Photosensitive composition, cured product and method for manufacturing the same, display element, and image sensor

Abstract

The present invention aims to provide a photosensitive composition with low film shedding (i.e., a high rate of residual film after development) and high sensitivity, a cured film formed from the photosensitive composition and a method for producing the same, a display element equipped with the cured film, and an image sensor equipped with the cured film. [Solution] The present invention relates to a photosensitive composition for forming an optical component, comprising particles (A), a radical polymerizable compound (B), and a photoradical generator (C), wherein the amount of water contained in the photosensitive composition is 2000 ppm by mass or more.

Description

[Technical Field]

[0001] The present invention relates to a photosensitive composition, a cured product and a method for manufacturing the same, a display element, and an image sensor, and more specifically, to a technique for forming an optical component for a display element or an image sensor. [Background technology]

[0002] Various image sensors, such as CCD (Charge-Coupled Device) image sensors and CMOS (Complementary Metal-Oxide-Semiconductor) image sensors, are used as solid-state image elements in imaging devices such as cameras. Solid-state image elements are equipped with hemispherical condensing lenses (hereinafter also called "microlenses") or intralayer lenses to concentrate light onto the photodiode (light-receiving element) and improve sensor sensitivity. In addition, in display elements such as organic EL elements, a structure is adopted in which microlenses are provided on the light-emitting side of each pixel for the purpose of improving light extraction efficiency and adjusting the viewing angle (see, for example, Patent Document 1). Lenses for solid-state image elements and display elements are also being formed in recent years using photolithography technology with photosensitive compositions.

[0003] As the above-mentioned photosensitive composition, for example, a film-forming composition containing inorganic particles, a polysilane compound, a polymerizable monomer, and a curing accelerator such as a dehydrating agent is known (see, for example, Patent Document 2). [Prior art documents] [Patent Documents]

[0004] [Patent Document 1] Japanese Patent Publication No. 2020-101659 [Patent Document 2] Japanese Patent Publication No. 2007-131714 [Overview of the project] [Problems that the invention aims to solve]

[0005] Even with photosensitive compositions from the same manufacturing lot, differences in storage conditions, as well as the storage conditions of the substrate after coating and before exposure, can lead to differences in the amount of exposure required for curing, resulting in a decrease in sensitivity, such as changes in the amount of film peeling after development. Investigations into the cause of this decrease in sensitivity revealed that the amount of water contained in the composition has a particularly significant impact.

[0006] The present invention aims to provide a photosensitive composition with low film shedding (i.e., a high rate of residual film after development) and high sensitivity, a cured film formed from the photosensitive composition and a method for producing the same, a display element equipped with the cured film, and an image sensor equipped with the cured film. [Means for solving the problem]

[0007] The inventors of this invention conducted extensive research to solve this problem and, as a result, discovered that the above objective can be achieved by using a photosensitive composition with the following configuration, thus completing the present invention.

[0008] In one embodiment, the present invention is A photosensitive composition for forming an optical component, comprising particles (A), a radical polymerizable compound (B), and a photoradical generator (C), The amount of water contained in the aforementioned photosensitive composition is 2000 ppm by mass or more. This invention relates to a photosensitive composition for forming optical components.

[0009] In another embodiment, the present invention is A step of applying a photosensitive composition for forming an optical component, comprising particles (A), a radical polymerizable compound (B), and a photoradical generator (C), onto a substrate, The process includes irradiating a photosensitive composition coated on the above substrate with radiation. The amount of water contained in the photosensitive composition during the process of irradiating with the aforementioned radiation is 2000 ppm or more. This relates to a method for manufacturing cured products.

[0010] In another embodiment, the present invention is The present invention relates to a cured product formed by curing the photosensitive composition, a display element including the cured film, and an image pickup device including the cured film.

Advantages of the Invention

[0011] According to the photosensitive composition of the present invention, it is possible to provide a photosensitive composition, a cured film and a method for producing the same, a display element including the cured film, and an image pickup device including the cured film, which have less film swelling (i.e., a high development residue film ratio) and high sensitivity.

[0012] The reason is speculated as follows. Usually, radicals that play an important role in the curing reaction have a property of being very likely to bind to oxygen, and the binding rate of radicals to oxygen is faster than the binding rate of radicals to monomers. Therefore, it is speculated that the curing reaction on the surface of the photosensitive composition exposed to oxygen is inhibited by oxygen, resulting in film swelling after development. In the present invention, by setting the water content in the photosensitive composition to 2000 ppm or more, it is possible to prevent oxygen from entering the coating film surface and suppress the inhibition of the curing reaction by oxygen on the surface of the photosensitive composition. As a result, it is speculated that film swelling after development can be suppressed.

Embodiments for Carrying Out the Invention

[0013] Hereinafter, embodiments of the present invention will be described in detail, but the present invention is not limited to these embodiments. In this specification, a numerical range described using "~" means that the numerical values described before and after "~" are included as the lower limit value and the upper limit value. The "structural unit" is a unit mainly constituting the main chain structure, and means a unit contained in at least two in the main chain structure.

[0014] In this specification, "hydrocarbon group" includes linear hydrocarbon groups, alicyclic hydrocarbon groups, and aromatic hydrocarbon groups. "Linear hydrocarbon group" means a linear hydrocarbon group or a branched hydrocarbon group that does not contain a cyclic structure in its main chain and consists only of a linear structure. However, it may be saturated or unsaturated. "Alicyclic hydrocarbon group" means a hydrocarbon group that contains only the structure of an alicyclic hydrocarbon as its ring structure and does not contain an aromatic ring structure. However, it is not necessary to consist only of the structure of an alicyclic hydrocarbon, and it may also include those that have a linear structure as part of it. "Aromatic hydrocarbon group" means a hydrocarbon group that contains an aromatic ring structure as its ring structure. However, it is not necessary to consist only of the structure of an aromatic ring, and it may also contain a linear structure or the structure of an alicyclic hydrocarbon as part of it. The ring structure of an alicyclic hydrocarbon group or an aromatic hydrocarbon group may have substituents consisting of hydrocarbon structures.

[0015] In this specification, "(meth)acryloyl" encompasses "acryloyl" and "methacryloyl," and "(meth)acrylic" encompasses "acrylic" and "methacrylic." "(meth)acrylate" encompasses "acrylate" and "methacrylate."

[0016] ≪Photosensitive composition≫ The photosensitive composition according to this embodiment (hereinafter also simply referred to as "this composition") is A photosensitive composition for forming an optical component, comprising particles (A), a radical polymerizable compound (B), and a photoradical generator (C), The amount of water contained in the photosensitive composition is 2000 ppm by mass or more.

[0017] The above-described photosensitive composition is a photosensitive composition for forming optical components for display elements such as organic EL elements and image sensors. Optical components formed by this composition can, for example, improve the light extraction efficiency in display elements or improve sensor sensitivity by focusing light on a photodetector (photodiode) in solid-state imaging devices. Preferably, the optical component is a pattern formed by repeatedly aligning planarization films or lenses. The shape of the lenses constituting the pattern can be hemispherical, cylindrical, or frustoconical. The shape of the lens as viewed from the top surface can be circular or polygonal, and each may have a curved surface such as a sphere, or a trapezoidal shape such as a columnar or frustoconical. The lenses are formed by the photosensitive composition of the present invention, and other transparent material layers such as a low-refractive index layer may be formed in the gaps between the lenses. The planarization film is formed on a substrate to planarize the surface of a substrate on which semiconductor elements or the like are formed. The pattern is a micro-light-collecting element (lens or trapezoidal / rectangular pattern) or interlayer lens provided on a display element or solid-state image sensor (e.g., CCD image sensor, CMOS image sensor). In display elements such as organic EL elements, it is provided on each pixel for the purpose of improving the light extraction efficiency and adjusting the viewing angle at each pixel, and in solid-state image sensors, it is provided for the purpose of concentrating light on the light-receiving element to improve sensor sensitivity. The composition is preferably a photosensitive composition for planarization film formation or a photosensitive composition for pattern formation. The components contained in the above photosensitive composition will be described below.

[0018] <Particle (A)> The above-mentioned particles (A) can be particles that are appropriate for the purpose of addition, such as adjusting the refractive index, and in the present invention, it is preferable to use particles that can increase the refractive index of the resulting cured product. The above-mentioned particles (A) may be inorganic particles or organic particles, and pigment particles can also be used.

[0019] The inorganic particles mentioned above are not particularly limited, and examples include particulate materials such as zirconium oxide, titanium oxide, aluminum oxide, silver oxide, zinc oxide, barium titanate, silicon dioxide (including silica and hollow silica), cerium oxide, silicon nitride, and palladium sulfide. Of these, at least one particle selected from the group consisting of zirconium oxide, titanium oxide, barium titanate, and silica is preferred from the viewpoint of particle stability, and zirconium oxide particles are particularly preferred in terms of high dispersion stability.

[0020] The above-mentioned organic particles are not particularly limited and include, for example, particles made of polymer compounds such as polystyrene, polyethylene, polyolefin resins such as polypropylene, and acrylic resins. Furthermore, organic particles include transparent particles, opaque particles, colored particles, and hollow particles.

