or in combination of two or more kinds.

[0158] The content of the thermal polymerization initiator (D) is preferably 0.1% by mass or more and 20% by mass or less, more preferably 0.5% by mass or more and 10% by mass or less in 100% by mass of the non-volatile content of the photosensitive composition.

[0159] It is preferable to use the photopolymerization initiator (C) and the thermal polymerization initiator (D) in combination in the photosensitive composition of the present invention. It is presumed that the resistance is further improved by performing the radical polymerization reaction in both the exposure step and the heating step.

[0160] The mass ratio of the photopolymerization initiator (C) to the thermal polymerization initiator (D) is preferably (C):(D)=90:10 to 10:90, more preferably 20:80 to 80:20.

[0161] [Thermosetting compound (F)] The photosensitive composition of the present invention contains a thermosetting compound (F).

[0162] The thermosetting compound (F) is not particularly limited as long as it is a compound having a thermosetting group, and known compounds can be used. The thermosetting compound (F) does not have a polymerizable unsaturated group, and in this specification, the thermosetting compound (F) is not contained in the alkali-soluble resin (A) and the polymerizable compound (B). The thermosetting compound (F) is a compound that does not have alkali solubility.

[0163] The thermosetting compound (F) can be used alone or in combination of two or more kinds.

[0164] The content of the thermosetting compound (F) is preferably 0.5% by mass or more and 40% by mass or less, more preferably 1% by mass or more and 30% by mass or less in 100% by mass of the non-volatile content of the photosensitive composition.

[0165] (Thermosetting compound (F1) having a blocked isocyanate group) The photosensitive composition of the present invention contains, as the thermosetting compound (F), a thermosetting compound (F1) having a blocked isocyanate group.

[0166] The thermosetting compound (F1) is a compound obtained by protecting the isocyanate groups of a compound having isocyanate groups with a blocking agent. The elimination temperature of the blocking agent for the blocked isocyanate group is preferably 60°C or higher and 160°C or lower, more preferably 70°C or higher and 130°C or lower, and particularly preferably 80°C or higher and 100°C or lower.

[0167] The thermosetting compound (F1) can be obtained by reacting a compound having an isocyanate group with a blocking agent by a known method. Examples include those described in JP-A-52-116420, JP-A-60-149572, JP-A-7-31953, JP-A-10-306136, JP-A-2012-012567, and the like.

[0168] Examples of the blocking agent include the above-mentioned compounds. Among these, at least one selected from the group consisting of an oxime compound, a lactam compound, a phenol compound, an alcohol compound, an amine compound, an active methylene compound, a pyrazole compound, a mercaptan compound, an imidazole compound, and an imide compound is preferable, and at least one selected from the group consisting of an oxime compound, a phenol compound, an active methylene compound, and a pyrazole compound is more preferable. From the viewpoint of resistance to low-temperature heating, an active methylene compound is particularly preferable. The elimination temperature of the active methylene compound or the temperature of the transesterification reaction is as low as 80 to 110°C, and the reaction proceeds sufficiently even at low-temperature heating, improving the resistance.

[0169] Examples of the compound having an isocyanate group include compounds having an aliphatic structure such as butane-1,4-diisocyanate, hexamethylene diisocyanate, isopropylenediisocyanate, methylene diisocyanate, 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(isocyanatomethyl)cyclohexane, methylcyclohexane diisocyanate, norbornane diisocyanate, bis(isocyanatomethyl)cyclohexane; Compounds having an aromatic structure such as 1,5-naphthylene diisocyanate, 4,4'-diphenylmethane diisocyanate, 4,4'-diphenyldimethylmethane diisocyanate, 4,4'-dibenzyl isocyanate, dialkyldiphenylmethane diisocyanate, tetraalkyldiphenylmethane diisocyanate, 1,3-phenylene diisocyanate, 1,4-phenylene diisocyanate, 2,4-toluene diisocyanate, 2,6-toluene diisocyanate, xylylene diisocyanate, m-tetramethylxylylene diisocyanate, 4,4-diphenylmethane diisocyanate, tolylene diisocyanate, bischloromethyldiphenylmethane diisocyanate, 2,6-diisocyanate-benzyl chloride, bis(isocyanatomethyl)benzene, etc. can be mentioned. In addition, burette bodies, isocyanurate bodies, adduct bodies, allophanate bodies of these compounds, and reaction products of these compounds with polyols, etc. can be mentioned.

[0170] From the viewpoint of resistance to low-temperature heating, compounds having an aliphatic structure, burette bodies, isocyanurate bodies, adduct bodies, allophanate bodies of compounds having an alicyclic structure are preferable for the compounds having an isocyanate group.

[0171] Examples of the thermosetting compound (F1) include the following compounds. In the following structural formulas, X represents a blocked isocyanate group. Note that the present invention is not limited to these.

[0172]

Chemical formula

[0173] The X (block isocyanate group) of the above compound includes, for example, the structures of the following (X-1) to (X-6). In the following structures, * represents the bonding part. Note that the present invention is not limited thereto.

[0174]

Chemical formula

[0175] Commercially available products of the thermosetting compound (F1) include, for example, as compounds having an aliphatic structure, Duranate SBN-70D, SBB-70P, SBF-70E, TPA-B80E, 17B-60P, MF-B60B, E402-B80B, MF-K60B, WM44-L70G manufactured by Asahi Kasei Corporation; Bronate 1227EV, 1232E manufactured by Daiwing Sangyo Co., Ltd.; Takenate B-882 manufactured by Mitsui Chemicals, Inc.; BI7960, BI7961, BI7982, BI7991, BI7992, etc. manufactured by Baxenden Chemical Co., Ltd. As compounds having an alicyclic structure, Takenate B-846N manufactured by Mitsui Chemicals, Inc.; Coronate BI-301, 2507, 2554 manufactured by Tosoh Corporation; BI7950, BI7951, BI7990, etc. manufactured by Baxenden Chemical Co., Ltd. As compounds having an aromatic structure, Takenate B-830, B-815N, etc. manufactured by Mitsui Chemicals, Inc. can be mentioned.

[0176] The number of block isocyanate groups of the thermosetting compound (F1) is preferably 1 or more and 20 or less, and more preferably 2 or more and 15 or less.

[0177] The weight average molecular weight of the thermosetting compound (F1) is preferably 500 or more and less than 4,000.

[0178] The acid value of the thermosetting compound (F1) is preferably 10 mgKOH / g or less.

[0179] The thermosetting compound (F1) can be used alone or in combination of two or more.

[0180] The content of the thermosetting compound (F1) is preferably 5 parts by mass or more and 400 parts by mass or less, more preferably 15 parts by mass or more and 250 parts by mass or less, based on 100 parts by mass of the compound (E1) having 2 to 3 alkoxysilyl groups. Thereby, the compound (E1) having 2 to 3 alkoxysilyl groups and the thermosetting compound (F1) are more likely to react, and the resistance after low-temperature heating is improved. Furthermore, from the viewpoint of improving the resistance at low-temperature heating, the total content of the thermosetting compound (F1) and the compound (E1) having 2 to 3 alkoxysilyl groups is preferably 5% by mass or more and 80% by mass or less in 100% by mass of the non-volatile content of the photosensitive composition.

[0181] (Thermosetting compound (F2) having an epoxy group) The photosensitive composition of the present invention preferably contains a thermosetting compound (F2) having an epoxy group (hereinafter, also simply referred to as the thermosetting compound (F2)) as the thermosetting compound (F). Thereby, the epoxy group is crosslinked by heating, and the resistance is further improved.

[0182] The epoxy group is a group having a three-membered cyclic ether structure, and an alicyclic epoxy group is also included. The compound having an epoxy group is not particularly limited, and known compounds can be used. For example, polyglycidyl ether compounds of bisphenols such as bisphenol A diglycidyl ether, bisphenol F diglycidyl ether, bisphenol S diglycidyl ether, hydrogenated bisphenol A diglycidyl ether, and hydrogenated bisphenol F diglycidyl ether; Polyglycidyl ether compounds of polyhydric alcohols such as 1,4-butanediol diglycidyl ether, 1,6-hexanediol diglycidyl ether, glycerin triglycidyl ether, trimethylolpropane triglycidyl ether, polyethylene glycol diglycidyl ether, and polypropylene glycol diglycidyl ether; Polyglycidyl ether compounds of polyether polyols obtained by adding an alkylene oxide to polyhydric alcohols such as ethylene glycol, propylene glycol, and glycerin; Compounds having two or more 3,4-epoxycyclohexyl groups in the molecule, such as 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-methadioxane, bis(3,4-epoxycyclohexylmethyl)adipate, 3,4-epoxy-6-methylcyclohexanecarboxylate, methylenebis(3,4-epoxycyclohexane), ethylenebis(3,4-epoxycyclohexanecarboxylate), dioctyl epoxyhexahydrophthalate, 1-epoxyethyl-3,4-epoxycyclohexane, tetrakis(3,4-epoxycyclohexylmethyl) butanetetracarboxylate modified ε-caprolactone; Examples include the 1,2-epoxy-4-(2-oxiranyl)cyclohexane adduct of 2,2-bis(hydroxymethyl)-1-butanol.

[0183] Commercially available products of the thermosetting compound (F2) include, for example, Epicoat 807, 815, 825, 827, 828, 190P, 191P manufactured by Yuka Shell Epoxy Co., Ltd., TECHMORE VG3101L manufactured by Mitsui Chemicals, Inc., EPPN-201, 501H, 502H manufactured by Nippon Kayaku Co., Ltd., EOCN-102S, 103S, 104S, 1020, Epicoat 1004, 1256 manufactured by Japan Epoxy Resins Co., Ltd., JER1032H60, 157S65, 157S70, 152, 154, Celloxide 2021, EHPE-3150, Epolead GT401 manufactured by Daicel Chemical Industries, Ltd., 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, Ltd., EPICLON 830, 840, 850, 860, 1050, 3050, 4050, N-660, N-670, N-740, N-770, N865, HP-7200, HP-4700, HP-4770, HP-5000, HP-6000, HP-9500 manufactured by DIC Corporation, etc.

[0184] The thermosetting compound (F2) is preferably a compound having 2 or more and 50 or less epoxy groups in the molecule.

[0185] The epoxy equivalent of the thermosetting compound (F2) is preferably 50 g / eq or more and 400 g / eq or less, and more preferably 100 g / eq or more and 200 g / eq or less. The epoxy equivalent is defined as the mass of an epoxy compound containing 1 equivalent of epoxy groups.

[0186] From the viewpoint of resistance at low-temperature heating, the thermosetting compound (F2) preferably contains a compound represented by the following general formula (3).

[0187] General formula (3)

Chemical formula

[0188] In the general formula (3), R represents a group obtained by removing m hydroxyl groups from an m-valent alcohol, m represents an integer of 1 or more and 6 or less, and n represents an integer of 1 or more and 30 or less.

[0189] R represents a group obtained by removing m hydroxyl groups from an m-valent alcohol. The group obtained by removing m hydroxyl groups from an m-valent alcohol is preferably an alkyl group having 2 to 20 carbon atoms, which may be linear, branched, cyclic, or a combination thereof. Examples of the alkyl group having 2 to 20 carbon atoms include ethyl group, methyl group, ethyl group, propyl group, isopropyl group, 2,2-dimethylpropyl group, butyl group, isobutyl group, tert-butyl group, 3,3-dimethylbutyl group, pentyl group, isopentyl group, hexyl group, heptyl group, octyl group, isooctyl group, 2-ethylhexyl group, nonyl group, isononyl group, decyl group, isodecyl group, undecyl group, dodecyl group, hexadecyl group, cyclopentyl group, cyclopentylmethyl group, cyclohexyl group, cyclohexylmethyl group, cyclohexylmethyl group, etc. Among these, a branched alkyl group having 3 to 12 carbon atoms is more preferable.

[0190] m represents an integer of 1 or more and 6 or less, and n represents an integer of 1 or more and 30 or less. When m is 2 or more, n in the groups within each pair of parentheses in the general formula (3) may be the same or different.

[0191] Specific examples of the compound represented by the general formula (3) include the 1,2-epoxy-4-(2-oxiranyl)cyclohexane adduct of 2,2-bis(hydroxymethyl)-1-butanol. Commercially available products include EHPE-3150, EHPE-3150CE, etc. manufactured by Daicel Corporation.

[0192] The thermosetting compound (F2) can be used alone or in combination of two or more.