[0021] Furthermore, either organic or inorganic pigments can be used as the pigment particles. Examples of such pigments include organic or inorganic pigments such as carbon black, graphite, activated carbon, carbon fiber, carbon nanotube, carbon microcoil, carbon nanohorn, carbon aerogel, fullerene, aniline black, pigment black 7, titanium black, lactam black, perylene black, chromium oxide green, miloli blue, cobalt green, cobalt blue, manganese-based pigments, ferrocyanides, phosphate ultramarine, Prussian blue, ultramarine, cerulean blue, pyridian, emerald green, lead sulfate, lead yellow, zinc yellow, red iron(III) oxide, cadmium red, amber, lake pigment, barium sulfate, calcium carbonate, hydrated magnesium silicate (talc), magnesium carbonate, calcium sulfate, diatomaceous earth, mica, and silica. Among these, perylene black is preferred.

[0022] The shape of the above-mentioned particle (A) is not particularly limited, but examples include spherical, granular, plate-like, columnar, etc.

[0023] Furthermore, the average particle diameter of particle (A) is not particularly limited, but from the viewpoint of obtaining a cured film with high surface flatness and transparency, it is preferably 100 nm or less, more preferably 50 nm or less, and even more preferably 30 nm or less. Also, from the viewpoint of dispersion stability, the average particle diameter of particle (A) is, for example, 1 nm or more, and preferably 2 nm or more. In this invention, the average particle diameter refers to the D50 particle diameter (median diameter, which is the particle diameter that shows the 50% integrated value of the integrated distribution curve) measured by dynamic light scattering, and can be measured, for example, using MicrotracWaveII-EX150 manufactured by MicrotracBell.

[0024] The above-mentioned particles (A) are preferably particles coated with a surface coating agent, and more preferably inorganic particles coated with a compound having an acidic group (hereinafter also referred to as "specific coating agent") (hereinafter also referred to as "coated particles"). Here, inorganic particles coated with a specific coating agent are specific coating agent-particle composites in which particles are surface-treated with a surface coating agent containing the above-mentioned specific coating agent.

[0025] Examples of acidic groups possessed by the above-mentioned specific coating agent include carboxyl groups, phenolic hydroxyl groups, sulfo groups, phosphoric acid groups, and phosphonic acid groups. From the viewpoint of improving particle dispersibility in solvents and alkali developability, carboxyl groups or phenolic hydroxyl groups are preferred among these, and carboxyl groups are particularly preferred. In terms of excellent alkali developability and the ability to suppress development residue, the coated particles are preferably particles whose surface is coated with a carboxyl group-containing compound selected from the group consisting of zirconium oxide, titanium oxide, and barium titanate, and zirconium oxide particles whose surface is coated with a carboxyl group-containing compound are more preferred.

[0026] The specified coating agent may be a low-molecular-weight compound (i.e., a compound without a molecular weight distribution) or a polymer. The specified coating agent preferably contains a carboxyl group-containing compound, and more preferably contains a monocarboxylic acid or a carboxyl group-containing polymer as the carboxyl group-containing compound.

[0027] Examples of the monocarboxylic acid used as the specific coating agent include compounds represented by the following formula (2). R 3 -COOH …(2) (In formula (2), R 3 is a monovalent hydrocarbon group or halogenated hydrocarbon group having 4 or more carbon atoms, or a monovalent group having one or more selected from the group consisting of an oxygen atom, a sulfur atom, and a nitrogen atom.)

[0028] In the above formula (2), examples of the monovalent hydrocarbon group having 4 or more carbon atoms represented by R 3 include a chain hydrocarbon group, an alicyclic hydrocarbon group, and an aromatic hydrocarbon group. Further, when the monovalent hydrocarbon group represented by R 3 is a chain hydrocarbon group or an alicyclic hydrocarbon group, it may be either saturated or unsaturated, and when it is a chain hydrocarbon group, it may be either linear or branched. The monovalent hydrocarbon group represented by R 3 is preferably a chain hydrocarbon group, more preferably an alkyl group or an alkenyl group. From the viewpoint of enhancing the dispersibility of the particles (A), the carbon number of R 3 is preferably 6 or more, more preferably 7 or more. Further, from the viewpoint of ease of coating, the carbon number of R 3 is preferably 30 or less, more preferably 20 or less. When R 3 is a monovalent halogenated hydrocarbon group having 4 or more carbon atoms, examples of the halogen atom possessed by R 3 include a fluorine atom, a chlorine atom, etc.)[[ID=3)]]

[0029] R 3When is a monovalent group having one or more atoms selected from the group consisting of oxygen, sulfur, and nitrogen atoms, examples of such monovalent groups include groups in which one or more atoms selected from the group consisting of -O-, -S-, and -NH- are present between the carbon-carbon bonds in the hydrocarbon group, and groups in which any hydrogen atom of the hydrocarbon group is substituted with one or more atoms selected from the group consisting of hydroxyl, thiol, and amino groups. Of these, groups in which -O- is present between the carbon-carbon bonds in the hydrocarbon group are preferred. 3 If R is a monovalent group having one or more atoms selected from the group consisting of oxygen atoms, sulfur atoms, and nitrogen atoms, 3 The number of carbon atoms is preferably 2 or more, more preferably 2 to 15, and even more preferably 2 to 8, from the viewpoint of improving the dispersibility of the particles (A).

[0030] A specific example of the compound represented by formula (2) above is R 3 Examples of monocarboxylic acids in which the hydrocarbon group is monovalent include pentanoic acid, hexanoic acid, heptanoic acid, octanoic acid, nonanoic acid, decanoic acid, dodecanoic acid, tridecanoic acid, tetradecanoic acid, hexadecanoic acid, octadecanoic acid, stearic acid, 2-ethylhexanoic acid, 2-methylheptanoic acid, neodecanoic acid, 2-hexyldecanoic acid, naphthenic acid, cyclohexanecarboxylic acid, oleic acid, linoleic acid, and linolenic acid.

[0031] R 3 Examples of monocarboxylic acids in which the monovalent group has one or more atoms selected from the group consisting of oxygen, sulfur, and nitrogen atoms include methoxyacetic acid, ethoxyacetic acid, 3-ethoxypropionic acid, 2-methoxyethoxyacetic acid, glyoxylic acid, pyruvate, hydroxybenzoic acid, thioglycolic acid, 2-[2-(2-methoxyethoxy)]ethoxyacetic acid, oxovaleric acid, asparagine, glutamine, methionine, glycolic acid, lactic acid, 2-hydroxyisobutyric acid, hydroxystearic acid, salicylic acid, and the like.

[0032] As the carboxyl group-containing polymer, polymers containing structural units having carboxyl groups can be preferably used. Specific examples of carboxyl group-containing polymers as specific coating agents include those similar to the polymers exemplified as specific examples of binder resin (G) described later.

[0033] As the surface coating agent, compounds other than the specified coating agent (hereinafter also referred to as "other coating agents") may be used alone or in combination with the specified coating agent. Examples of other coating agents include titanium alkoxides, alkoxysilyl group-containing compounds, and unsaturated carbon-carbon bond-containing compounds. Specific examples of these include titanium alkoxides such as titanium tetra-n-butoxide, titanium tetra-t-butoxide, and titanium tetraethoxide. Examples of alkoxysilyl group-containing compounds include vinyltrimethoxysilane, vinyltriethoxysilane, 3-(meth)acryloyloxypropyltrimethoxysilane, 3-(meth)acryloyloxypropyltriethoxysilane, N-(2-aminoethyl)-3-aminopropylmethyldimethoxysilane, N-(2-aminoethyl)-3-aminopropyltrimethoxysilane, p-styryltrimethoxysilane, p-styryltriethoxysilane, phenyltrimethoxysilane, and phenyltriethoxysilane. Examples of unsaturated carbon-carbon bond-containing compounds include silane compounds having carbon-carbon unsaturated bonds, which were exemplified as alkoxysilyl group-containing compounds. Furthermore, compounds having basic groups can also be used as the surface coating agent.

[0034] When the above-mentioned specific coating agent is used in combination with other coating agents, the proportion of the other coating agent used is preferably 50% by mass or less, and more preferably 40% by mass or less, relative to the total amount of surface coating agent used to coat the particles (A).

[0035] When particle (A) is a coated particle, the manufacturing method is not particularly limited and can be manufactured by contacting the particle to be treated with a surface coating agent according to a known method. In this case, the coated particle may be manufactured by a top-down method or a bottom-up method. Furthermore, the coated particle may be manufactured in the gas phase or in the liquid phase. For example, coated particles can be obtained by contacting the particle to be treated with a surface coating agent, preferably in the presence of water. Alternatively, coated particles can be obtained by mixing the particle to be treated with a surface coating agent in an organic solvent, preferably in the presence of a dispersant, and then stirring with beads. The temperature and pressure when contacting the particle to be treated with the surface coating agent can be appropriately set according to the manufacturing method adopted. When contacting the particle to be treated with the surface coating agent, the ratio of the particle to the surface coating agent can be, for example, 0.5 to 20 parts by mass of surface coating agent per 100 parts by mass of particle to be treated, and preferably 1 to 20 parts by mass of surface coating agent per 100 parts by mass of particle to be treated.

[0036] Furthermore, as particles (A), titanium oxide particles (inorganic oxide-coated titanium oxide particles) whose surfaces are coated with inorganic oxides such as silicon, zinc, tin, zirconium, and aluminum, as described in Japanese Patent Publication No. 2013-008428 and Japanese Patent Publication No. 2009-179678, can also be suitably used.

[0037] This composition may contain one or more of the above-mentioned particles (A).

[0038] From the viewpoint of achieving a high refractive index in the resulting cured product, the lower limit of the particle (A) content (total content if multiple types are included) is preferably 10% by mass, more preferably 15% by mass, even more preferably 35% by mass, even more preferably 45% by mass, and particularly preferably 55% by mass, relative to the total amount of solids (i.e., components other than the solvent) contained in this composition. Furthermore, from the viewpoint of ensuring the stability of the dispersion, the upper limit of the particle (A) content is preferably 95% by mass, more preferably 90% by mass, relative to the total amount of solids contained in this composition.

[0039] <Radical polymerizable compound (B)> Examples of radical polymerizable compounds (B) include monofunctional polymerizable compounds (B1) and polyfunctional polymerizable compounds (B2). Radical polymerizable compounds (B) are compounds that, upon irradiation of this composition with radiation, can react with other polymerizable compounds (B) to form polymers.

[0040] As monofunctional polymerizable compounds (B1), compounds having one radical polymerizable group can be preferably used, such as (meth)acryloyl group-containing compounds, linear vinyl compounds, aromatic vinyl compounds, and maleimide compounds. Specific examples of (meth)acryloyl group-containing compounds include unsaturated carboxylic acids, unsaturated carboxylic acid anhydrides, (meth)acrylic acid esters having a linear structure, (meth)acrylic acid esters having an alicyclic structure, (meth)acrylic acid esters having an aromatic ring structure, (meth)acrylamide compounds, linear vinyl compounds, and compounds having a phosphate group and a (meth)acryloyl group. These compounds can be preferably used because they have good polymerizability and relatively high plasticity. As monofunctional polymerizable compounds (B1), (meth)acryloyl group-containing compounds can be preferably used from the viewpoint of achieving a high refractive index and transparency.

[0041] Examples of the above unsaturated carboxylic acids include (meth)acrylic acid, crotonic acid, maleic acid, itaconic acid, fumaric acid, etc. Examples of the above unsaturated carboxylic acid anhydrides include maleic anhydride, itaconic anhydride, citraconic anhydride, etc.

[0042] Examples of (meth)acrylic acid esters having the above-mentioned chain structure include alkyl (meth)acrylates, hydroxyalkyl (meth)acrylates, alkoxyalkyl (meth)acrylates, polyoxyalkylene (meth)acrylates, alkoxypolyoxyalkylene (meth)acrylates, polyoxycarbonylalkylene (meth)acrylates, alkoxypolyoxycarbonylalkylene (meth)acrylates, and mono(meth)acryloyloxyalkyl esters of dicarboxylic acids.

[0043] Examples of the alkyl (meth)acrylates mentioned above include methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, isopropyl (meth)acrylate, butyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, isodecyl (meth)acrylate, n-lauryl (meth)acrylate, n-stearyl (meth)acrylate, etc. Examples of the above-mentioned hydroxyalkyl (meth)acrylates include 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 3-hydroxypropyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, etc. Examples of the above-mentioned (meth)acrylate alkoxyalkyl esters include methoxyethyl (meth)acrylate, ethoxyethyl (meth)acrylate, and propoxyethyl (meth)acrylate; The above-mentioned polyoxyalkylene (meth)acrylates and alkoxy polyoxyalkylene (meth)acrylates include methoxydiethylene glycol (meth)acrylate, methoxytetraethylene glycol (meth)acrylate, ethoxydiethylene glycol (meth)acrylate, methoxydipropylene glycol (meth)acrylate, ethoxydipropylene glycol (meth)acrylate, 2-ethylhexyloxydiethylene glycol (meth)acrylate, α-(meth)acryloyloxy-ω-carboxymethyl polyethylene glycol (AA-PEG-COOH), etc. The above (meth)acrylic acid polyoxycarbonyl alkylene esters include ω-carboxy-polycaprolactone mono(meth)acrylate, etc. Examples of mono(meth)acryloyloxyalkyl esters of the above-mentioned dicarboxylic acids include mono(2-(meth)acryloyloxyethyl) succinate and mono(2-(meth)acryloyloxyethyl) phthalate.

[0044] Examples of (meth)acrylic acid esters having the above alicyclic structure include cyclohexyl (meth)acrylate, 2-methylcyclohexyl (meth)acrylate, 4-butylcyclohexyl (meth)acrylate, 4-hydroxymethylcyclohexyl (meth)acrylate, and tricyclo(meth)acrylate [5.2.1.0 2,6 ] Decane-8-yl, (meth)acrylate tricyclo[5.2.1.0 2,5 Examples include decane-8-yloxyethyl and isobornyl (meth)acrylate.

[0045] Examples of (meth)acrylic acid esters having the above aromatic ring structure include phenyl (meth)acrylate, benzyl (meth)acrylate, naphthylmethyl (meth)acrylate, naphthylethyl (meth)acrylate, phenoxyethyl (meth)acrylate, phenylthioethyl (meth)acrylate, m-phenoxyphenylmethyl (meth)acrylate, p-phenoxyphenylmethyl (meth)acrylate, o-phenylphenoxyethyl (meth)acrylate, 2-hydroxy-3-phenoxypropyl (meth)acrylate, polyethyleneoxynonylphenyl (meth)acrylate, (1-naphthyl)methyl (meth)acrylate, (2-naphthyl)methyl (meth)acrylate, (1,1'-biphenyl-4-yl)methyl (meth)acrylate, 4'-(6-acryloyloxyhexyloxy)biphenyl-4-carboxylic acid (CAS number: 134903-88-1), and the like.

[0046] Examples of the above-mentioned (meth)acrylamide compounds include (meth)acryloylmorpholine, N-(2-hydroxyethyl)(meth)acrylamide, N-vinyl-2-pyrrolidone, and N-vinyl-ε-caprolactam.

[0047] Examples of the above-mentioned chain-like vinyl compounds include propene, butene, pentene, and hexene. Examples of the above-mentioned aromatic vinyl compounds include styrene, methylstyrene, α-methylstyrene, t-butoxystyrene, o-hydroxystyrene, m-hydroxystyrene, p-hydroxystyrene, o-vinylbenzoic acid, m-vinylbenzoic acid, p-vinylbenzoic acid, and vinylnaphthalene. Examples of the above-mentioned maleimide compounds include N-methylmaleimide, N-cyclohexylmaleimide, N-phenylmaleimide, and N-(p-methylphenyl)maleimide.

[0048] Examples of compounds having the above-mentioned phosphate group and (meth)acryloyl group include 2-hydroxyethyl methacrylate phosphate (CAS No.: 52628-03-2), beta-(2-furyl)acrylamide phosphate (CAS No.: 16655-99-5), bis(2-methylacryloxyethyl) phosphate (CAS No.: 32435-46-4), polyethylene glycol methacrylate phosphate (CAS No.: 35705-94-3), bis(2-(acryloyloxy)ethyl) phosphate (CAS No.: 40074-34-8), and 10-(2-methacryloyloxy group) monodecyl phosphate (CAS No.: 85590-00-7).

[0049] Further specific examples of monofunctional polymerizable compounds (B1) include compounds represented by formulas (b1-1) to (b1-28) below.

[0050] [ka]

[0051] [ka] (In formulas (b1-1) to (b1-28), R 20 R is a hydrogen atom or a methyl group. 21 (where n is an integer between 0 and 10, n is a monovalent hydrocarbon group with 1 to 20 carbon atoms.)

[0052] As the polyfunctional polymerizable compound (B2) mentioned above, compounds having two or more radical polymerizable groups can be preferably used. Examples include polyfunctional (meth)acryloyl group-containing compounds, polyfunctional aromatic vinyl compounds, and polyfunctional chain vinyl compounds.

[0053] Specific examples of the polyfunctional (meth)acryloyl group-containing compounds mentioned above include difunctional (meth)acrylic acid esters and trifunctional or more (meth)acrylic acid esters. Specific examples of these include, as difunctional (meth)acrylic acid esters, ethylene glycol di(meth)acrylate, polyethylene glycol di(meth)acrylate, propylene glycol di(meth)acrylate, polypropylene glycol di(meth)acrylate, neopentyl glycol di(meth)acrylate, EO-modified neopentyl glycol di(meth)acrylate, PO-modified neopentyl glycol di(meth)acrylate, bisphenol A di(meth)acrylate, EO-modified bisphenol A di(meth)acrylate, PO-modified bisphenol A di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, 1,9-nonanediol di(meth)acrylate, 1,10-decanediol di(meth)acrylate, diethylene glycol di(meth)acrylate, tetraethylene glycol di(meth)acrylate, and the like.

[0054] Examples of trifunctional or more (meth)acrylic acid esters include trimethylolpropane tri(meth)acrylate, ethylene oxide-modified trimethylolpropane tri(meth)acrylate, pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, dipentaerythritol penta(meth)acrylate, dipentaerythritol hexa(meth)acrylate, ethylene oxide-modified dipentaerythritol hexa(meth)acrylate, tri(2-(meth)acryloyloxyethyl)phosphate, Examples include succinic acid-modified pentaerythritol tri(meth)acrylate, succinic acid-modified dipentaerythritol penta(meth)acrylate, tris(2-(meth)acryloyloxyethyl) isocyanurate, carboxyl group-containing polybasic acid-modified (meth)acrylic oligomers, and polyfunctional urethane acrylate compounds obtained by reacting a compound having a linear alkylene group and an alicyclic structure and two or more isocyanate groups with a compound having one or more hydroxyl groups in the molecule and three, four, or five (meth)acryloyloxy groups.