[0193] The content of the thermosetting compound (F2) is preferably 5 parts by mass or more and 200 parts by mass or less, more preferably 15 parts by mass or more and 150 parts by mass or less, with respect to 100 parts by mass of the compound (E1) having 2 to 3 alkoxysilyl groups. It is presumed that this makes it easier for the compound (E1) having 2 to 3 alkoxysilyl groups and the thermosetting compound (F2) to react, improving the resistance at low-temperature heating.

[0194] <Colorant> The colorant in the present invention is not particularly limited, and may be either a pigment or a dye, and they can be used in combination. The pigment may be either an organic pigment or an inorganic pigment, and they can be used in combination.

[0195] The photosensitive composition of the present invention preferably contains one or more of a pigment (G) and a dye (H) as a colorant. Thereby, the transmittance in each wavelength region of the optical filter can be controlled.

[0196] [Pigment (G)] From the viewpoint of resistance, the colorant contained in the photosensitive composition of the present invention is more preferably the pigment (G).

[0197] The pigment (G) can be used alone or in combination of two or more.

[0198] The content of the pigment (G) is preferably 0.5% by mass or more and 60% by mass or less, more preferably 1% by mass or more and 50% by mass or less, in 100% by mass of the non-volatile content of the photosensitive composition.

[0199] The pigment (G) is preferably used after being refined. The refining method is not particularly limited, and for example, any of wet grinding, dry grinding, and solvent precipitation methods can be used. Among these, the salt milling treatment by the kneader method, which is a type of wet grinding, is preferred. The average primary particle diameter determined by TEM (transmission electron microscope) of the refined pigment is preferably 5 nm or more and 90 nm or less. From the viewpoint of dispersibility, the average primary particle diameter is more preferably 10 nm or more and 70 nm or less.

[0200] For the salt milling process, resin may be added as necessary. By adding resin, the pigment (G) is coated with the resin, improving stability, light resistance, etc. The type of the resin is not particularly limited, and examples include natural resins, modified natural resins, synthetic resins, synthetic resins modified with natural resins, etc. Among these, it is preferably solid at room temperature, water-insoluble, and partially soluble in organic solvents. The addition amount of the resin is preferably 2 parts by mass or more and 200 parts by mass or less with respect to 100 parts by mass of the pigment (G).

[0201] The pigment (G) is not particularly limited, and examples include colored pigments, white pigments, black pigments, and near-infrared absorbing pigments. 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.

[0202] When the photosensitive composition of the present invention is used for a color filter, a colored pigment is preferably used as the pigment (G). The colored pigment can 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, a near-infrared absorbing pigment is preferably used as the pigment. The near-infrared absorbing pigment can be used alone or in combination of two or more. When used for a near-infrared transmission filter, it is preferable to use two or more kinds of black pigments and colored pigments in combination to form black. Further, a near-infrared absorbing pigment may be used in combination.

[0203] (Colored pigment) The colored pigment is not particularly limited, and known colored pigments can be used. For example, compounds classified as pigments in the Color Index can be mentioned.

[0204] Examples of the colored pigments include red pigments such as C.I. Pigment Red 1, 2, 3, 4, 5, 6, 7, 8, 9, 12, 14, 15, 16, 17, 21, 22, 23, 31, 32, 37, 38, 41, 47, 48, 48:1, 48:2, 48:3, 48:4, 49, 49:1, 49:2, 50:1, 52:1, 52:2, 53, 53:1, 53:2, 53:3, 57, 57:1, 57:2, 58:4, 60, 63, 63:1, 63:2, 64, 64:1, 68, 69, 81, 81:1, 81:2, 81:3, 81:4, 83, 88, 90:1, 101, 101:1, 104, 108, 108:1, 109, 112, 113, 114, 122, 123, 144, 146, 147, 149, 151, 166, 168, 169, 170, 172, 173, 174, 175, 176, 177, 178, 179, 181, 184, 185, 187, 188, 190, 193, 194, 200, 202, 206, 207, 208, 209, 210, 214, 216, 220, 221, 224, 230, 231, 232, 233, 235, 236, 237, 238, 239, 242, 243, 245, 247, 249, 250, 251, 253, 254, 255, 256, 257, 258, 259, 260, 262, 263, 264, 265, 266, 267, 268, 269, 270, 271, 272, 273, 274, 275, 276, 277, 278, 279, 280, 281, 282, 283, 284, 285, 286, 287, 291, 295, 296, the pigments described in JP-A-2014-134712, the pigments described in Patent No. 6368844, etc.

[0205] Examples of the orange pigments include C.I. Pigment Orange 36, 38, 43, 64, 71, 73, etc.

[0206] C.I. Pigment Yellow 1, 2, 3, 4, 5, 6, 10, 12, 13, 14, 15, 16, 17, 18, 24, 31, 32, 34, 35, 35:1, 36, 36:1, 37, 37:1, 40, 42, 43, 53, 55, 60, 61, 62, 63, 65, 73, 74, 77, 81, 83, 93, 94, 95, 97, 98, 100, 101, 104, 106, 108, 109, 110, 113, 114, 115, 116, 117, 118, 119, 120, 123, 126, 127, 128, 129, 138, 139, 147, 150, 151, 152, 153, 154, 155, 156, 161, 162, 164, 166, 167, 168, 169, 170, 171, 172, 173, 174, 175, 176, 177, 179, 180, 181, 182, 185, 187, 188, 192, 193, 194, 196, 198, 199, 213, 214, 231, 233, and the yellow pigments described in JP-A-2012-226110 are exemplified.

[0207] Further, examples of the yellow pigment include a metal azo pigment containing at least one anion selected from the group consisting of mono, di, tri, and tetra anions of an azo compound represented by the following general formula (4) and its azo compound of a tautomeric structure, 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 (5).

[0208] General formula (4)

Chemical formula

[0209] In general formula (4), two R1s each independently represent -OH, -NH2, -NH-CN, an acylamino group, an alkylamino group, or an arylamino group, and two R2s each independently represent -OH or -NH2.

[0210] General formula (5)

Chemical formula

[0211] In general formula (5), the three R3s each independently represent a hydrogen atom or an alkyl group.

[0212] Examples of the metal azo pigment include the metal azo pigments described in, for example, JP-A-2014-12838, JP-A-2017-171912, JP-A-2017-171913, JP-A-2017-171914, JP-A-2017-171915, JP-A-2022-61494, and the like.

[0213] Examples of the green pigments include C.I. Pigment Green 1, 2, 4, 7, 8, 10, 13, 14, 15, 17, 18, 19, 26, 36, 37, 45, 48, 50, 51, 54, 55, 58, 59, 62, 63, 64, 65, 66, etc.

[0214] Examples of the blue pigments include C.I. Pigment Blue 1, 1:2, 9, 14, 15, 15:1, 15:2, 15:3, 15:4, 15:6, 16, 17, 19, 25, 27, 28, 29, 33, 35, 36, 56, 56:1, 60, 61, 61:1, 62, 63, 66, 67, 68, 71, 72, 73, 74, 75, 76, 78, 79, 80, 87, 88, etc.

[0215] Examples of the violet pigments include C.I. Pigment Violet 1, 1:1, 2, 2:2, 3, 3:1, 3:3, 5, 5:1, 14, 15, 16, 19, 23, 25, 27, 29, 31, 32, 37, 39, 42, 44, 47, 49, 50, etc.

[0216] The colored pigments can be used alone or in combination of two or more. For example, in the case of black, in addition to using the black pigment described later, it can be obtained (combined) using two or more colored pigments selected from the group consisting of red pigments, yellow pigments, green pigments, blue pigments, and violet pigments. Examples of the combination include the following embodiments. (1) Containing a yellow pigment and a violet pigment. (2) Containing a red pigment, a yellow pigment, and a violet pigment. (3) It contains a red pigment, a yellow pigment, and a blue pigment. (4) It contains a red pigment, a yellow pigment, and a green pigment. (5) It contains a yellow pigment, a blue pigment, and a purple pigment. (6) It contains a red pigment, a yellow pigment, a blue pigment, and a purple pigment. (7) It contains a yellow pigment, a blue pigment, a green pigment, and a purple pigment.

[0217] For the aspect of (1) above, for example, the yellow pigment is one or more selected from C.I. Pigment Yellow 139, 185, 231, 233, and the purple pigment is C.I. Pigment Violet 23. For the aspect of (2) above, for example, the red pigment is one or more selected from C.I. Pigment Red 177, 254, 291, 295, 296, the yellow pigment is one or more selected from C.I. Pigment Yellow 139, 185, 231, 233, and the purple pigment is C.I. Pigment Violet 23. For the aspect of (3) above, for example, the red pigment is one or more selected from C.I. Pigment Red 177, 254, 291, 295, 296, the yellow pigment is one or more selected from C.I. Pigment Yellow 139, 185, 231, 233, and the blue pigment is one or more selected from C.I. Pigment Blue 15:3, 15:4, 15:6. For the aspect of (4) above, for example, the red pigment is one or more selected from C.I. Pigment Red 177, 254, 291, 295, 296, the yellow pigment is one or more selected from C.I. Pigment Yellow 139, 185, 231, 233, and the green pigment is one or more selected from C.I. Pigment Green 7, 36, 58, 59, 63. For the aspect of (5) above, for example, the yellow pigment is one or more selected from C.I. Pigment Yellow 139, 185, 231, 233, the blue pigment is one or more selected from C.I. Pigment Blue 15:3, 15:4, 15:6, and the purple pigment is C.I. Pigment Violet 23. In the aspect of (6) above, for example, the red pigment is one or more selected from C.I. Pigment Red 177, 254, 291, 295, 296, the yellow pigment is one or more selected from C.I. Pigment Yellow 139, 185, 231, 233, the blue pigment is one or more selected from C.I. Pigment Blue 15:3, 15:4, 15:6, and the violet pigment is C.I. Pigment Violet 23. In the aspect of (7) above, for example, the yellow pigment is one or more selected from C.I. Pigment Yellow 139, 185, 231, 233, the blue pigment is one or more selected from C.I. Pigment Blue 15:3, 15:4, 15:6, the green pigment is one or more selected from C.I. Pigment Green 7, 36, 58, 59, 63, and the violet pigment is C.I. Pigment Violet 23.

[0218] These combinations of the above-mentioned (1) to (7) colored pigments are preferable when the photosensitive composition of the present invention is used for a near-infrared transmission filter.

[0219] (White Pigment) The white pigment is not particularly limited, and known white pigments can be used. For example, 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, compounds described in JP 2011-075786 A, WO 2013 / 061621, JP 2015-047520 A, JP 2015-164881 A, etc. In addition, as compounds classified as pigments in the Color Index, C.I. 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, 33, etc.

[0220] (Black pigment) The black pigment is not particularly limited, and known black pigments can be used. For example, carbon black, titanium black, acetylene black, lamp black, graphite, aniline black, cyanine black, perylene black, compounds described in JP-A-1-170601, JP-A-2-34664, JP-A-2007-302836, WO2010 / 534726, WO2012 / 515233, etc. are included. In addition, as compounds classified as pigments in the Color Index, C.I. Pigment Black 1, 6, 7, 12, 20, 31, etc. are included.

[0221] (Near-infrared absorbing pigment) The near-infrared absorbing pigment is a compound having a maximum absorption in the range of 700 nm or more and 2,000 nm or less in wavelength, and may be either an organic pigment (also referred to as a near-infrared absorbing organic pigment) or an inorganic pigment (also referred to as a near-infrared absorbing inorganic pigment). Further, a near-infrared absorbing organic pigment and a near-infrared absorbing inorganic pigment may be used in combination.

[0222] 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. are included. Among these, from the viewpoints of near-infrared absorbency and heat resistance, naphthalocyanine compounds, pyrrolopyrrole compounds, squarylium compounds, and indigo compounds are preferable, and naphthalocyanine compounds, squarylium compounds, and indigo compounds are more preferable.

[0223] The near-infrared absorbing inorganic pigment is not particularly limited, and known near-infrared absorbing inorganic pigments can be used. For example, metal oxide particles or metal particles such as indium tin oxide, antimony tin oxide, zinc oxide, Al-doped zinc oxide, fluorine-doped tin dioxide, niobium-doped titanium dioxide, cesium tungsten oxide, lanthanum boride, copper, nickel, silver, and gold can be mentioned.

[0224] [Dye (H)] The photosensitive composition of the present invention can contain dye (H).

[0225] There are no particular restrictions on dye (H), and known compounds can be used. For example, acid dyes, direct dyes, basic dyes, salt-forming dyes, oil-soluble dyes, disperse dyes, reactive dyes, mordant dyes, building dyes, sulfur dyes, etc. can be mentioned. Also, derivatives thereof and lake pigments obtained by lake-forming dyes are also included.