[0055] Examples of the above polyfunctional aromatic vinyl compounds include 1,3-divinylbenzene and 1,4-divinylbenzene. Examples of the above polyfunctional chain vinyl compounds include 1,5-hexadiene, 1,6-heptadiene, and 1,7-octadiene.

[0056] Further specific examples of polyfunctional polymerizable compounds (B2) include compounds represented by formulas (b2-29) to (b2-53) below.

[0057] [ka]

[0058] [ka]

[0059] [ka] (In formulas (b2-29) to (b2-53), R 20 (where m is a hydrogen atom or a methyl group; m and n are independent integers between 0 and 10; x, y, and z are independent integers between 0 and 3, satisfying the condition 1 ≤ x + y + z ≤ 3.)

[0060] As for the polyfunctional polymerizable compound (B2), from the viewpoint of achieving a high refractive index and transparency, compounds containing (meth)acryloyl groups can be preferably used among the above.

[0061] Furthermore, as a radical polymerizable compound (B), a polymerizable compound (B3) having both a radical polymerizable group and a cationic polymerizable group can also be mentioned, and it is preferable to use it in combination with the monofunctional polymerizable compound (B1) or polyfunctional polymerizable compound (B2) mentioned above. Examples of cationic polymerizable groups include epoxy groups, oxetanyl groups, or vinyl ether groups.

[0062] As polymerizable compounds (B3) having both radical polymerizable groups and cationic polymerizable groups, compounds having a vinyl group or (meth)acryloyl group as the radical polymerizable group and an epoxy group or oxetanyl group as the cationic polymerizable group are preferred. Examples of polymerizable compounds (B3) include glycidyl (meth)acrylate, 3,4-epoxycyclohexyl (meth)acrylate, 3,4-epoxycyclohexylmethyl (meth)acrylate, 2-(3,4-epoxycyclohexyl)ethyl (meth)acrylate, and 3,4-epoxytricyclo[5.2.1.0 2,6 ] Decyl (meth)acrylate, 2-hydroxyethyl methacrylate [3,4-epoxytricyclo(5.2.1.0 2,6 ) Decane-9-yl], methacrylic acid [3,4-epoxytricyclo(5.2.1.0 2,6Examples include )decane-9-yl, (3-methyloxetan-3-yl)methyl(meth)acrylate, (3-ethyloxetan-3-yl)(meth)acrylate, (3-ethyloxetan-3-yl)methyl(meth)acrylate, (oxetan-3-yl)methyl(meth)acrylate, 3-(meth)acryloyloxymethyl-3-ethyloxetane, o-vinylbenzylglycidyl ether, m-vinylbenzylglycidyl ether, p-vinylbenzylglycidyl ether, 3-[(4-vinylbenzyl)oxymethyl]-3-ethyloxetane, etc., with 3-[(4-vinylbenzyl)oxymethyl]-3-ethyloxetane being preferred.

[0063] This composition may contain one or more of the above-mentioned radical polymerizable compounds (B).

[0064] When the radical polymerizable compound (B) contains both a monofunctional polymerizable compound (B1) and a polyfunctional polymerizable compound (B2), the content of the monofunctional polymerizable compound (B1) is preferably 20% by mass or more, more preferably 30% by mass or more, and even more preferably 40% by mass or more, relative to the total amount of the monofunctional polymerizable compound (B1) and the polyfunctional polymerizable compound (B2). Furthermore, the content of the monofunctional polymerizable compound (B1) is preferably 100% by mass or less, preferably 90% by mass or less, more preferably 80% by mass or less, and even more preferably 70% by mass or less, relative to the total amount of the monofunctional polymerizable compound (B1) and the polyfunctional polymerizable compound (B2).

[0065] Furthermore, if the radical polymerizable compound (B) contains the polymerizable compound (B3), its content is preferably 50% by mass or less, and more preferably 30% by mass or less, of the radical polymerizable compound (B).

[0066] The lower limit of the content of radical polymerizable compound (B) in this composition (the total content if multiple polymerizable compounds (B1) to (B3) are included) is preferably 5 parts by mass, more preferably 10 parts by mass, and still more preferably 20 parts by mass per 100 parts by mass of particles (A). The upper limit of the content of radical polymerizable compound (B) is preferably 350 parts by mass, more preferably 200 parts by mass, even more preferably 100 parts by mass, still more preferably 50 parts by mass, still more preferably 45 parts by mass, and particularly preferably 35 parts by mass per 100 parts by mass of particles (A). By setting the content of radical polymerizable compound (B) in this composition within the above range, the refractive index can be increased, the sensitivity of this composition can be improved, and a cured product with good heat resistance and chemical resistance can be obtained.

[0067] <A cationic polymerizable compound (B4) that does not have a radical polymerizable group but has a cationic polymerizable group> In the present invention, a cationic polymerizable compound (B4) that does not have a radical polymerizable group but has a cationic polymerizable group can be used. The cationic polymerizable compound (B4) is preferably a compound having an epoxy group (oxyranyl group) or a compound having an oxetanyl group (oxetane compound). The cationic polymerizable compound (B4) only needs to have one or more cationic polymerizable groups, and preferably has one to three.

[0068] Examples of compounds having the epoxy group mentioned above include alicyclic compounds having an epoxy group (alicyclic epoxy compounds), aromatic compounds having an epoxy group (aromatic epoxy compounds), and acyclic compounds having an epoxy group (acyclic epoxy compounds), with alicyclic epoxy compounds being preferred. Examples of alicyclic epoxy compounds include 3',4'-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate, 3,4-epoxycyclohexylalkyl (meth)acrylate (for example, 3,4-epoxycyclohexylmethyl (meth)acrylate), (3,3',4,4'-diepoxy)bicyclohexyl, hydrogenated bisphenol A type epoxy resin, and hydrogenated bisphenol F type epoxy resin.

[0069] Examples of the above-mentioned oxetane compounds include 3-ethyl-3-hydroxymethyloxetane (such as Aronoxetane OXT-101, manufactured by Toagosei Co., Ltd.), 1,4-bis[(3-ethyl-3-oxetanyl)methoxymethyl]benzene (such as OXT-121), 3-ethyl-3-(phenoxymethyl)oxetane (such as OXT-211), di(1-ethyl-(3-oxetanyl))methyl ether (such as OXT-221), and 3-ethyl-3-(2-ethylhexyloxymethyl)oxetane (such as OXT-212).

[0070] Compounds having both an epoxy group and an oxetanyl group can also be used. An example of such a compound is 3-ethyl-3-(2,3-epoxypropoxymethyl)oxetane.

[0071] When this composition contains the above-mentioned cationic polymerizable compound (B4), the lower limit of the content ratio of cationic polymerizable compound (B4) (total content ratio if multiple types are included) is preferably 5 parts by mass, more preferably 10 parts by mass, and even more preferably 20 parts by mass per 100 parts by mass of particles (A). Furthermore, the upper limit of the content ratio of cationic polymerizable compound (B4) is preferably 100 parts by mass, more preferably 80 parts by mass, and even more preferably 60 parts by mass per 100 parts by mass of particles (A). By setting the content ratio of cationic polymerizable compound (B4) in this composition within the above range, the refractive index can be increased, the sensitivity of this composition can be improved, and a cured product with good heat resistance and chemical resistance can be obtained.

[0072] As the radical polymerizable compound (B) above, polymerizable compounds (B1) to (B4) can be used in appropriate combinations, but among these, polymerizable compounds having alkylene oxide chains such as ethylene oxide chains and propylene oxide chains, and polymerizable compounds having acidic groups are preferred from the viewpoint of bending resistance and dispersibility.

[0073] <Photoradical Generator (C)> As the photoradical generator (C), a photoradical polymerization initiator that generates radicals in response to radiation and can initiate polymerization of the radical polymerizable compound (B) can preferably be used. The photopolymerization initiator used is not particularly limited, but examples include O-acyloxime compounds, acetophenone compounds, biimidazole compounds, acylphosphine oxide compounds, and the like.

[0074] Examples of O-acyloxime compounds include 1,2-octanedione 1-[4-(phenylthio)-2-(O-benzoyloxime)], ethane-1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazole-3-yl]-1-(O-acetyloxime), 1-(9-ethyl-6-benzoyl-9.H.-carbazole-3-yl)-octan-1-oneoxime-O-acetate, 1-[9-ethyl-6-(2-methylbenzoyl)-9.H.-carbazole-3-yl]-ethane-1-oneoxime-O-benzoate, 1-[9-n-butyl-6-(2-ethylbenzoyl)-9.H.-carbazole-3-yl]-ethane-1-oneoxime-O-benzoate, and ethane-1 Examples include -[9-ethyl-6-(2-methyl-4-tetrahydrofuranylbenzoyl)-9.H.-carbazol-3-yl]-1-(O-acetyloxime), ethanoone-1-[9-ethyl-6-(2-methyl-4-tetrahydropyranylbenzoyl)-9.H.-carbazol-3-yl]-1-(O-acetyloxime), ethanoone-1-[9-ethyl-6-(2-methyl-5-tetrahydrofuranylbenzoyl)-9.H.-carbazol-3-yl]-1-(O-acetyloxime), and ethanoone-1-[9-ethyl-6-{2-methyl-4-(2,2-dimethyl-1,3-dioxolanyl)methoxybenzoyl}-9.H.-carbazol-3-yl]-1-(O-acetyloxime). Other commercially available products include, for example, the ADEKA Arclus N-1919T, NCI-831E, NCI-930, and NCI-730 (all manufactured by ADEKA Corporation), and the Irgacure OXE01, OXE2, OXE3, and OXE4 (all manufactured by BASF).

[0075] Examples of acetophenone compounds include α-aminoketone compounds and α-hydroxyketone compounds. Specific examples of these include α-aminoketone compounds such as 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)-butan-1-one, 2-dimethylamino-2-(4-methylbenzyl)-1-(4-morpholin-4-ylphenyl)-butan-1-one, and 2-methyl-1-(4-methylthiophenyl)-2-morpholinopropan-1-one. Examples of α-hydroxyketone compounds include 1-phenyl-2-hydroxy-2-methylpropan-1-one, 1-(4-i-propylphenyl)-2-hydroxy-2-methylpropan-1-one, 4-(2-hydroxyethoxy)phenyl-(2-hydroxy-2-propyl)ketone, and 1-hydroxycyclohexylphenyl ketone. Other commercially available products include, for example, Irgacure 369, 369E, 379EG, 651, 184, and 907 (all manufactured by BASF).

[0076] Examples of biimidazole compounds include 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetraphenyl-1,2'-biimidazole, 2,2'-bis(2,4-dichlorophenyl)-4,4',5,5'-tetraphenyl-1,2'-biimidazole, or 2,2'-bis(2,4,6-trichlorophenyl)-4,4',5,5'-tetraphenyl-1,2'-biimidazole.

[0077] Examples of acylphosphine oxide compounds include 2,4,6-trimethylbenzoyl-diphenylphosphine oxide and phenylbis(2,4,6-trimethylbenzoyl)phosphine oxide.

[0078] This composition may contain one or more of the above-mentioned photoradical generators (C).

[0079] The lower limit of the content of the photoradical generator (C) in this composition (total content if multiple types are included) is preferably 0.5 parts by mass, more preferably 1 part by mass, per 100 parts by mass of particles (A) contained in this composition. The upper limit of the content of the photoradical generator (C) is preferably 40 parts by mass, more preferably 30 parts by mass, even more preferably 15 parts by mass, even more preferably 10 parts by mass, and particularly preferably 5 parts by mass, per 100 parts by mass of particles (A) contained in this composition. By setting the content of the photoradical generator (C) within the above range, a photosensitive composition exhibiting good curability and transparency can be obtained.

[0080] This composition may contain components other than the above-mentioned particles (A), radical polymerizable compound (B), and photoradical generator (C). Other components may include photoacid generator (E), solvent (F), binder resin (G), surfactant (H), adhesion aid (I), sensitizer (J), dehydrating agent, etc.

[0081] <Photoacid Generator (E)> The photoacid generator (E) refers to a compound that generates acid upon irradiation with light or other radiation. Examples of radiation include ultraviolet rays, far ultraviolet rays, X-rays, and charged particle beams. The generation of this acid can initiate the cationic polymerization of the cationic polymerizable compound. Therefore, if the radical polymerizable compound (B) contains a polymerizable compound (B3), it is preferable that it also contains the photoacid generator (E).

[0082] Examples of photoacid generators (E) include oximesulfonate compounds, sulfonimide compounds, halogen-containing compounds, diazomethane compounds, sulfone compounds, sulfonic acid ester compounds, carboxylic acid ester compounds, and onium salts. Specific examples of these compounds include those described in Japanese Patent Publication No. 2020-026515. Among these, onium salts are preferred.

[0083] Examples of the above-mentioned onium salts include diphenyliodonium salt, triphenylsulfonium salt, sulfonium salt, benzothiazonium salt, and tetrahydrothiophenium salt. Examples of diphenyliodonium salts include diphenyliodonium tetrafluoroborate and 4-isobutylphenyl-4'-toluyliodohexafluorophosphate. Examples of triphenylsulfonium salts include triphenylsulfonium trifluoromethanesulfonate, triphenylsulfonium hexafluoroantimonate, triphenylsulfonium hexafluorophosphate, triphenylsulfonium tetrakis(pentafluorophenyl)borate, and diphenyl[4-(phenylthio)phenyl]sulfonium hexafluorophosphate. Among these, triphenylsulfonium hexafluoroantimonate, diphenyl[4-(phenylthio)phenyl]sulfonium hexafluorophosphate, and 4-isobutylphenyl-4'-toluyliodohexafluorophosphate are preferred.

[0084] This composition may contain one or more of the above-mentioned photoacid generators (E).

[0085] When this composition contains a photoacid generator (E), the lower limit of the content ratio of the photoacid generator (E) (total content ratio if multiple types are included) is preferably 0.1 parts by mass, more preferably 0.2 parts by mass, even more preferably 0.5 parts by mass, and still more preferably 1 part by mass, per 100 parts by mass of particles (A) contained in this composition. The upper limit of the content ratio of the photoacid generator (E) is preferably 10 parts by mass, more preferably 5 parts by mass, per 100 parts by mass of particles (A) contained in this composition. By setting the content ratio of the photoacid generator (E) within the above range, a photosensitive composition exhibiting good curability can be obtained.

[0086] When using a photoacid generator (E) in this composition, polymerizable compounds (B3), adhesion aids (I) having cationic polymerizable groups such as oxiranil groups or oxetanil groups, or polymerizable compounds (B4) can be used. Furthermore, when using a photoacid generator (E) in this composition, a sensitizer (J) can be used to improve sensitivity.

[0087] <Solvent (F)> The composition is preferably a liquid composition in which the above-mentioned particles (A), radical polymerizable compound (B), photoradical generator (C), and other components as needed are dissolved or dispersed in a solvent. As the solvent (F), an organic solvent is preferred that dissolves the above-mentioned particles (A), radical polymerizable compound (B), and photoradical generator (C) and does not react with each component.

[0088] Specific examples of solvent (F) include, for example, alcohols such as methanol, ethanol, isopropanol, butanol, octanol, and diacetone alcohol; esters such as ethyl acetate, butyl acetate, ethyl lactate, γ-butyrolactone, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, dipropylene glycol methyl ether acetate, 3-methoxybutyl acetate, methyl 3-methoxypropionate, and ethyl 3-ethoxypropionate; ethers such as ethylene glycol monobutyl ether, propylene glycol monomethyl ether, ethylene diglycol monomethyl ether, ethylene diglycol ethyl methyl ether, dimethyl glycol dimethyl ether, diethylene glycol dimethyl ether, and diethylene glycol ethyl methyl ether; amides such as dimethylformamide, N,N-dimethylacetamide, and N-methylpyrrolidone; ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclopentanone, and cyclohexanone; and aromatic hydrocarbons such as benzene, toluene, xylene, and ethylbenzene. Of these, the solvent (F) preferably contains at least one selected from the group consisting of alcohols, ethers, and esters, and more preferably contains at least one selected from the group consisting of propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, 3-methoxybutyl acetate, diethylene glycol ethyl methyl ether, diacetone alcohol, and dipropylene glycol methyl ether acetate.

[0089] As for the solvent (F), it is preferable to include a solvent with a high boiling point (for example, 160°C or higher) from the viewpoint of coating properties over time.

[0090] <Binder resin (G)> The binder resin (G) is preferably a polymer having an acidic group. Examples of acidic groups include carboxyl groups, phenolic hydroxyl groups, and fluorinated hydroxyalkyl groups. The binder resin is preferably an alkali-soluble resin. Here, "alkali-soluble" means a polymer that can dissolve or swell in a 2.38% by mass aqueous solution of tetramethylammonium hydroxide (TMAH) at 25°C. A fluorinated hydroxyalkyl group refers to a group of a hydroxyalkyl group in which any hydrogen atom bonded to carbon is substituted with a fluorine atom.

[0091] As the binder resin (G) described above, a polymer having ethylenically unsaturated monomers as constituent units can be preferably used. Examples of ethylenically unsaturated monomers constituting the polymer include compounds similar to those exemplified as monofunctional polymerizable compounds (B1), and it is preferable that they contain carboxyl group-containing compounds. In this case, the binder resin (G) preferably contains 5% by mass or more of structural units derived from the carboxyl group-containing compound, more preferably 10% by mass or more, and even more preferably 20% by mass or more, relative to the total structural units constituting the binder resin (G).

[0092] When the binder resin (G) is a polymer composed of ethylenically unsaturated monomers, the polymer can be produced, for example, by using the ethylenically unsaturated monomers described above, in a suitable solvent, in the presence of a polymerization initiator, etc., according to known methods such as radical polymerization. Examples of polymerization initiators include azo compounds such as 2,2'-azobis(isobutyronitrile), 2,2'-azobis(2,4-dimethylvaleronitrile), and 2,2'-azobis(isobutyric acid)dimethyl. The amount of polymerization initiator used is preferably 0.01 to 30 parts by mass per 100 parts by mass of the total amount of monomers used in the reaction. Examples of polymerization solvents include alcohols, ethers, ketones, esters, hydrocarbons, etc., and specifically those listed as solvent (F) above. The amount of polymerization solvent used is preferably such that the total amount of monomers used in the reaction is 0.1 to 60% by mass of the total amount of reaction solution. In polymerization, the reaction temperature is typically between 30°C and 180°C. The reaction time varies depending on the type of polymerization initiator and monomer, as well as the reaction temperature, but is usually between 0.5 and 10 hours.