[0226] The acid dye preferably has an acidic group such as a sulfonic acid or a carboxylic acid. Also, a salt-forming compound that 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. Also, a salt-forming compound that is a salt of a resin component having these functional groups and an acid dye is also preferred. Further, the salt-forming compound is easily sulfonamidated and modified into a sulfonic acid amide compound to obtain a photosensitive composition excellent in resistance (light resistance, solvent resistance). Also, a salt-forming compound of an acid dye and a compound having an onium base is also preferred because it is excellent in resistance (light resistance, solvent resistance). The compound having an onium base is preferably a resin having a cationic group.

[0227] Basic dyes can be used as they are, but salt-forming compounds that form salts with organic acids, perchloric acid, or their metal salts are preferred. The salt-forming compounds of basic dyes are preferred because of their excellent resistance (light resistance, solvent resistance) and affinity with pigments. In addition, among the salt-forming compounds of basic dyes, the anionic components that act as counterions are organic sulfonic acids, organic sulfuric acids, fluorine group-containing phosphorus anion compounds, fluorine group-containing boron anion compounds, cyano group-containing nitrogen anion compounds, anion compounds having a conjugated base of an organic acid having a halogenated hydrocarbon group, and salt-forming compounds formed by salting with acid dyes. Note that the salt-forming compound has improved resistance when it contains a polymerizable unsaturated group in the molecule.

[0228] The chemical structure of the dye (H) is derived from a dye selected from, for example, azo dyes, disazo dyes, azomethine dyes (such as indoaniline dyes, indophenol dyes, etc.), dipyrromethene dyes, quinone dyes (such as benzoquinone dyes, naphthoquinone dyes, anthraquinone dyes, anthrapyridone dyes, etc.), carbonium dyes (such as diphenylmethane dyes, triphenylmethane dyes, xanthene dyes, acridine dyes, etc.), quinoneimine dyes (such as oxazine dyes, thiazine dyes, etc.), azine dyes, polymethine dyes (such as 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.

[0229] Among these, from the viewpoint of color characteristics such as hue, color separation property, and color unevenness, a pigment structure derived from a pigment 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 preferable, and a pigment structure derived from a pigment selected from xanthene dyes, cyanine dyes, triphenylmethane dyes, anthraquinone dyes, dipyrromethene dyes, and phthalocyanine dyes is more preferable.

[0230] The dye (H) can be used alone or in combination of two or more.

[0231] The content of the dye (H) is preferably 0.5% by mass or more and 60% by mass or less, more preferably 1% by mass or more and 50% by mass or less in 100% by mass of the non-volatile components of the photosensitive composition.

[0232] [Pigment Derivative (I)] The photosensitive composition of the present invention can contain the pigment derivative (I). When the pigment derivative (I) is used, the pigment (G) can be stably dispersed.

[0233] The pigment derivative (I) 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. Specifically, compounds having acidic substituents such as sulfo groups, carboxy groups, and phosphate groups, and amine salts thereof, compounds having basic substituents such as sulfonamide groups and tertiary amino groups at the terminals, and compounds having neutral substituents such as phenyl groups and phthalimidoalkyl groups can be mentioned. Examples of the pigment include diketopyrrolopyrrole compounds, phthalocyanine compounds, anthraquinone compounds, quinacridone compounds, dioxazine compounds, perinone compounds, perylene compounds, thiazine indigo compounds, triazine compounds, benzimidazolone compounds, benzisoindole compounds, isoindoline compounds, isoindolinone compounds, quinophthalone compounds, naphthol compounds, squarylium compounds, threne compounds, naphthalocyanine compounds, and the like.

[0234] The pigment derivative (I) is preferably added during the micronization of the above-described pigment (G) or during the dispersion treatment of the pigment (G) described later. The average primary particle diameter of the pigment derivative (I) is preferably 5 nm or more and 200 nm or less.

[0235] The pigment derivative (I) can be used alone or in combination of two or more.

[0236] The content of the pigment derivative (I) is preferably 1 part by mass or more and 50 parts by mass or less, more preferably 2 parts by mass or more and 40 parts by mass or less, based on 100 parts by mass of the pigment (G).

[0237] [Dispersion resin (J)] The photosensitive composition of the present invention can contain a dispersion resin (J). The dispersion resin (J) can stably disperse the pigment (G) which is a component of the photosensitive composition. In the present specification, the dispersion resin (J) is not included in the alkali-soluble resin (A).

[0238] The dispersion resin (J) is preferably a resin having an adsorption group with high affinity for the pigment (G). The adsorption group preferably has at least one of a basic group and an acidic group.

[0239] Examples of the basic group include groups containing a nitrogen atom such as a primary amino group, a secondary amino group, a tertiary amino group, a quaternary ammonium base, and a nitrogen-containing heterocyclic ring.

[0240] Examples of the acidic group include a carboxyl group, a phosphoric acid group, and a sulfonic acid group.

[0241] The resin type of the dispersion resin (J) is, for example, urethane resin, polycarboxylic acid esters such as polyacrylate, unsaturated polyamide, polycarboxylic acid, polycarboxylic acid (partial) amine salt, polycarboxylic acid ammonium salt, polycarboxylic acid alkylamine salt, polysiloxane, long-chain polyaminoamidinate, hydroxyl group-containing polycarboxylic acid ester, and modified products thereof, amides formed by the reaction of poly(lower alkyleneimine) and polyester having a free carboxyl group and salts thereof, etc., (meth)acrylic acid-styrene copolymer, (meth)acrylic acid-(meth)acrylate copolymer, styrene-maleic acid copolymer, polyvinyl alcohol, water-soluble resins and water-soluble polymer compounds such as polyvinylpyrrolidone, polyester-based, modified polyacrylate-based, ethylene oxide / propylene oxide adduct compounds, phosphate ester-based, etc.

[0242] Examples of the structure of the dispersion resin (J) 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, a block structure, a graft structure, and a comb structure are preferable.

[0243] From the viewpoint of resistance to low-temperature heating, the dispersion resin (J) preferably has a thermosetting group and / or a polymerizable unsaturated group. Examples of the thermosetting group include a hydroxyl group, an epoxy group, an oxetanyl group, a tert-butyl group, a blocked isocyanate group, etc.

[0244] Examples of the dispersion resin (J) include resins described in paragraph numbers 0122 to 0155 of International Publication No. 2013 / 175978, resins described in paragraph numbers 0317 to 0321 of Japanese Patent Application Laid-Open No. 2019-78878, resins described in paragraph number 0083 of International Publication No. 2018 / 139534, resins described in paragraph numbers 0167 to 0191 of International Publication No. 2019 / 163505, resins described in paragraph numbers 0299 to 0310 of International Publication No. 2021 / 131927, resins described in paragraph numbers 0080 to 0085 of International Publication No. 2022 / 102367, resins described in paragraph numbers 0099 to 0109 of International Publication No. 2022 / 172607, etc.

[0245] Commercially available products of the dispersion resin (J) 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, or Anti-Terra-U 203, 204, or BYK-P104, P104S, 220S, or Lactimon, Lactimon-WS, or 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, 76500, etc. manufactured by Lubrizol 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, etc. manufactured by BASF Japan, Aji Super PA111, PB711, PB821, PB822, PB824, etc. manufactured by Ajinomoto Fine-Techno Co., Ltd., resins described in JP-A No. 2008-029901, JP-A No. 2009-155406, JP-A No. 2010-185934, JP-A No. 2011-157416, WO 2008 / 007776, JP-A No. 2008-029901, JP-A No. 2009-155406, JP-A No. 2010-185934, JP-A No. 2011-157416, JP-A No. 2009-251481, JP-A No. 2007-23195, JP-A No. 1996-143651, etc.

[0246] The dispersion resin (J) can be used alone or in combination of two or more kinds.

[0247] From the viewpoint of dispersion stability, the content of the dispersion resin (J) is preferably 3 parts by mass or more and 200 parts by mass or less, more preferably 5 parts by mass or more and 150 parts by mass or less with respect to 100 parts by mass of the pigment (G).

[0248] [Sensitizer (K)] The photosensitive composition of the present invention can contain a sensitizer (K).

[0249] Examples of the sensitizer (K) include chalcone compounds, unsaturated ketones typified by dibenzalacetone, 1,2-diketone compounds typified by benzyl and camphorquinone, benzoin compounds, fluorene compounds, naphthoquinone compounds, anthraquinone compounds, xanthene compounds, thioxanthene compounds, xanthone compounds, thioxanthone compounds, coumarin compounds, ketocoumarin compounds, polymethine dyes such as cyanine compounds, merocyanine compounds, oxonol compounds, acridine compounds, azine compounds, thiazine compounds, oxazine compounds, indoline compounds, azulene compounds, azulenium compounds, squarylium compounds, porphyrin compounds, tetraphenylporphyrin compounds, triarylmethane compounds, tetrabenzoporphyrin compounds, tetrapyrazinoporphyrazine compounds, phthalocyanine compounds, tetraazaporphyrazine compounds, tetraquinoxalyloporphyrazine compounds, naphthalocyanine compounds, subphthalocyanine compounds, pyrylium compounds, thiopyrylium compounds, tetraphyrin compounds, annulene compounds, spiropyran compounds, spirooxazine compounds, thiospiropyran compounds, metal arene complexes, organoruthenium complexes, or benzophenone compounds. Among these, thioxanthone compounds and benzophenone compounds are preferred.

[0250] The sensitizer (K) can be used alone or in combination of two or more kinds.

[0251] The content of the sensitizer (K) is preferably 10 parts by mass or more and 400 parts by mass or less, more preferably 20 parts by mass or more and 300 parts by mass or less, based on 100 parts by mass of the photopolymerization initiator (C).

[0252] [Hardening agent (hardening accelerator)] In order to assist the curing of the thermosetting compound (F), the photosensitive composition of the present invention can be used in combination with a hardening agent (hardening accelerator). Examples of the hardening agent include amine compounds, acid anhydrides, active esters, carboxylic acid compounds, sulfonic acid compounds, etc. Examples of the hardening agent include amine compounds (for example, dicyandiamide, benzyldimethylamine, 4-(dimethylamino)-N,N-dimethylbenzylamine, 4-methoxy-N,N-dimethylbenzylamine, 4-methyl-N,N-dimethylbenzylamine, etc.), quaternary ammonium salt compounds (for example, triethylbenzylammonium chloride, etc.), blocked isocyanate compounds (for example, dimethylamine, etc.), imidazole derivatives, bicyclic amidine compounds and their salts (for example, 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 (for example, triphenylphosphine, etc.), S-triazine derivatives (for example, 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.).

[0253] The hardening agent can be used alone or in combination of two or more.

[0254] The content of the hardening agent is preferably 0.01 parts by mass or more and 15 parts by mass or less, based on 100 parts by mass of the thermosetting compound (F).

[0255] [Thiol-based chain transfer agent (L)] The photosensitive composition of the present invention can contain a thiol-based chain transfer agent (L). When the thiol-based chain transfer agent (L) is used in combination with a photopolymerization initiator (C), during radical polymerization after light irradiation, thiyl radicals that are less susceptible to polymerization inhibition by oxygen are generated, improving the photosensitivity of the photosensitive composition.

[0256] 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, 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-mercaptinicotinic acid, 2-mercaptopropionic acid, 3-mercaptopropionic acid, 4-mercaptobutanoic acid, octyl thioglycolate, mercaptosuccinic acid, 11-mercaptoundecanoic acid, 2-mercaptoethanesulfonic acid; Hexanedithiol, decanedithiol, 1,4-butanediol bisthiopropionate, 1,4-butanediol bisthioglycolate, ethylene glycol bisthioglycolate, ethylene glycol bisthiopropionate, trimethylolpropane tristhioglycolate, trimethylolpropane tristhiopropionate, trimethylolpropane tris(3-mercaptobutyrate), pentaerythritol tetrakisthioglycolate, pentaerythritol tetrakis(3-mercaptopropionate), tris(2-hydroxyethyl) isocyanurate trimercaptopropionate, 1,4-dimethylmercaptobenzene, 2,4,6-trimercapto-s-triazine, 2-(N,N-dibutylamino)-4,6-dimercapto-s-triazine and other polyfunctional thiol compounds can be mentioned.

[0257] The thiol-based chain transfer agent (L) can be used alone or in combination of two or more.

[0258] The content of the thiol-based chain transfer agent (L) is preferably 1% by mass or more and 10% by mass or less in 100% by mass of the non-volatile content of the photosensitive composition.

[0259] [Ultraviolet absorber (M)] The photosensitive composition of the present invention can contain an ultraviolet absorber (E). Thereby, the influence of the exposure amount change, the polymerization initiator type and amount is suppressed, and a stable line width can be obtained.