[0093] Examples of binder resins (G) include polymers whose constituent units are ethylenically unsaturated monomers, as well as phenolic hydroxyl group-containing polymers such as novolac resins, phenol-xylylene glycol condensation resins, cresol-xylylene glycol condensation resins, and phenol-dicyclopentadiene condensation resins. Alternatively, alkali-soluble polyorganosiloxanes, alkali-soluble polyimides, and alkali-soluble polybenzoxazoles may be used as binder resins (G). Specific examples of alkali-soluble polyorganosiloxanes include polymers described in International Publication No. 2017 / 188047 and International Publication No. 2017 / 169763, for example. Specific examples of alkali-soluble polyimides and polybenzoxazoles include polymers described in International Publication No. 2017 / 169763 and International Publication No. 2017 / 159876, for example.

[0094] While the alkali developability can be improved by including a binder resin (G) in this composition, the surface flatness of the resulting cured product tends to decrease. Therefore, the presence or absence of binder resin (G) and the amount it is included can be determined according to the intended use of the resulting cured product. Specifically, it is preferable not to use binder resin (G) in applications where surface flatness of the resulting cured product is required, and it is preferable to use binder resin (G) in applications where improved alkali developability is required.

[0095] This composition may contain one or more of the above-mentioned binder resins (G).

[0096] If the composition contains a binder resin (G), the content ratio of the binder resin (G) (total content ratio if multiple types are included) is preferably 1 part by mass or more and 30 parts by mass or less, and more preferably 5 parts by mass or more and 20 parts by mass or less, per 100 parts by mass of particles (A) contained in the composition.

[0097] <Surfactant (H)> Surfactants (H) can be used to improve the applicability of this composition (wetting spread and reduction of uneven application). Examples of surfactants (H) include fluorinated surfactants, silicone surfactants, and nonionic surfactants.

[0098] Specific examples of surfactants (H) include fluorine-based surfactants such as Megafac F-171, F-172, F-173, F-251, F-430, F-554, F-563 (manufactured by DIC Corporation); Florard FC430, FC431 (manufactured by Sumitomo 3M Co., Ltd.); Asahiguard AG710, Surflon S-382, SC-101, SC-102, SC-103, SC-104, SC-105, SC-106, S-611 (manufactured by AGC Seimi Chemical Co., Ltd.); Polyflow No. 75, No. 95 (manufactured by Kyoeisha Chemical Co., Ltd.); FTX-218 (manufactured by Neos Co., Ltd.); Ftop EF301, EF303, EF352 (manufactured by Shin Akita Chemical Co., Ltd.).

[0099] Examples of silicone-based surfactants include the following product names: SH200-100cs, SH-28PA, SH-30PA, SH-89PA, SH-190, SH-8400, FLUID, SH-193, SZ-6032, SF-8428, DC-57, DC-190, PAINTAD19, FZ-2101, FZ-77, FZ-2118, L-7001, L-7002 (manufactured by Toray Dow Corning Silicone Co., Ltd.); Organosiloxane Polymer KP341 (manufactured by Shin-Etsu Chemical Co., Ltd.); BYK-300, BYK-306, BYK-310, BYK-313, BYK-320, BYK-330, BYK-331, BYK-335, BYK-341, BYK-344, BYK-370, BYK-340, BYK-345 (manufactured by BIC Chemie Japan Co., Ltd.).

[0100] Examples of nonionic surfactants include polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene oleyl ether, polyoxyethylene n-octylphenyl ether, polyoxyethylene n-nonylphenyl ether, polyethylene glycol dilaurate, and polyethylene glycol distearate.

[0101] This composition may contain one or more of the above-mentioned surfactants (H).

[0102] When surfactant (H) is incorporated into this composition, the content ratio of surfactant (H) (total content ratio if multiple types are included) is preferably 0.01 parts by mass or more and 15 parts by mass or less, more preferably 0.01 parts by mass or more and 5 parts by mass or less, still preferably 0.01 parts by mass or more and 3 parts by mass or less, still more preferably 0.01 parts by mass or more and 1.5 parts by mass or less, and particularly preferably 0.02 parts by mass or more and 1.2 parts by mass or less, per 100 parts by mass of particles (A) contained in this composition.

[0103] <Adhesion enhancer (I)> Adhesion aid (I) is a component that improves the adhesion between the resulting cured film and the substrate. Preferred adhesion aid (I) is a functional silane coupling agent having reactive functional groups such as a carboxyl group, methacryloyl group, vinyl group, isocyanate group, or oxyranyl group.

[0104] Examples of the above-mentioned functionalized silane coupling agents include trimethoxysilylbenzoic acid, γ-methacryloxypropyltrimethoxysilane, vinyltriacetoxysilane, vinyltrimethoxysilane, γ-isocyanatepropyltriethoxysilane, γ-glycidoxypropyltrimethoxysilane, β-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, and β-(3,4-epoxycyclohexyl)ethyltriethoxysilane.

[0105] This composition may contain one or more of the above-mentioned adhesion aids (I).

[0106] If the composition contains an adhesion aid (I), the content ratio of the adhesion aid (I) (total content ratio if multiple types are included) is preferably 1 to 60 parts by mass, more preferably 1 to 50 parts by mass, even more preferably 1 to 35 parts by mass, even more preferably 1 to 15 parts by mass, and particularly preferably 3 to 10 parts by mass, per 100 parts by mass of particles (A) contained in the composition.

[0107] <Sensitizer (J)> In the present invention, sensitizers can be used to enhance polymerization. Examples of sensitizers include amine-based sensitizers and alkoxyanthracene-based sensitizers. Examples of amine-based sensitizers include triethanolamine, methyldiethanolamine, triisopropanolamine, methyl 4-dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate, isoamyl 4-dimethylaminobenzoate, 2-dimethylaminoethylbenzoate, 2-ethylhexyl 4-dimethylaminobenzoate, ethyl 4-(dimethylamino)benzoate, N,N-dimethyl p-toluidine, 4,4'-bis(dimethylamino)benzophenone (commonly known as Michler's ketone), 4,4'-bis(diethylamino)benzophenone, and 4,4'-bis(ethylmethylamino)benzophenone. Examples of the alkoxyanthracene-based sensitizers include 9,10-dimethoxyanthracene, 9,10-dibutoxyanthracene, 2-ethyl-9,10-dimethoxyanthracene, 9,10-diethoxyanthracene, and 2-ethyl-9,10-diethoxyanthracene.

[0108] If the composition contains a sensitizer (J), the content ratio of the sensitizer (J) (total content ratio if multiple types are included) is preferably 0.01 parts by mass or more and 10 parts by mass or less, more preferably 0.01 parts by mass or more and 5 parts by mass or less, even more preferably 0.05 parts by mass or more and 5 parts by mass or less, and even more preferably 0.05 parts by mass or more and 3 parts by mass or less, per 100 parts by mass of particles (A) contained in the composition.

[0109] <Dehydrating agent> This composition only needs to have a moisture content of 2000 ppm by mass or more and does not require a dehydrating agent. However, if the moisture content is too high, a dehydrating agent can be added to adjust the moisture content of the composition.

[0110] Examples of dehydrating agents include the orthoester compounds described in Japanese Patent No. 7397419.

[0111] If this composition contains a dehydrating agent, the upper limit of the dehydrating agent content is preferably 10 parts by mass, more preferably 5 parts by mass, and even more preferably 3 parts by mass, per 100 parts by mass of particles (A) contained in this composition. Furthermore, this composition does not need to contain a dehydrating agent.

[0112] Other components, in addition to those mentioned above, include polymerization inhibitors, antioxidants, softeners, plasticizers, and UV absorbers. The proportions of these components are appropriately selected according to each component, within a range that does not impair the effects of this disclosure.

[0113] This composition can be obtained by mixing the above-mentioned particles (A), a radical polymerizable compound (B), a photoradical generator (C), and other optionally included components in a predetermined proportion. The composition obtained by mixing each component may be filtered, for example, through a filter with a pore size of 0.5 μm or less.

[0114] The solid content concentration of this composition (i.e., the ratio of the total mass of components other than the solvent in the photosensitive composition to the total mass of the photosensitive composition) is appropriately selected considering viscosity, volatility, etc. The solid content concentration of this composition is preferably in the range of 3 to 60% by mass. A solid content concentration of 3% by mass or more is preferable because it ensures sufficient film thickness when this composition is applied to a substrate. Furthermore, a solid content concentration of 60% by mass or less is preferable because it prevents the film thickness from becoming excessively large, and allows for a moderately high viscosity of this composition, ensuring good coatability. The solid content concentration in this composition is more preferably 5 to 55% by mass, and even more preferably 10 to 50% by mass.

[0115] <Moisture content> The amount of water contained in this composition is 2000 ppm or more by mass, preferably 2100 ppm or more, more preferably 2500 ppm or more, and even more preferably 3000 ppm or more.

[0116] Furthermore, excessive moisture content can lead to aggregation of particles in the photosensitive composition, affecting long-term storage stability. Therefore, the upper limit is preferably 10,000 ppm, more preferably 7,000 ppm, and even more preferably 5,000 ppm.

[0117] Maintaining a moisture content within the above range allows for good sensitivity and development residue rate. The moisture content in the composition can be measured by the method described in the examples.