[0260] Examples of the ultraviolet absorber (M) include benzotriazole compounds, benzophenone compounds, triazine compounds, conjugated diene compounds, methyldibenzoyl compounds, coumarin compounds, acrylonitrile compounds, benzothiazole compounds, salicylate compounds and the like.

[0261] (Benzotriazole compound) Benzotriazole compounds include, for example, 2-(5-tert-butyl-2-hydroxyphenyl)benzotriazole, benzenepropanoic acid and 3-(2H-benzotriazol-2-yl)-5-(1,1-dimethylethyl)-4-hydroxy (C7-9 side chain and straight-chain alkyl) ester compounds, 2-[5-chloro-(2H)-benzotriazol-2-yl]-4-methyl-6-(tert-butyl)phenol, 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 and the like. Commercially available products include, for example, Tinuvin PS, 99-2, 326, 384-2, 900, 928, 970, 1130 manufactured by BASF Japan, UVA-903KT, Adeka Stab LA-31RG, LA-31G manufactured by ADEKA Corporation, and the like.

[0262] (Benzophenone compound) Benzophenone compounds include, for example, 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, hexyl diethylaminohydroxybenzoate, 4,4'-bis(dimethylamino)benzophenone, 4,4'-bis(diethylamino)benzophenone, 2-aminobenzophenone, etc. Commercially available products include, for example, Uvinul A, 3049, 3050 manufactured by BASF Japan, UVA-935LH, AdekaStab 1413 manufactured by ADEKA, etc.

[0263] (Triazine compound) Triazine compounds include, for example, the reaction product of 2-(4,6-bis(2,4-dimethylphenyl)-1,3,5-triazin-2-yl)-5-hydroxyphenyl and [(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-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. Commercially available products include, for example, Tinuvin 400, 405, 406, 477, 479 manufactured by BASF Japan, Adeka Stab LA-46, LA-F70 manufactured by ADEKA, etc.

[0264] (Conjugated diene compound) Examples of conjugated diene compounds include UV503 manufactured by Daito Chemical Co., Ltd.

[0265] (Methyldibenzoyl compound) Examples of methyldibenzoyl compounds include 1,3-diphenyl-1,3-propanedione, 1-(4-tert-butylphenyl)-3-(4-methoxyphenyl)-1,3-propanedione, 1,3-bis(4-methoxyphenyl)-1,3-propanedione, etc.

[0266] (Coumarin compound) Examples of coumarin compounds include 4-hydroxycoumarin, 7-hydroxycoumarin, etc.

[0267] The ultraviolet absorber (M) can be used alone or in combination of two or more kinds.

[0268] The content of the ultraviolet absorber (M) is preferably 30 parts by mass or more and 300 parts by mass or less, more preferably 60 parts by mass or more and 200 parts by mass or less with respect to 100 parts by mass of the photopolymerization initiator (C).

[0269] [Polymerization inhibitor (N)] The photosensitive composition of the present invention can contain a polymerization inhibitor (N).

[0270] Examples of the polymerization inhibitor (N) include alkyl catechol compounds such as catechol, resorcinol, 1,4-hydroquinone, 2-methylcatechol, 3-methylcatechol, 4-methylcatechol, 2-ethylcatechol, 3-ethylcatechol, 4-ethylcatechol, 2-propylcatechol, 3-propylcatechol, 4-propylcatechol, 2-n-butylcatechol, 3-n-butylcatechol, 4-n-butylcatechol, 2-t-butylcatechol, 3-t-butylcatechol, 4-t-butylcatechol, 3,5-di-t-butylcatechol; alkyl resorcinol compounds such as 2-methylresorcinol, 4-methylresorcinol, 2-ethylresorcinol, 4-ethylresorcinol, 2-propylresorcinol, 4-propylresorcinol, 2-n-butylresorcinol, 4-n-butylresorcinol, 2-t-butylresorcinol, 4-t-butylresorcinol; alkyl hydroquinone compounds such as methylhydroquinone, ethylhydroquinone, propylhydroquinone, tert-butylhydroquinone, 2,5-di-t-butylhydroquinone; phosphine compounds such as tributylphosphine, trioctylphosphine, tricyclohexylphosphine, triphenylphosphine, tribenzylphosphine; phosphine oxide compounds such as trioctylphosphine oxide, triphenylphosphine oxide; phosphite compounds such as triphenyl phosphite, trisnonylphenyl phosphite; pyrogallol, phloroglucin, and the like.

[0271] The content of the polymerization inhibitor (N) is preferably 0.01% by mass or more and 0.4% by mass or less in 100% by mass of the non-volatile content of the photosensitive composition.

[0272] [Antioxidant (O)] The photosensitive composition of the present invention can contain an antioxidant (O). The antioxidant (O) prevents the photoinitiator (C) and the thermosetting compound (F) in the photosensitive composition from being oxidized by heat during the heating process or during ITO annealing and turning yellow.

[0273] Examples of the antioxidant (O) 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.

[0274] Commercially available products of hindered phenol-based antioxidants include, for example, ADEKA STAB AO-20, AO-30, AO-40, AO-50, AO-60, AO-80, AO-330 manufactured by ADEKA Corporation; KEMINOX 101, 179, 76, 9425 manufactured by Chemipro Kasei Co., Ltd.; IRGANOX 1010, 1035, 1076, 1098, 1135, 1330, 1726, 1425WL, 1520L, 245, 259, 3114, 5057, 565 manufactured by BASF Japan Ltd.; CYANOX CY-1790, CY-2777 manufactured by Sankyo Chemical Co., Ltd., etc.

[0275] Commercially available products of hindered amine-based antioxidants include, for example, ADEKA STAB LA-52, LA-57, LA-63P, LA-68, LA-72, LA-77Y, LA-77G, LA-81, LA-82, LA-87, LA-402F, LA-502XP manufactured by ADEKA Corporation; KAMISTAB 29, 62, 77, 94 manufactured by Chemipro Kasei Co., Ltd.; Tinuvin 111FDL, 123, 144, 249, 292, 5100 manufactured by BASF Japan Ltd.; CYASORB UV-3346, UV-3529, UV-3853 manufactured by Sankyo Chemical Co., Ltd., etc.

[0276] Commercially available phosphorus-based antioxidants include, for example, Adekastab PEP-36, PEP-8, HP-10, 2112, 1178, 1500, C, 135A, 3010, TPP manufactured by ADEKA Corporation; IRGAFOS 168 manufactured by BASF Japan Ltd.; Hostanox P-EPQ manufactured by Clariant Chemicals, etc.

[0277] Commercially available sulfur-based antioxidants include, for example, Adekastab AO-412S, AO-503 manufactured by ADEKA Corporation; KEMINOX PLS manufactured by Chemipro Kasei Co., Ltd., etc.

[0278] The antioxidant (O) can be used alone or in combination of two or more.

[0279] The content of the antioxidant (O) is preferably 0.5% by mass or more and 5.0% by mass or less in 100% by mass of the non-volatile content of the photosensitive composition.

[0280] [Leveling agent (P)] The photosensitive composition of the present invention can contain a leveling agent (P). Thereby, the wettability and drying property with respect to the substrate during coating are improved.

[0281] Examples of the leveling agent (P) include silicone-based surfactants, fluorine-based surfactants, nonionic surfactants, cationic surfactants, anionic surfactants, amphoteric surfactants, etc.

[0282] Examples of the silicone-based surfactant include linear polymers composed of siloxane bonds and modified siloxane polymers having organic groups introduced into the side chains or terminals.

[0283] Commercially available products include, for example, BYK-300, 306, 310, 313, 315N, 320, 322, 323, 330, 331, 333, 342, 345, 346, 347, 348, 349, 370, 377, 378, 3455, UV3510, 3570 manufactured by BYK-Chemie GmbH; FZ-7002, 2110, 2122, 2123, 2191, 5609 manufactured by Toray Dow Corning Co., Ltd.; X-22-4952, X-22-4272, X-22-6266, KF-351A, KF-354L, KF-355A, KF-945, KF-640, KF-642, KF-643, X-22-4515, KF-6004, KP-341 manufactured by Shin-Etsu Chemical Co., Ltd., etc.

[0284] Fluorine-based surfactants include, for example, surfactants or leveling agents having a fluorocarbon chain.

[0285] Commercially available products include, for example, Surfynol S-242, 243, 420, 611, 651, 386 manufactured by AGC Seimi Chemical Co., Ltd.; Megafac F-253, 477, 551, 552, 555, 558, 560, 570, 575, 576, R-40-LM, R-41, RS-72-K, DS-21 manufactured by DIC Corporation; FC-4430, 4432 manufactured by Sumitomo 3M Limited; EF-PP31N09, EF-PP33G1, EF-PP32C1 manufactured by Mitsubishi Materials Electronic Chemicals Co., Ltd.; Ftergent 602A manufactured by Neos Co., Ltd., etc.

[0286] Commercially available nonionic surfactants include, for example, Emulgen 103, 104P, 106, 108, 109P, 120, 123P, 130K, 147, 150, 210P, 220, 306P, 320P, 350, 404, 408, 409PV, 420, 430, 705, 707, 709, 1108, 1118S-70, 1135S-70, 1150S-60, 2020G-HA, 2025G, LS-106, LS-110, LS-114, MS-110, A-60, A-90, B-66, PP-290 manufactured by Kao Corporation; Latemul PD-420, PD-430, PD-430S, PD-450; Leodol SP-L10, SP-P10, SP-S10V, SP-S20, SP-S30V, SP-O10V, SP-O30V; Super SP-L10, AS-10V, AO-10V, AO-15V, TW-L120, TW-L106, TW-P120, TW-S120V, TW-S320V, TW-O120V, TW-O106V, TW-IS399C; Super TW-L120, 430V, 440V, 460V, MS-50, MS-60, MO-60, MS-165V; Emanon 1112, 3199V, 3299V, 3299RV, 4110, CH-25, CH-40, CH-60(K), Amite 102, 105, 105A, 302, 320; Aminon PK-02S; L-02; Homogenol L-95; Adeka Pluronic (registered trademark) L-23, 31, 44, 61, 62, 64, 71, 72, 101, 121 manufactured by ADEKA Corporation; TR-701, 702, 704, 913R; Polyflow No. 75, No. 90, No. 95, (meth)acrylic acid-based (co)polymers manufactured by Kyoeisha Chemical Co., Ltd.; EFS-801 manufactured by DIC Corporation, etc.

[0287] Commercially available cationic surfactants include, for example, Acetamine 24, Cotamine 24P, 60W, 86P Conc. etc. manufactured by Kao Corporation.

[0288] Commercially available anionic surfactants include, for example, Ftergent 100, 150 manufactured by Neos Corporation; Adeka Hope YES-25; Adeka Cole TS-230E, PS-440E, EC-8600 etc. manufactured by ADEKA Corporation.

[0289] Commercially available amphoteric surfactants include Amhitole 20AB, 20BS, 24B, 55AB, 86B, 20Y-B, 20N, etc. manufactured by Kao Corporation.

[0290] The leveling agent (P) can be used alone or in combination of two or more.

[0291] The content of the leveling agent (P) is preferably 0.001% by mass or more and 2.0% by mass or less, more preferably 0.005% by mass or more and 1.0% by mass or less in 100% by mass of the non-volatile content of the photosensitive composition.

[0292] [Storage stabilizer (Q)] The photosensitive composition of the present invention can contain a storage stabilizer (Q). Thereby, the viscosity of the photosensitive composition over time is stabilized.

[0293] 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 tetraphenyl, and phosphites.

[0294] The content of the storage stabilizer (Q) is preferably 0.05% by mass or more and 5% by mass or less in 100% by mass of the non-volatile content of the photosensitive composition.

[0295] [Organic solvent (R)] The photosensitive composition of the present invention can contain an organic solvent (R).

[0296] The organic solvent (R) is, 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, ethyl 3-ethoxypropionate, 3-methyl-1,3-butanediol, 3-methoxy-3-methyl-1-butanol, 3-methoxy-3-methylbutyl 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-butylbenzene, 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 and the like can be mentioned. Among these, from the viewpoints of resin solubility and coatability, glycol acetates such as ethyl lactate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, alcohols such as diacetone alcohol, and ketones such as cyclohexanone are preferred.

[0297] From the environmental aspect, it is preferable that the photosensitive composition of the present invention substantially does not contain organic solvents which are aromatic hydrocarbons (such as toluene, xylene, benzene, chlorobenzene, etc.). Substantially not containing means that in the photosensitive composition, it is 50 mass ppm or less, preferably 30 mass ppm or less, and more preferably 10 mass ppm or less.