[0118] The method for adjusting the moisture content in the photosensitive composition is not particularly limited, and any commonly used method can be employed. Specifically, one method is to leave the photosensitive composition in a sealed, humidified environment for a certain period of time. The humidity and standing time in the humidified environment can be appropriately changed according to the required moisture content, but for example, one method is to leave it in an environment with a humidity of 50-90% for about 0.1 to 10 hours. In addition, if the moisture content in the photosensitive composition is high, the moisture content can be adjusted by adding the above-mentioned dehydrating agent, etc.

[0119] ≪Method for manufacturing hardened products≫ A cured product can be manufactured using the photosensitive composition prepared as described above. This composition is particularly suitable as a negative-type pattern-forming material in which a pattern (i.e., the portion formed by the photosensitive composition) obtained by exposing a portion of the film formed by the photosensitive composition to light and dissolving the unexposed portion in an alkaline developer solution is cured by heat treatment.

[0120] The cured products of this disclosure are manufactured, for example, by a method comprising the following steps (I) and (II). (I) A step of applying a photosensitive composition onto a substrate, (II) A step of irradiating a photosensitive composition coated on the above substrate with radiation, wherein the amount of water contained in the photosensitive composition in the step of irradiating with radiation is 2000 ppm or more.

[0121] Furthermore, the method for producing the cured product of the present invention may further include the following steps (III) and (IV). (III) A process of developing the composition after irradiation with radiation. (IV) A step of curing the developed composition by heating it at a temperature of 100°C or lower. The following describes each step (steps (I) to (IV)) of the manufacturing method disclosed herein.

[0122] <Process (I): Coating process> Step (I) is a step of forming a coating film on a substrate by applying the composition onto the substrate. Examples of substrates include glass substrates, silicon wafers, plastic substrates, plastic films, and substrates on which a colored resist, overcoat, anti-reflective film, various metal thin films, sealing films, etc., are formed on their surface. Examples of plastic substrates and plastic films include resin substrates and films made of plastics such as polyethylene terephthalate (PET), polybutylene terephthalate (PBT), polyethersulfone, polycarbonate, and polyimide. Various elements (for example, light-receiving elements such as photodiodes and light-emitting elements such as organic light-emitting diodes) may be pre-installed on these substrates.

[0123] As for the application method of this composition, suitable methods such as spraying, roll coating, rotary coating (spin coating), slit die coating, bar coating, and inkjet coating can be used. Of these, spin coating, bar coating, and slit die coating are preferred application methods.

[0124] After applying this composition to a substrate, a preheating process (pre-bake) may be performed to prevent dripping and other purposes. The pre-bake conditions can be appropriately set depending on the type and usage ratio of each component. For example, the pre-bake conditions can be 60 to 100°C for 30 seconds to 10 minutes. From the viewpoint of applicability to organic EL elements, the pre-bake temperature is preferably 60 to 90°C. The film thickness of the formed coating after pre-bake is preferably 0.1 to 20 μm, and more preferably 0.2 to 15 μm.

[0125] <Process (II): Exposure process> Step (II) is a step of irradiating the photosensitive composition coated on the above substrate with radiation, wherein the amount of water contained in the photosensitive composition in the step of irradiating with radiation is 2000 ppm or more.

[0126] This radiation irradiation causes a curing reaction to proceed in the exposed area. In step (II), radiation irradiation of the coating film is usually carried out through a mask. The mask may be a multi-tone mask such as a halftone mask or a graytone mask.

[0127] Examples of radiation used to irradiate the coating include ultraviolet light, far ultraviolet light, X-rays, and charged particle beams. Examples of ultraviolet light include g-rays (wavelength 436 nm), i-rays (wavelength 365 nm), and KrF excimer laser light (wavelength 248 nm). Examples of X-rays include synchrotron radiation. Examples of charged particle beams include electron beams. Of these, ultraviolet light is preferred for irradiating the coating, and ultraviolet light with a wavelength of 200 nm to 380 nm is more preferred. Examples of light sources used include low-pressure mercury lamps, high-pressure mercury lamps, deuterium lamps, metal halide lamps, argon resonance lamps, xenon lamps, and excimer lasers. The radiation exposure dose is 500 J / m². 2 ~5,000 J / m 2 (50~500mJ / cm 2 ) is preferable.

[0128] In the present invention, the amount of water contained in the photosensitive composition during the radiation irradiation process is 2000 ppm or more. Here, "the amount of water contained in the photosensitive composition during the radiation irradiation process" means that the above amount of water should be satisfied when the radiation is irradiated. As a method for adjusting the amount of water contained in the photosensitive composition during the radiation irradiation process, one method is to adjust the amount of water in the photosensitive composition before coating to a predetermined range. Another method is to provide a settling step between the coating step (I) and the exposure step (II), and adjust the amount of water by storing the coated substrate for a predetermined time under a predetermined humidity. The humidity and storage time in the settling step can be appropriately changed according to the required amount of water, but for example, one method is to store it in an environment with a humidity of 50 to 90% for about 0.1 to 10 hours.

[0129] <Step (III): Development step> Step (III) is a process of forming a pattern on the substrate by developing the coating film that has been irradiated with radiation in step (II). This development process removes the unexposed parts of the coating film formed on the substrate, and a pattern consisting of the exposed parts can be formed on the substrate.

[0130] Examples of developers include aqueous solutions of alkalis (basic compounds) such as sodium hydroxide, potassium hydroxide, sodium carbonate, sodium silicate, sodium metasilicate, ammonia, ethylamine, n-propylamine, diethylamine, diethylaminoethanol, di-n-propylamine, triethylamine, methyldiethylamine, dimethylethanolamine, triethanolamine, tetramethylammonium hydroxide (TMAH), tetraethylammonium hydroxide, pyrrole, piperidine, 1,8-diazabicyclo[5.4.0]-7-undecene, and 1,5-diazabicyclo[4.3.0]-5-nonane. Alternatively, aqueous solutions obtained by adding an appropriate amount of water-soluble organic solvents such as methanol or ethanol, or a surfactant, to an aqueous solution of alkali, or by adding a small amount of various organic solvents capable of dissolving this composition, may be used as a developer.

[0131] As for the development method, appropriate methods such as the liquid-filling method, dipping method, agitation immersion method, and shower method can be employed. The development time should be adjusted as appropriate depending on the composition of this composition. For example, the development time is 20 seconds to 120 seconds.

[0132] <Process (IV): Heating process> Step (IV) is a step of heating the developed pattern at a temperature of 100°C or lower. The heat treatment in step (IV) further hardens the pattern, resulting in a cured product exhibiting good heat resistance and chemical resistance. The heat treatment can be carried out using a heating device such as an oven or a hot plate. When obtaining microlenses as cured products, hemispherical microlenses may be obtained by thermal flowing the developed pattern through the heat treatment in step (IV).

[0133] The heating temperature in step (IV) is 100°C or lower, preferably 95°C or lower, and more preferably 90°C or lower, from the viewpoint of enabling application to organic EL elements. Furthermore, from the viewpoint of obtaining a cured product with high heat resistance and chemical resistance, the heating temperature in step (IV) is preferably 60°C or higher, and more preferably 80°C or higher. The heating time can be set appropriately depending on the type of heating device, etc. For example, when heating is performed using a hot plate, the heating time is, for example, 5 to 60 minutes. When heating is performed using an oven, the heating time is, for example, 10 to 90 minutes. In step (IV), a step bake method in which multiple heat treatments are performed may be used.

[0134] The manufacturing method of the present disclosure may further include, as an optional step, a step of irradiating the cured product with radiation before or after the heating step in step (IV) (hereinafter also referred to as the "post-exposure step"). By irradiating with radiation in the post-exposure step (hereinafter also referred to as the "post-exposure step"), heat resistance, chemical resistance, etc., can be further improved, and a more reliable cured product can be obtained. The type of radiation and exposure conditions in post-exposure can be the same as those in step (II). The wavelength of the irradiation light, irradiation amount, light source, etc., during post-exposure may be the same as or different from those in step (II).

[0135] ≪Cured film≫ The cured film of the present invention can be formed by curing the above-mentioned photosensitive composition. According to this composition, a cured product with a high refractive index can be obtained, specifically, a cured product with a refractive index of 1.60 or higher at a wavelength of 550 nm can be obtained. Furthermore, according to this composition, a cured film with a high refractive index of preferably 1.68 or higher, more preferably 1.70 or higher, at a wavelength of 550 nm can also be obtained.

[0136] This composition is highly sensitive and can suppress film peeling when forming a cured film from it. Therefore, with this composition, a cured product having a desired pattern shape can be obtained by exposure treatment and development treatment of the composition.

[0137] The above-mentioned cured film is suitable as an optical component for display elements or image sensors. The optical component is preferably a component that improves the light extraction efficiency in a display element (an optical path adjusting component that adjusts the path of light) or an optical path adjusting component that adjusts the path of light in order to focus it on a light-receiving element (photodiode) in an image sensor such as a camera.

[0138] ≪Display Elements≫ The display element of the present invention comprises a cured film formed from the above-mentioned photosensitive composition. Examples of display elements include liquid crystal display elements, organic EL display elements, and micro-LED (Light Emitting Diode) display elements.