[0298] The organic solvent (R) can be used alone or in combination of two or more.

[0299] The content of the organic solvent (R) is preferably an amount such that the nonvolatile content of the photosensitive composition is 5 mass% or more and 60 mass% or less.

[0300] [Content of specific metal elements] In the photosensitive composition of the present invention, the total content of Li, Na, K, Mg, Ca, Fe, and Cr (hereinafter also referred to as specific metal elements) contained in the photosensitive composition is preferably 500 mass ppm or less.

[0301] When the total amount of specific metal elements is within the above range in the photosensitive composition, it has excellent dispersion stability and sensitivity even after storage over time. The content of specific metal elements can be measured by inductively coupled plasma optical emission spectrometry (ICP).

[0302] [Content of water] In the photosensitive composition of the present invention, the water content contained in the photosensitive composition is preferably 2.0 mass% or less.

[0303] When the water content is within the above range in the photosensitive composition, it 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.

[0304] [Method for producing photosensitive composition] The photosensitive composition of the present invention can be prepared by mixing the above-mentioned components. When adjusting, each component may be blended all at once, or each component may be dissolved or dispersed in the polymerizable compound (B) or the organic solvent (R) and then sequentially blended. When using components with low solubility, such as the pigment (G), it is preferable to perform a dispersion treatment first. For example, a dispersion is produced by adding the pigment (G), the dispersion resin (J), the organic solvent (R), etc. and performing a dispersion treatment. Thereafter, it can be produced by blending and mixing the alkali-soluble resin (A), the polymerizable compound (B), the photopolymerization initiator (C), the thermosetting compound (F), etc. into the dispersion. The timing of blending each material is arbitrary. Also, the dispersion step can be performed multiple times.

[0305] Dispersion machines that perform dispersion processing include, for example, two-roll mills, three-roll mills, ball mills, horizontal sand mills, vertical sand mills, annular bead mills, or attritors, etc.

[0306] The average dispersed particle diameter (secondary particle diameter) of the particles in the dispersion is preferably 30 to 200 nm, more preferably 40 to 200 nm. A photosensitive composition with high dispersion stability is easily obtained when it has an appropriate particle diameter.

[0307] As a method for measuring the average dispersed particle diameter (secondary particle diameter), for example, using the Microtrac UPA-EX150 of Nikkiso Co., Ltd. that employs the dynamic light scattering method (FFT power-spectrum method), set the particle permeability to the absorption mode, the particle shape to non-spherical, and the D50 particle diameter as the average diameter. For the dilution solvent used for measurement, use the organic solvents used for dispersion respectively. When measuring the sample immediately after sample preparation for the sample treated with ultrasonic waves, results with less variation are easily obtained and are preferable.

[0308] It is preferable to remove coarse particles of 5 μm or more, preferably 1 μm or more, more preferably 0.5 μm or more, and mixed dust from the photosensitive composition by means such as centrifugation, filtration using a sintered filter or a membrane filter. 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.

[0309] The photosensitive composition of the present invention can be preferably used for pattern formation by the photolithography method. Note that the present invention is not limited to this.

[0310] <Film> The film of the present invention is formed using the above-described photosensitive composition. The film is preferably a film with a pattern formed, but it can also be used as a flat film.

[0311] [Method for manufacturing film] The method for manufacturing the film is not particularly limited, and known methods can be used. In the present invention, when creating the film, the heating temperature is preferably 150°C or lower, more preferably 130°C or lower, and even more preferably 100°C or lower throughout all steps. By performing heating at 150°C or lower, when an organic EL element is used as the light-emitting light source of the image display device, or when the photoelectric conversion film of the image sensor is an organic material, or when a heat-sensitive substrate such as a plastic film is used, these performances can be maintained. Note that the heating temperature is preferably 50°C or higher.

[0312] For manufacturing the film, first, the photosensitive composition of the present invention is coated on a substrate. Examples of the substrate include a substrate made of a material such as glass, resin, or silicon. The glass may be colorless and transparent, or colored glass such as blue glass may be used depending on the application. An organic light-emitting layer may be formed on these substrates. Also, an imaging element such as a CCD or CMOS may be formed on the substrate. Further, a primer layer may be provided on the substrate as needed for improving adhesion with an upper layer, preventing diffusion of substances, and planarizing the surface.

[0313] Known coating methods can be used. For example, the dropping method, slit coating method, spray method, roll coating method, spin coating method, casting coating method, inkjet method, flexographic printing, screen printing, gravure printing, offset printing, etc. can be mentioned.

[0314] The thickness of the film can be appropriately adjusted according to the purpose. The thickness of the film is preferably 0.05 μm or more and 20.0 μm or less, and more preferably 0.3 μm or more and 10.0 μm or less.

[0315] Next, a pattern is formed. Examples of the method for forming the pattern include the photolithography method and the dry etching method. Among these, the photolithography method is preferred. Note that when used as a flat film, the step of forming a pattern does not need to be performed, and after coating, drying or overall exposure may be performed as needed.

[0316] Hereinafter, a method for forming a pattern by photolithography will be described in detail.

[0317] When forming a pattern by photolithography, a layer formed by coating the photosensitive composition of the present invention on a substrate is dried at a temperature of 150°C or lower as necessary, and then exposed in a pattern through a mask (exposure step). After removing the unexposed portion by alkali development (development step), the pattern is heat-treated (heating step).

[0318] 〔Exposure step〕 In the exposure step, the layer formed by coating is exposed to a specific pattern through a mask using an exposure apparatus such as a stepper. Thereby, the exposed portion can be cured. Examples of the active energy ray used for exposure include ultraviolet rays such as g-line (wavelength 436 nm), h-line (wavelength 405 nm), and i-line (wavelength 365 nm). In addition, light having a wavelength of 300 nm or less can also be used. Examples of the light having a wavelength of 300 nm or less include KrF line (wavelength 248 nm), ArF line (wavelength 193 nm), and the like. In addition, at the time of exposure, the light may be continuously irradiated for exposure, or the light may be repeatedly irradiated and stopped in a short time (for example, at the millisecond level or less) for exposure (pulse exposure).

[0319] 〔Development step〕 Next, by treating with an alkali developer, the layer of the unexposed portion is eluted in the alkali developer, and only the cured portion remains to obtain a patterned film. Examples of the alkali developer include alkaline compounds such as sodium hydroxide, potassium hydroxide, sodium carbonate, sodium silicate, sodium metasilicate, aqueous ammonia, ethylamine, diethylamine, dimethylethanolamine, tetramethylammonium hydroxide, tetraethylammonium hydroxide, choline, pyrrole, piperidine, and 1,8-diazabicyclo-[5.4.0]-7-undecene. The concentration of the alkaline developer is preferably 0.001% by mass or more and 10% by mass or less, more preferably 0.01% by mass or more and 1% by mass or less. The pH of the alkaline developer is preferably 11 or more and 13 or less, more preferably 11.5 or more and 12.5 or less. When used at an appropriate pH, roughness and peeling of the pattern are suppressed, and the residual film rate after development is improved. Examples of the development method include dip method, spray method, paddle method, etc. The development temperature is preferably 15°C or more and 40°C or less. After alkaline development, it is preferably washed with pure water.

[0320] 〔Heating step〕 After development, heat treatment is performed. By heating, the resistance of the film is improved. The heating temperature is preferably 150°C or less, more preferably 130°C or less, and still more preferably 100°C or less. The heating time is preferably about 2 minutes to 2 hours.

[0321] <Optical filter> The optical filter of the present invention has the above-mentioned film. The optical filter is used, for example, in color filters, black matrices, light-shielding filters, antireflection filters, infrared cut filters, infrared transmission filters, microlenses, etc. The optical filter of the present invention can be manufactured by the same method as the above-mentioned film.

[0322] <Solid-state imaging device> The solid-state imaging device of the present invention has the above-mentioned optical filter. The solid-state imaging device includes the optical filter of the present invention and is not particularly limited as long as it functions as a solid-state imaging device. Examples of the configuration include the following.

[0323] On a substrate, there are a plurality of photodiodes constituting a light-receiving area of a solid-state imaging device (such as a CCD image sensor, a CMOS image sensor, etc.) and transfer electrodes made of polysilicon or the like. There is a light-shielding film with an opening only in the light-receiving part of the photodiode on the photodiodes and the transfer electrodes. There is a device protection film made of silicon nitride or the like formed so as to cover the entire surface of the light-shielding film and the light-receiving part of the photodiode on the light-shielding film. On the device protection film, there is a configuration having the optical filter (color filter) of the present invention. Further, a configuration having condensing means (for example, a microlens, etc. The same applies hereinafter) on the device protection film and below the optical filter (closer to the substrate side), or a configuration having condensing means on the optical filter may be used. Also, the filter may have a structure in which a cured film forming each colored pixel is embedded in a space partitioned, for example, in a lattice shape by partition walls. In this case, the partition walls preferably have a low refractive index with respect to each colored pixel. The imaging device provided with the solid-state imaging device of the present invention can be used for various applications such as, for example, a digital camera, an electronic device having an imaging function (such as a mobile phone, a smartphone, etc.), an in-vehicle camera, and a surveillance camera.

[0324] <Image display device> The image display device of the present invention has the above optical filter. Examples of the image display device include a liquid crystal display, an organic EL display, and the like. The form used in the image display device only needs to function as an image display device and is not particularly limited. For example, the configurations described in "Next-generation liquid crystal display technology" (written by Tatsuo Uchida, published by Kogyo Chosa Kai, Inc., in 1994) and the like can be mentioned. Regarding the definition of the image display device and the details of each image display device, they are described in, for example, "Electronic display devices" (written by Akio Sasaki, published by Kogyo Chosa Kai, Inc., in 1990), "Display devices" (written by Junsho Ibuki, published by Sangyo Tosho Co., Ltd., in 1989), and the like.

[0325] <Infrared sensor> The infrared sensor of the present invention has the above optical filter. The form used for the infrared sensor is not particularly limited as long as it includes the optical filter of the present invention and functions as an infrared sensor. For example, the following configurations can be mentioned.

[0326] On a substrate, there are a plurality of photodiodes that constitute the light-receiving area of a solid-state imaging device (such as a CCD image sensor, a CMOS image sensor, etc.) and transfer electrodes made of polysilicon or the like. On these photodiodes and transfer electrodes, there is a light-shielding film with an opening only in the light-receiving part of the photodiodes. On this light-shielding film, there is a device protection film, and further on this device protection film, there is the optical filter of the present invention. Furthermore, a configuration having condensing means (for example, a microlens, etc. The same applies hereinafter) on the device protection film and below the optical filter (the side closer to the substrate) or a configuration having condensing means on the optical filter may also be used.

[0327] FIG. 1 is a schematic cross-sectional view showing a configuration example of an infrared sensor including the optical filter of the present invention. The infrared sensor shown in FIG. 1 is 100 and includes a solid-state imaging device 110.

[0328] The imaging area provided on the solid-state imaging device 110 is configured by combining an infrared cut filter 111 and a color filter 112.

[0329] The infrared cut filter 111 can be formed using the photosensitive composition of the present invention. The infrared cut filter 111 transmits light in the visible light region (for example, light with a wavelength of 400 to 700 nm) and shields light in the infrared region (for example, light with a wavelength of 800 to 1,300 nm).

[0330] The color filter 112 is a color filter in which pixels that transmit and absorb light of specific wavelengths in the visible light region are formed. For example, a color filter in which pixels of red (R), green (G), and blue (B) are formed is used.

[0331] Between the infrared transmission filter 113 and the solid-state imaging device 110, a resin film 114 that can transmit light with the wavelength transmitted through the infrared transmission filter 113 is disposed.

[0332] The infrared transmission filter 113 can be formed using the photosensitive composition of the present invention, has visible light shielding properties, and is a filter that transmits infrared rays of a specific wavelength. The infrared transmission filter 113 preferably shields light with wavelengths of 400 to 830 nm and transmits light with wavelengths of 900 to 1,300 nm, for example.

[0333] 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.

[0334] In the form shown in FIG. 1, a resin film 114 is disposed, but an infrared transmission filter 113 may be formed instead of the resin film 114.

[0335] According to this infrared sensor, since image information can be captured simultaneously, motion sensing or the like for recognizing an object to be detected for motion is possible. Further, according to this infrared sensor, since distance information can be obtained, photographing of an image including 3D information is also possible. Furthermore, this infrared sensor can also be used as a biometric authentication sensor.

Example

[0336] Hereinafter, the present invention will be described more specifically with reference to examples. However, the present invention is not limited to the examples. In addition, "parts" means "parts by mass" and "%" means "% by mass". In the present invention, the nonvolatile content or the nonvolatile content concentration refers to the mass residue after standing in an oven at 110 ° C for 3 hours.

[0337] Prior to the examples, each measurement method will be described.

[0338] The measurement of the weight average molecular weight (Mw), number average molecular weight (Mn), acid value (mgKOH / g), and amine value (mgKOH / g) of the resin is as follows.

[0339] (Average molecular weight) The number average molecular weight (Mn) and weight average molecular weight (Mw) were measured by gel permeation chromatography (GPC) equipped with an RI detector. HLC-8220GPC (manufactured by Tosoh Corporation) was used as the apparatus. Two separation columns were connected in series, and for both packing materials, two "TSK-GEL SUPER HZM-N" were connected in series and used. The measurement was carried out at an oven temperature of 40 °C, using a tetrahydrofuran (THF) solution as the eluent, and at a flow rate of 0.35 ml / min. The sample was dissolved in a solvent consisting of 1 mass% of the above eluent and 20 microliters were injected. The molecular weight is in terms of polystyrene conversion value.

[0340] (Acid value) To 0.5 - 1 g of the sample solution, 80 ml of acetone and 10 ml of water were added and stirred until uniformly dissolved. Using 0.1 mol / L aqueous KOH solution as the titrant, titration was carried out using an automatic titrator ("COM-555" manufactured by Hiranuma Sangyo Co., Ltd.), and the acid value (mgKOH / g) was measured. Then, from the acid value of the solution and the non-volatile content concentration of the solution, the acid value per non-volatile content was calculated.

[0341] (Amine value) The amine value is the value obtained by converting the measured total amine value (mgKOH / g) into non-volatile content in accordance with the method of ASTM D 2074.

[0342] (Production of alkali-soluble resin (A)) (Alkali-soluble resin (A1-1) solution) Into a flask equipped with a stirring device, a dropping funnel, a condenser, a thermometer, and a gas introduction tube, 100 parts of propylene glycol monomethyl ether acetate (hereinafter, PGMAc) was placed. After nitrogen substitution and stirring, the temperature was raised to 78°C. Next, 25.2 parts of Karenz MOI-DEM (malonic acid-2-[[[[(2-methyl-1-oxo-2-propenyl)oxy]ethyl]amino]carbonyl]-1,3-diethyl ester, a blocking agent that is an active methylene compound), 31.2 parts of 2-hydroxyethyl methacrylate, 37.5 parts of dicyclopentanyl methacrylate, 20.7 parts of methacrylic acid, and a mixture of 27.0 parts of methyl methacrylate, and a solution prepared by adding 12.0 parts of 2,2'-azobis(2,4-dimethylvaleronitrile) (a polymerization initiator) to 50 parts of PGMAc and dissolving them were each dropped into the flask from the dropping funnel. After the dropping was completed, stirring was carried out at 78°C for 3 hours. Thereafter, PGMAc was added so that the nonvolatile content became 40% by mass to adjust an alkali-soluble resin (A1-1) solution. The alkali-soluble resin (A1-1) had an acid value of 74 mgKOH / g and a weight-average molecular weight of 8,000. In Table 1, the blending amounts are expressed in mol%.

[0343] (Alkali-soluble resin (A1-2) to (A1-6) solutions, alkali-soluble resin (A2-1) to (A2-2) solutions) The types and amounts of monomers were changed so as to achieve the constituent ratios and weight-average molecular weights described in Table 1 to synthesize alkali-soluble resins (A1-2) to (A1-6) and alkali-soluble resins (A2-1) to (A2-2), and PGMAc was added to make the nonvolatile content 40% by mass. The weight-average molecular weight of the resin was adjusted by changing the amount of the polymerization initiator used.

[0344]

Table 1

[0345] The Calenz MOI-BP described in Table 1 is 2-(3,5-diethylpyrazol-1-yl)carbonylaminoethyl methacrylate manufactured by Showa Denko K.K., where the blocking agent is a pyrazole compound. The Calenz MOI-BM is 2-[O-(1'-methylpropylideneamino)carboxamido]ethyl methacrylate manufactured by Showa Denko K.K., where the blocking agent is an oxime compound. GMA+AA represents a polymerizable unsaturated group-containing monomer unit (a6) obtained by reacting the carboxyl group of acrylic acid (AA) with the epoxy group of glycidyl methacrylate (GMA). GMA+AA+THPA represents a polymerizable unsaturated group-containing monomer unit (a6) obtained by reacting tetrahydrophthalic anhydride (THPA) with the hydroxyl group of GMA+AA.

[0346] <Manufacture of Pigment (G)> (Yellow Pigment (G-13)) 46.2 parts of diazobarbituric acid and 38.4 parts of barbituric acid were added to 1,100 parts of distilled water at 85°C in a reaction vessel. Next, an aqueous potassium hydroxide solution was added to adjust the pH to approximately 5, and then the mixture was stirred for 90 minutes to synthesize a diazobarbituric acid precursor. 0.3 mol of the obtained diazobarbituric acid precursor was mixed with 1,500 parts of distilled water at 82°C. After dropping 10 parts of 30% hydrochloric acid, 0.6 mol of melamine was added. Next, 0.195 mol of a nickel chloride solution, 0.09 mol of a zinc chloride solution, and 0.015 mol of a copper chloride solution were mixed and dropped, and the mixture was stirred at 82°C for 3 hours to conduct the reaction. Thereafter, potassium hydroxide was added to adjust the pH to approximately 5.2, 100 parts of distilled water was added, and the temperature was raised to 90°C. Next, 21 parts of 30% hydrochloric acid was dropped, and the mixture was stirred for 12 hours to conduct the reaction. Thereafter, potassium hydroxide was added to adjust the pH to approximately 5, and the product was taken out by filtration. The product was washed with ion-exchanged water and filtered. After drying at 80°C, it was pulverized to obtain a yellow pigment (G-13) with a molar ratio of Ni, Zn, and Cu of 65:30:5.

[0347] (Near-Infrared Absorbing Pigment (G-17)) 400 parts of toluene were mixed with 40.0 parts of 1,8-diaminonaphthalene, 32.2 parts of 3,5-dimethylcyclohexanone, and 0.087 part of p-toluenesulfonic acid monohydrate, and the mixture was heated and stirred in an atmosphere of nitrogen gas and reacted while refluxing for 3 hours. The water generated during the reaction was removed from the reaction system by azeotropic distillation. After completion of the reaction, the dark brown solid obtained by distilling toluene was extracted with acetone and purified by recrystallization from a mixed solvent of acetone and ethanol. The obtained brown solid was dissolved in a mixed solvent of 240 parts of toluene and 160 parts of n-butanol, 13.8 parts of 3,4-dihydroxy-3-cyclobutene-1,2-dione was added, and the mixture was heated and stirred in an atmosphere of nitrogen gas and refluxed for 8 hours. The water generated during the reaction was removed from the reaction system by azeotropic distillation. After completion of the reaction, the solvent was distilled off, and while stirring the obtained reaction mixture, 200 parts of hexane was added. After the obtained blackish brown precipitate was filtered off, it was washed successively with hexane, ethanol, and acetone and dried under reduced pressure to obtain a near-infrared absorbing pigment (G-17) represented by the following chemical formula (5). 50 parts of the obtained near-infrared absorbing pigment (G-17), 500 parts of sodium chloride, and 60 parts of diethylene glycol were charged into a stainless steel gallon kneader (manufactured by Inoue Seisakusho Co., Ltd.) and kneaded at 60 °C for 12 hours. Next, the kneaded mixture was put into warm water, stirred for 1 hour while heating to about 80 °C to make it slurry-like, and filtration and washing with ion-exchanged water were repeated a plurality of times, and then dried at 80 °C for a whole day and night and pulverized to obtain a micronized near-infrared absorbing pigment (G-17).

[0348] Chemical formula (5)

Chemical formula

[0349] (Near-infrared absorbing pigment (G-18)) In a reaction vessel, 26 parts of phthalonitrile, 143 parts of 2,3-dicyanonaphthalene, 890 parts of n-amyl alcohol, 137 parts of DBU (1,8-Diazabicyclo[5.4.0]undec-7-ene), and 34 parts of aluminum trichloride were mixed and stirred. After heating up, the mixture was refluxed at 136 °C for 5 hours. The reaction solution, which was cooled to 30 °C while stirring, was poured into a mixed solvent consisting of 5,000 parts of methanol and 10,000 parts of ion-exchanged water while stirring to obtain a blue slurry. This slurry was filtered, washed with a mixed solvent consisting of 2,000 parts of methanol and 4,000 parts of ion-exchanged water, and dried to obtain Compound a. Next, 140 parts of Compound a were added to 1,500 parts of concentrated sulfuric acid in an ice bath in a reaction vessel, and stirring was carried out for 1 hour. Subsequently, this sulfuric acid solution was poured into 1,000 parts of cold water at 3 °C, and the resulting precipitate was treated in the order of filtration, washing with water, washing with a 2.5% aqueous sodium hydroxide solution, and washing with water, and then dried to obtain Compound b. 5 parts of diphenylphosphoric acid were added to 200 parts of N-methylpyrrolidone, and after thorough stirring and mixing, the mixture was heated to 50 °C. To this solution, 10 parts of Compound b were added little by little, and then stirring was carried out at 90 °C for 120 minutes. The end point of the reaction was confirmed, for example, by dropping the reaction solution onto filter paper and taking the point where there was no bleeding as the end point. Subsequently, this reaction solution was poured into 2,000 parts of ion-exchanged water, and the resulting precipitate was filtered and washed with ion-exchanged water repeatedly a plurality of times, and then dried to obtain a mixture of compounds represented by the following Chemical Formula (6) (mass ratio: n1:n2:n3:n4 = 7:19:59:15), which is a near-infrared absorbing pigment (G-18). Next, it was micronized in the same manner as the near-infrared absorbing pigment (G-17).

[0350] Chemical Formula (6)

Chemical Formula

[0351] (Near-infrared absorbing pigment (G-19)) According to the description in International Publication No. 2019 / 058882, a near-infrared absorbing pigment (G-19) represented by the following Chemical Formula (7) was obtained. Next, it was micronized in the same manner as the near-infrared absorbing pigment (G-17).

[0352] Chemical formula (7)

Chem.

[0353] (Near-infrared absorbing pigment (G-20)) In a reaction vessel, 10.7 parts of aniline, 120 parts of bromobenzene, and 25.7 parts of diazabicyclooctane were added and stirred. Then, 95.2 parts of a 1 mol / l toluene solution of titanium tetrachloride was added dropwise. After the dropwise addition, 10.0 parts of indigo was added and refluxed for 10 hours. After completion of the reaction, methanol was added and filtration was carried out to obtain a green powder. This was separated by dichloromethane and water, and the organic layer was concentrated to obtain 14.6 parts of compound c. In a reaction vessel, 13.5 parts of compound c, 9.0 parts of bis(2,4-pentanedionato)zinc(II), and 120 parts of tetrahydrofuran were mixed and stirred, and after heating, the mixture was stirred at 40 °C for 5 hours. The reaction solution cooled to 30 °C while stirring was poured into 500 parts of methanol with stirring to obtain a blue slurry. This slurry was filtered, washed with 500 parts of methanol, washed multiple times with 500 parts of ion-exchanged water, and dried to obtain a near-infrared absorbing pigment (G-20) which is a mixture of compounds represented by the following chemical formula (8) (mass ratio of dimer:trimer:tetramer = 81:17:2). Then, it was micronized in the same manner as the near-infrared absorbing pigment (G-17).

[0354] Chemical formula (8)

Chem.

[0355] <Production of dispersion resin (J)> (Dispersion resin (J-1) solution) Into a reaction vessel equipped with a gas inlet tube, a thermometer, a condenser, and a stirrer, 108 parts of 1-thioglycerol, 174 parts of pyromellitic dianhydride, 650 parts of PGMAc, and 0.2 part of monobutyltin oxide as a catalyst were charged. After purging with nitrogen gas, the mixture was reacted at 120 °C for 5 hours (the first step). It was confirmed by acid value measurement that 95% or more of the acid anhydride was half-esterified. Next, 160 parts of the compound obtained in the first step in terms of non-volatile content, 200 parts of 2-hydroxypropyl methacrylate, 200 parts of ethyl acrylate, 150 parts of tert-butyl acrylate, 200 parts of 2-methoxyethyl acrylate, 200 parts of methyl acrylate, 50 parts of methacrylic acid, and 663 parts of PGMAc were charged. The inside of the reaction vessel was heated to 80 °C, 1.2 parts of 2,2'-azobis(2,4-dimethylvaleronitrile) was added, and the mixture was reacted for 12 hours (the second step). It was confirmed by non-volatile content measurement that 95% or more had reacted. Finally, 500 parts of a 50% PGMAc solution of the compound obtained in the second step, 27.0 parts of 2-methacryloyloxyethyl isocyanate (MOI), and 0.1 part of hydroquinone were charged, and the reaction was carried out until the disappearance of the peak at 2270 cm -1 based on the isocyanate group was confirmed by IR (the third step). After cooling, PGMAc was added so that the non-volatile content became 30% by mass to obtain a dispersion resin (J-1) solution having a polymerizable unsaturated group. The acid value was 68 mgKOH / g and the weight average molecular weight was 13,000.

[0356] (Dispersion resin (J-2) solution) Into a reaction vessel equipped with a gas inlet tube, a temperature controller, a condenser, and a stirrer, 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 were charged and replaced with nitrogen gas. The inside of the reaction vessel was heated and stirred at 50 °C, and 12 parts of 3-mercapto-1,2-propanediol were added. The temperature was raised to 90 °C, and a solution prepared by adding 0.1 part of 2,2'-azobisisobutyronitrile to 90 parts of PGMAc was added while reacting for 7 hours. It was confirmed by non-volatile content measurement that 95% of the reaction had occurred. 19 parts of pyromellitic dianhydride, 50 parts of PGMAc, 50 parts of cyclohexanone, and 0.4 part 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. It was confirmed by acid value measurement that 98% or more of the acid anhydride was half-esterified, and the reaction was terminated. After cooling, PGMAc was added so that the non-volatile content became 30% by mass to obtain a dispersion resin (J-2) solution. The acid value was 70 mgKOH / g, and the weight average molecular weight was 8,500.

[0357] (Dispersion resin (J-3) solution) In a reactor equipped with a gas inlet pipe, a condenser, a stirring blade, 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. While flowing nitrogen, the mixture was stirred at 50 °C for 1 hour, and the inside of the system was purged 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. Under a nitrogen stream, the temperature was raised to 110 °C to initiate the polymerization of the first block (B block). After 4 hours of polymerization, the polymerization solution was sampled for non-volatile content measurement, and it was confirmed that the polymerization conversion rate was 98% or more in terms of non-volatile content. Next, 50 parts of PGMAc, 40 parts of dimethylaminoethyl methacrylate as the second block (A block) monomer, and 10 parts of methacryloyloxyethylbenzyldimethylammonium chloride were added to this reactor, and the mixture was stirred while maintaining the temperature at 110 °C in a nitrogen atmosphere to continue the reaction. Two hours after the addition, the polymerization solution was sampled for non-volatile content measurement, and it was confirmed that the polymerization conversion rate of the second block (A block) was 98% or more in terms of non-volatile content. After cooling, PGMAc was added so that the non-volatile content became 30% by mass to prepare a dispersion resin (J-3) solution. The amine value was 169.8 mgKOH / g.

[0358] (Dispersion resin (J-4) solution) According to Example A3 of International Publication No. 2022 / 172607, a dispersion resin (J-4) having a polymerizable unsaturated group was synthesized, and PGMAc was added so that the non-volatile content became 30% by mass. The amine value was 67 mgKOH / g, and the weight average molecular weight was 5,600.

[0359] <Production of dispersion> (Dispersion 1) The following raw materials were stirred and mixed uniformly, and then dispersed with zirconia beads having a diameter of 0.5 mm using an Eiger mill ("Mini Model M-250 MKII" manufactured by Eiger Japan Co., Ltd.) for 3 hours, and then filtered through a filter with a pore size of 1.0 μm to prepare Dispersion 1. The non-volatile content was 22.0% by mass. Pigment (G-1): 15.0 parts Pigment derivative (I-1): 1.0 part Dispersed resin (J-1) solution: 10.0 parts Dispersed resin (J-2) solution: 10.0 parts Organic solvent (R-1): 64.0 parts

[0360] (Dispersion 2 - 15) Dispersions 2 - 15 were prepared in the same manner as Dispersion 1, except that the raw materials and amounts described in Table 2-1 and Table 2-2 were changed. The non-volatile content of Dispersions 2 - 15 was 22.0 mass%.

[0361]

Table 2-1

[0362]

Table 2-2

[0363] Each component described in Table 2-1 and Table 2-2 is as follows.

[0364] [Pigment (G)] G-1: C.I. Pigment Blue 15:3 G-2: C.I. Pigment Blue 15:6 G-3: C.I. Pigment Violet 23 G-4: C.I. Pigment Green 58 G-5: C.I. Pigment Green 59 G-6: C.I. Pigment Green 36 G-7: C.I. Pigment Green 62 G-8: C.I. Pigment Green 63 G-9: C.I. Pigment Red 177 G-10: C.I. Pigment Yellow 138 G-11: C.I. Pigment Yellow 139 G-12: C.I. Pigment Yellow 150 G-13: The yellow pigment (G-13) G-14: C.I. Pigment Yellow 231 G-15: C.I. Pigment Red 254 G-16: C.I. Pigment Red 264

[0365] The pigments (G-1) to (G-16) were all micronized by salt milling treatment, thoroughly washed and dried before use.

[0366] [Pigment Derivative (I)] Pigment Derivative (I) is a compound represented by Pigment Derivatives (I-1) to (I-4) below [Chemical Formula]

[0367] [Organic Solvent (R)] R-1: Propylene Glycol Monomethyl Ether Acetate

[0368] [Production of Photosensitive Composition] [Example 1] (Photosensitive Composition 1) The following raw materials were mixed, stirred, and filtered through a filter with a pore size of 1.0 μm to obtain Photosensitive Composition 1. The non-volatile content was 17.0% by mass. Dispersion 2: 0.4 part Dispersion 9: 1.8 parts Dispersion 13: 30.5 parts Alkali-soluble Resin (A1-1) Solution: 3.0 parts Alkali-soluble Resin (A2-2) Solution: 3.0 parts Urethane (meth)acrylate (B1-1) having a secondary or tertiary amine structure: 0.4 part Other (meth)acrylate (B2-6): 3.4 parts Oxime Ester-based Compound (C1-1): 0.3 part Thermal Polymerization Initiator (D-1): 0.2 part Compound (E1-1) having 2 to 3 alkoxysilyl groups: 0.9 part Thermosetting Compound (F1-1): 2.8 parts Thermosetting Compound (F2-1): 0.9 part Leveling agent (P): 1.0 part Organic solvent (R): 51.8 parts

[0369] [Examples 2 to 63 and Comparative Examples 1 to 3] (Photosensitive compositions 2 to 66) Photosensitive compositions 2 to 66 were prepared in the same manner as in Example 1, except that the raw materials and amounts described in Tables 3-1 to 3-7 were changed. The nonvolatile content of Photosensitive compositions 2 to 66 was 17.0 mass%.

[0370]

Table 3-1

[0371]

Table 3-2

[0372]

Table 3-3

[0373]

Table 3-4

[0374]

Table 3-5

[0375]

Table 3-6

[0376]

Table 3-7

[0377] Regarding each of the raw materials described in Tables 3-1 to 3-7, it is as follows.

[0378] [Coincidence compound (B)] [Urethane (meth) acrylate (B1) having a secondary or tertiary amine structure] B1-1: CN9906NS (manufactured by Arkema, aliphatic polyfunctional urethane acrylate having a tertiary amine structure)

[0379] [Other (meth) acrylates (B2)] B2-1: NK Ester A-DCP (manufactured by Shin-Nakamura Chemical Co., Ltd., tricyclodecane dimethanol diacrylate) B2-2: NK Ester A-HD-N (manufactured by Shin-Nakamura Chemical Co., Ltd., 1,6-hexanediol diacrylate) B2-3: NK Ester A-9300 (manufactured by Shin-Nakamura Chemical Co., Ltd., isocyanuric acid triacrylate) B2-4: Miramer SP-1106 (manufactured by Miwon Specialty Chemical Co., Ltd., compound having a dendrimer structure with an average acryloyl group number of 18) B2-5: Aronix M-306 (manufactured by Toagosei Co., Ltd., mixture of pentaerythritol triacrylate and pentaerythritol tetraacrylate) B2-6: Aronix M-402 (manufactured by Toagosei Co., Ltd., mixture of dipentaerythritol pentaacrylate and dipentaerythritol hexaacrylate) B2-7: Aronix M-520 (manufactured by Toagosei Co., Ltd., polybasic acid-modified acrylic oligomer) B2-8: Aronix M-309 (manufactured by Toagosei Co., Ltd., trimethylolpropane triacrylate) B2-9: Aronix M-930 (manufactured by Toagosei Co., Ltd., glycerin triacrylate)

[0380] [Photopolymerization initiator (C)] [Oxime ester-based compound (C1)] C1-1: The above-mentioned compound (C1-1) (molar absorption coefficient of light with a wavelength of 365 nm is 13,410 L / mol·cm) C1-2: The above compound (C1-2) (molar absorption coefficient of light at a wavelength of 365 nm is 14,214 L / mol·cm) C1-3: The above compound (C1-3) (molar absorption coefficient of light at a wavelength of 365 nm is 2,041 L / mol·cm) C1-4: The above compound (C1-5) (molar absorption coefficient of light at a wavelength of 365 nm is 18,334 L / mol·cm) C1-5: The above compound (C1-6) (molar absorption coefficient of light at a wavelength of 365 nm is 14,127 L / mol·cm) C1-6: The above compound (C1-10) (molar absorption coefficient of light at a wavelength of 365 nm is 7,051 L / mol·cm) C1-7: The above compound (C1-16) (molar absorption coefficient of light at a wavelength of 365 nm is 27,257 L / mol·cm)

[0381] (Other compound (C2)) C2-1: The above compound (C2-1)

[0382] [Thermal polymerization initiator (D)] D-1: Benzophenone (manufactured by Tokyo Chemical Industry Co., Ltd., non-volatile content 100 mass%) D-2: Perhexa HC (manufactured by NOF Corporation, 1,1-bis(tert-hexylperoxy)cyclohexane, non-volatile content 100 mass%) D-3: Perhexyl D (manufactured by NOF Corporation, di-tert-hexyl peroxide, non-volatile content 100 mass%) D-4: Pertert A (manufactured by NOF Corporation, 2,2-bis(4,4-di-tert-butylperoxycyclohexyl)propane, non-volatile content 100 mass%)

[0383] [Silane coupling agent (E)] E1-1: KBM-3086 (manufactured by Shin-Etsu Silicone Co., Ltd., 1,8-bis(trimethoxysilyl)octane, non-volatile content 100 mass%) E1-2: X-12-5263HP (manufactured by Shin-Etsu Silicone Co., Ltd., N,N-bis(trimethoxysilyl)ethylenediamine, non-volatile content 100 mass%) E1-3: KBM-9659 (manufactured by Shin-Etsu Silicone Co., Ltd., tris(trimethoxysilylpropyl)isocyanurate, non-volatile content 100% by mass) E2-1: KBM-403 (manufactured by Shin-Etsu Silicone Co., Ltd., 3-glycidoxypropyltrimethoxysilane, non-volatile content 100% by mass) E2-2: KBM-5103 (manufactured by Shin-Etsu Silicone Co., Ltd., 3-acryloxypropyltrimethoxysilane, non-volatile content 100% by mass) E2-3: KBM-5803 (manufactured by Shin-Etsu Silicone Co., Ltd., 3-methacryloxyoctyltrimethoxysilane, non-volatile content 100% by mass)

[0384] [Thermosetting compound (F)] (Solution of thermosetting compound (F1)) F1-1: Bronate 1227EV (manufactured by Dainichi Kogyo Co., Ltd., a compound blocked with an active methylene compound, non-volatile content 61% by mass) F1-2: Bronate 1232E (manufactured by Dainichi Kogyo Co., Ltd., a compound blocked with an active methylene compound, non-volatile content 100% by mass) F1-3: Duranate MF-K60B (manufactured by Asahi Kasei Co., Ltd., a compound blocked with an active methylene compound, non-volatile content 60% by mass) F1-4: BI7982 (manufactured by Baxenden Chemical Co., Ltd., a compound blocked with a pyrazole compound, non-volatile content 70% by mass) F1-5: BI7984 (manufactured by Baxenden Chemical Co., Ltd., a compound blocked with an oxime compound, non-volatile content 75% by mass)

[0385] (Thermosetting compound (F2)) F2-1: EHPE-3150 (manufactured by Daicel Co., Ltd., a compound represented by the general formula (2), average number of epoxy groups is 15, epoxy equivalent is 170 - 190 g / eq) F2-2: Denacol EX-611 (manufactured by Nagase ChemteX Co., Ltd., average number of epoxy groups is 4, epoxy equivalent is 155 - 175 g / eq)

[0386] [Leveling agent (P)] The following raw materials were mixed and dissolved to obtain the leveling agent (P). BYK-330 (manufactured by BYK-Chemie, polyether-modified dimethylsiloxane): 0.5 part Block copolymer having the following structure (n:m = 50:50 (mol%)): 0.5 part Propylene glycol monomethyl ether acetate: 99 parts [Chemical formula]

[0387] [Organic solvent (R)] R-1: Propylene glycol monomethyl ether acetate R-2: Cyclopentanone R-3: Ethyl 3-ethoxypropionate R-4: Propylene glycol monomethyl ether The above R-1, R-2, R-3, and R-4 were mixed at a mass ratio of 7:1:1:1 to obtain an organic solvent (R-5).

[0388] [Evaluation of photosensitive composition] The following evaluations were performed on the obtained photosensitive compositions 1 to 66. The evaluation results are shown in Table 4.

[0389] [Line width evaluation] The obtained photosensitive composition was applied by spin coating onto a glass substrate (Eagle 2000 manufactured by Corning) with a length of 100 mm, a width of 100 mm, and a thickness of 0.7 mm so that the film thickness after drying was 2.5 μm, and then dried on a hot plate at 90°C for 2 minutes. Next, after cooling this substrate to room temperature, using an ultra-high pressure mercury lamp, it was exposed through a photomask with a mask opening of 50 μm wide stripe pattern at an illuminance of 30 mW / cm 2 , 100 mJ / cm 2 . Then, this substrate was spray developed using an aqueous developer containing 0.12 mass% of a non-ionic surfactant and 0.04 mass% of potassium hydroxide at 23°C, washed with ion-exchanged water, air-dried, and heated in a clean oven at 100°C for 60 minutes. The spray development was performed at the shortest time capable of forming a pattern without remaining development for each film of the photosensitive compositions. The pattern of the obtained substrate was observed with an optical microscope, and the line width was evaluated. The evaluation criteria are as follows, and a value of 3 or more is considered practical. 5: -1 μm ≤ line width ≤ 1 μm with respect to the mask opening width. 4: -2 μm ≤ line width < -1 μm or 1 μm < line width < 2 μm with respect to the mask opening width. 3: -3 μm ≤ line width < -2 μm or 2 μm < line width < 3 μm with respect to the mask opening width. 2: -5 μm ≤ line width < -3 μm or 3 μm < line width < 5 μm with respect to the mask opening width. 1: line width < -5 μm or line width > 5 μm with respect to the mask opening width

[0390] [Adhesion evaluation] The obtained photosensitive composition was applied by spin coating onto a glass substrate (Eagle 2000 manufactured by Corning) with a length of 100 mm, a width of 100 mm, and a thickness of 0.7 mm so that the film thickness after drying was 2.5 μm, and dried on a hot plate at 90 °C for 2 minutes. Next, after cooling this substrate to room temperature, using an ultra-high pressure mercury lamp, through a photomask with a stripe pattern having a width of 5 to 25 μm in 5-μm increments, the illuminance was 30 mW / cm 2 and exposed at 100 mJ / cm 2 . Thereafter, this substrate was spray-developed using an aqueous developer containing 0.12% by mass of a nonionic surfactant and 0.04% by mass of potassium hydroxide at 23 °C, then washed with ion-exchanged water, air-dried, and heated in a clean oven at 100 °C for 60 minutes. The spray development was performed at the shortest time capable of forming a pattern without remaining development for the film of each photosensitive composition. Regarding the patterns on the obtained substrate with widths of 5, 10, 15, 20, and 25 μm, they were observed with an optical microscope, and the minimum line width of the remaining patterns was confirmed. The evaluation criteria are as follows, and a value of 3 or more is considered practical. 5: Fine lines of 5 μm or more or 10 μm or more remain. 4: Fine lines of 15 μm or more remain. 3: Fine lines of 20 μm or more remain. 2: Fine lines of 25 μm remain. 1: No fine lines remain.

[0391] [Pattern Shape Evaluation] The obtained photosensitive composition was applied onto a glass substrate (Eagle 2000 manufactured by Corning Inc.) with a size of 100 mm in length × 100 mm in width and a thickness of 0.7 mm by spin coating so that the film thickness after drying was 2.5 μm, and then dried on a hot plate at 90°C for 2 minutes. Next, after cooling this substrate to room temperature, using an ultra-high pressure mercury lamp, through a photomask with a 100-μm-wide stripe pattern, the illuminance was 30 mW / cm 2 , 100 mJ / cm 2 and exposed. Then, this substrate was spray-developed using an aqueous developer containing 0.12% by mass of a nonionic surfactant and 0.04% by mass of potassium hydroxide at 23°C, washed with ion-exchanged water, air-dried, and heated in a clean oven at 100°C for 60 minutes. The spray development was carried out at the shortest time capable of forming a pattern without any remaining development for the film of each photosensitive composition. The cross-sectional shape of the pattern was confirmed using a scanning electron microscope ("S-3000H" manufactured by Hitachi High-Technologies Corporation). The evaluation was performed by capturing an SEM image of the cross-section of a 100-μm-wide stripe pattern and measuring the taper angle between the substrate and the end of the pattern cross-section for pattern shape evaluation. The evaluation criteria are as follows, and a value of 3 or more is considered practical. 5: Taper angle is 40 degrees or more and less than 50 degrees 4: Taper angle is 50 degrees or more and less than 60 degrees 3: Taper angle is 30 degrees or more and less than 40 degrees, or 60 degrees or more and less than 70 degrees 2: Taper angle is 20 degrees or more and less than 30 degrees, or 70 degrees or more and less than 90 degrees 1: Taper angle is less than 20 degrees, or 90 degrees or more

[0392] [High Temperature and High Humidity Resistance Evaluation] The obtained photosensitive composition was applied onto a glass substrate (Eagle 2000 manufactured by Corning Inc.) with a size of 100 mm in length × 100 mm in width and a thickness of 0.7 mm by spin coating so that the film thickness after drying was 2.5 μm, and then dried on a hot plate at 90°C for 2 minutes. Next, after cooling this substrate to room temperature, using an ultra-high pressure mercury lamp, the illuminance was 30 mW / cm 2, 100 mJ / cm 2 It was exposed at 2 . After that, the substrate was cooled to room temperature, 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, and air-dried. Then, it was heat-treated in a clean oven at 100°C for 60 minutes to obtain a substrate for evaluation. The obtained substrate for evaluation was stored for 200 hours under the conditions of a temperature of 85°C and a humidity of 85%. After storage, a cut was made in the film with a cutter knife to form a 1 mm square lattice pattern (a total of 100 squares), a transparent adhesive tape (CT-24 manufactured by Nichiban Co., Ltd.) was strongly pressed, peeled in a direction of about 180 degrees, and then the state of the lattice pattern was observed and the number of peeled lattice patterns was counted. The evaluation criteria are as follows, and 3 or more is considered practical. 5: Less than 2 4: 2 or more and less than 5 3: 5 or more and less than 10 2: 10 or more and less than 15 1: 15 or more

[0393] [Solvent Resistance Evaluation] The obtained photosensitive composition was applied by spin coating onto a glass substrate (Eagle 2000 manufactured by Corning Inc.) with a length of 100 mm, a width of 100 mm, and a thickness of 0.7 mm so that the film thickness after drying was 2.5 μm, and dried on a hot plate at 90°C for 2 minutes. Next, after cooling this substrate to room temperature, using an ultra-high pressure mercury lamp, it was exposed through a photomask with a 100 μm wide stripe pattern at an illuminance of 30 mW / cm 2 , 100 mJ / cm 2 at 2 . After that, this substrate was spray-developed using an aqueous developer containing 0.12% by mass of a nonionic surfactant and 0.04% by mass of potassium hydroxide at 23°C, then washed with ion-exchanged water, air-dried, and heated in a clean oven at 100°C for 60 minutes. The spray development was performed at the shortest time capable of forming a pattern without remaining development for each film of the photosensitive composition. The obtained evaluation substrate was immersed in propylene glycol monomethyl ether acetate at room temperature for 15 minutes, washed with ion-exchanged water, air-dried, and observed using an optical microscope for the stripe pattern portion with a width of 100 μm. The evaluation criteria are as follows, and a value of 3 or more is considered practical. 5: No change in appearance or color. 4: Slight wrinkles or the like occur, but there is no change in color. 3: Wrinkles or the like occur in part, but there is no change in color. 2: Wrinkles or the like occur over the entire surface, and there is a slight fading. 1: Peeling or fading occurs.

[0394] [Flexural resistance] The obtained photosensitive composition was applied by spin coating onto a polyethylene terephthalate (PET) film with a thickness of 25 μm so that the film thickness after drying was 2.5 μm, and dried on a hot plate at 90 °C for 2 minutes. Next, after cooling this substrate to room temperature, it was exposed using an ultra-high pressure mercury lamp with an illuminance of 30 mW / cm 2 and 100 mJ / cm 2 . Then, this substrate was spray-developed using an aqueous developer containing 0.12% by mass of a nonionic surfactant and 0.04% by mass of potassium hydroxide at 23 °C, washed with ion-exchanged water, air-dried, and heated in a clean oven at 100 °C for 60 minutes. The obtained evaluation film was cut into pieces with a width of 2 cm and a length of 10 cm, and a flexure test (bending width 2 mm, frequency 117 Hz, number of cycles 100,000) was performed using a flexure tester ("DMLHB" manufactured by YUASA SYSTEM). After the test, the coating film was observed using an optical microscope. The evaluation criteria are as follows, and a value of 3 or more is considered practical. 5: No cracks 4: 1 or more and less than 5 cracks 3: 5 or more and less than 10 cracks 2: 10 or more and less than 20 cracks 1: 20 or more cracks

[0395]

Table 4

[0396] As shown in Table 4, in the photosensitive compositions 1 to 63 of Examples 1 to 63, although there was an evaluation of 3 in part in all evaluations of line width, adhesion, pattern shape, high temperature and high humidity resistance, solvent resistance, and bending resistance, they were generally at a usable level of 4 to 5. That is, while having a line width of a pattern nearly equivalent to the opening width of the photomask, it can be seen that the adhesion is achieved, and further, the pattern shape at low temperature heating after conventional low temperature heating and the compatibility of various resistances (high temperature and high humidity resistance, solvent resistance, bending resistance) are achieved. On the other hand, in the photosensitive compositions 64 to 66 of Comparative Examples 1 to 3, although there was an evaluation of 3 at a usable level in part in all evaluations of the line width of a pattern nearly equivalent to the opening width of the photomask, adhesion, and further after conventional low temperature heating, they were generally at an unusable level of 2 to 1. That is, it was difficult to achieve the compatibility with the pattern shape at low temperature heating and various resistances (high temperature and high humidity resistance, solvent resistance, bending resistance). From the above, according to the present invention, it has become possible to provide a photosensitive composition capable of forming a film excellent in adhesion, having an excellent pattern shape at low temperature heating, and achieving compatibility of various resistances.

Explanation of Reference Numerals

[0397] 100 Infrared sensor 110 Solid-state imaging device 111 Infrared cut filter 112 Color filter 113 Infrared transmission filter 114 Resin film 115 Microlens 116 Flat film

Claims

1. A photosensitive composition comprising an alkali-soluble resin (A), a polymerizable compound (B), a photopolymerization initiator (C), and a silane coupling agent (E), wherein the silane coupling agent (E) comprises a compound (E1) having 2 to 3 alkoxysilyl groups, the photosensitive composition.

2. The photosensitive composition according to claim 1, comprising a thermal polymerization initiator (D).

3. The photosensitive composition according to claim 1, wherein the alkali-soluble resin (A) comprises an alkali-soluble resin (A1) having a blocked isocyanate group-containing monomer unit (a1) and a hydroxyl group-containing monomer unit (a2).

4. The photosensitive composition according to claim 1, comprising a thermosetting compound (F).

5. The photosensitive composition according to claim 1, containing 0.5 to 10% by mass of the compound (E1) having 2 to 3 or more alkoxysilyl groups in the non-volatile content of the photosensitive composition.

6. The photosensitive composition according to claim 1, comprising a colorant.

7. A film formed from the photosensitive composition according to any one of claims 1 to 6.

8. An optical filter having the film according to claim 7.

9. A solid-state imaging device having the optical filter according to claim 8.

10. An image display device having the optical filter according to claim 8.

11. An infrared sensor having the optical filter according to claim 8.

Images