[0139] Image sensor The image sensor of the present invention comprises a cured film formed from the above-mentioned photosensitive composition. The cured film of the present invention is preferably used as an optical path adjusting member to adjust the path of light in order to focus it onto a light-receiving element (photodiode) in an image sensor such as a camera. [Examples]

[0140] The present invention will be described in detail below with reference to examples, but the present invention is not limited to these examples. In the examples and comparative examples, "parts" and "%" refer to mass unless otherwise specified. In this example, the weight-average molecular weight (Mw) of the polymer (binder resin) was measured by the following method.

[0141] [Weight average molecular weight (Mw)] The Mw of the polymer (binder resin) is a polystyrene equivalent value measured by the following method and conditions. • Measurement method: Gel permeation chromatography (GPC) method • Equipment: GPC-101 manufactured by Showa Denko Corporation • GPC columns: GPC-KF-801, GPC-KF-802, GPC-KF-803, and GPC-KF-804 manufactured by Shimadzu GLC Co., Ltd. • Mobile phase: tetrahydrofuran Column temperature: 40°C ·Flow rate: 1.0mL / min • Sample concentration: 1.0% by mass • Sample injection volume: 100 μL • Detector: Differential refractometer • Standard material: Monodisperse polystyrene

[0142] [Average particle size] The average particle diameter was measured using the D50 particle diameter (median diameter, which represents the particle diameter showing the 50% integrated value of the integrated distribution curve) measured by dynamic light scattering, using a MicrotracWaveII-EX150 from MicrotracBell.

[0143] <Synthesis of Binder Resin (G-1)> [Synthesis Example 1] 100 parts by mass of propylene glycol monomethyl ether acetate was charged into a flask equipped with a condenser and a stirrer, and nitrogen purged. The mixture was heated to 80°C, and at the same temperature, a mixed solution of 100 parts by mass of propylene glycol monomethyl ether acetate, 15 parts by mass of methacrylic acid, 15 parts by mass of styrene, 5 parts by mass of benzyl methacrylate, 15 parts by mass of 2-hydroxyethyl methacrylate, 23 parts by mass of 2-ethylhexyl methacrylate, 12 parts by mass of N-phenylmaleimide, 15 parts by mass of mono(2-acryloyloxyethyl) succinate, and 6 parts by mass of 2,2'-azobis(2,4-dimethylvaleronitrile) was added dropwise over 1 hour, and polymerization was carried out while maintaining this temperature for 2 hours. Subsequently, the temperature of the reaction solution was raised to 100°C, and polymerization was carried out for a further 1 hour to obtain a binder resin solution (solid content concentration: 33% by mass). The Mw of the obtained binder resin solution was 12,200. This binder resin solution will be referred to as "Binder Resin (G-1)".

[0144] <Preparation of particle dispersion> [Preparation Example 1] Zirconia particle dispersion (A-1) 782 g of zirconium 2-ethylhexanoate mineral spirit solution (manufactured by Daiichi Rare Elements Chemical Industry Co., Ltd.) was mixed with 268 g of pure water. The resulting mixture was placed in an autoclave equipped with a stirrer, and the atmosphere in the reaction vessel was replaced with nitrogen gas. The reaction solution was then heated to 180°C and reacted for 16 hours to synthesize zirconium oxide. The pressure in the vessel at 180°C was 1.03 MPa. The solution after the reaction was removed, the precipitate accumulated at the bottom was filtered off, washed with acetone, and then dried. When 100 g of the dried precipitate was dispersed in 800 mL of toluene, a cloudy solution was obtained. Next, as a purification step, the solution was filtered again using quantitative filter paper (Advantec Toyo Co., Ltd., No. 5C) to remove coarse particles from the precipitate. Then, white zirconium oxide particles were recovered by removing toluene concentrated under reduced pressure from the filtrate. 10 g of zirconium oxide particles obtained above were dispersed in 90 g of toluene to obtain a clear dispersion. 1.5 g of 3-methacryloxypropyltrimethoxysilane (Shin-Etsu Chemical Co., Ltd., KBM-503) was added to the clear dispersion as a surface coating agent, and the mixture was heated under reflux at 90°C for 1 hour. Next, n-hexane was added to the dispersion after reflux treatment to agglomerate the dispersed particles, causing the dispersion to become cloudy. After separating the agglomerated particles from the cloudy liquid using filter paper, the mixture was heated and dried at room temperature to prepare zirconium oxide particles surface-treated with 2-ethylhexanoic acid and 3-methacryloxypropyltrimethoxysilane. The average particle size of the obtained coated zirconium oxide particles was measured to be 12 nm. In addition, propylene glycol monomethyl ether (PGME) was added to the white powder and stirred to obtain a zirconia particle dispersion containing 80% by mass of coated zirconia particles (this is referred to as "Zirconia Particle Dispersion (A-1)"). The average particle size of aggregated particles in the zirconia particle dispersion (A-1) was 12 nm.

[0145] [Preparation Example 2] Zirconia particle dispersion (A-2) Zirconia particle dispersion (A-2) was prepared in the same manner as in Preparation Example 1, except that the solvent (PGME) in particle dispersion (A-1) was changed to propylene glycol monomethyl ether acetate (PGMEA). The average particle size of the particles in zirconia particle dispersion (A-2) was 12 nm.

[0146] [Preparation Example 3] Zirconia particle dispersion (A-3) A particle dispersion (A-3) was prepared by mixing zirconium dioxide particles, a dispersant, a binder resin (G-1), and a solvent so that the amounts of zirconium dioxide particles, a dispersant, a binder resin (G-1), and the solvent in the dispersion were as follows. The amount of solvent as follows is the total amount including the amount of solvent contained in the dispersant and binder resin (G-1) used in preparing the particle dispersion (A-3). • Zirconium dioxide particles (manufactured by Daiichi Rare Elements Chemical Industry Co., Ltd., UEP) 100.00 parts by mass • Dispersant (DISPERBYK-111, manufactured by BIC Chemie): 6.67 parts by mass / based on solid content • Binder resin (G-1): 6.67 parts by mass / based on solid content • Solvent (PGMEA) 138.51 parts by mass The above components were thoroughly stirred to obtain a mixture (referred to as mixture Lqb). Next, 20 g of 0.3 mm diameter zirconia beads and 10 g of mixture Lqb were dispersed using a paint shaker at 25-45°C for 6 hours. After the dispersion was complete, the beads and dispersion were separated by filtration to prepare a zirconia dispersion (A-3) with a total solid content of 45% by mass. The average particle size of the particles in the zirconia particle dispersion (A-3) was 38 nm.

[0147] [Preparation Example 4] Titania particle dispersion (A-4) (1) Production of rutile-type titanium dioxide hydrosol In a 1L glass beaker, 240g of titanium oxychloride aqueous solution with a TiO2 concentration of 25% (60g as TiO2) and 5g of zirconium oxychloride powder with a ZrO2 concentration of 35% (1.8g as ZrO2) were added, and water was added to make a total volume of 1L. It was confirmed that the zirconium oxychloride powder was dissolved. This solution is called Solution A. In a 2L flask equipped with a stirring device and reflux condenser, 1kg of water and 20g of stannic chloride aqueous solution with a SnO2 concentration of 30% (6g as SnO2) were charged, and the flask was heated with stirring. When the temperature reached 60°C, Solution A was added dropwise over 15 minutes while maintaining the temperature at 60°C. After the dropwise addition was complete, the flask was heated until it boiled, and maintained at a boil under reflux for 3 hours. After that, it was cooled to 40°C, the pH was adjusted to 7.0 with 28% ammonia aqueous solution, filtered, and washed to obtain a cake. Water and 36% hydrochloric acid were added to this cake and stirred to produce 300 g of titanium dioxide hydrosol with a pH of 1.3 and a TiO2 concentration of 20%, containing 10% SnO2 and 3% ZrO2 relative to the TiO2. (2) Hydrosol coating treatment In a 2L glass beaker, 200g of titanium dioxide hydrosol with a TiO2 concentration of 20% (40g as TiO2) obtained in (1) above was placed, and deionized water was added to dilute it to a TiO2 concentration of 4%. 5.2g of 3-glycidoxypropyltrimethoxylane (organosilane KBM-403, manufactured by Shin-Etsu Chemical Co., Ltd.) was added to this while stirring. This solution is called solution B. In another 5L glass beaker, 40g of sodium silicate aqueous solution with an SiO2 concentration of 10% (4g as SiO2) and 2g of 48% sodium hydroxide aqueous solution were placed, and diluted with deionized water to a total volume of 1200g. Solution B was added dropwise to this solution over 15 minutes while stirring. The pH after the dropwise addition was complete was 10. Next, 20g of a 30% SnO2 aqueous solution of stannic chloride (6g as SnO2) was added dropwise to this mixed solution over 15 minutes while maintaining a pH of 10, simultaneously with a 48% sodium hydroxide aqueous solution. Subsequently, 20g of a 10% SiO2 aqueous solution of sodium silicate (2g as SiO2) was added, the mixture was heated to 80°C, the pH was adjusted to 8 with 1% hydrochloric acid, and the mixture was aged at the same temperature for 120 minutes. This mixture was cooled to 20°C, the pH was adjusted to 3 with a 10% citric acid aqueous solution, and this solution was passed through an ultrafiltration module (Asahi Kasei Chemicals Corporation, Microza SLP-1 053) while replenishing with an equal amount of deionized water to obtain an electrical conductivity of 3 × 10⁻¹⁰ at a TiO2 concentration of 3%. -3 The electrolyte components were reduced to below S / cm. At this stage, the citric acid used as a pH adjuster was removed and no residue remained. The pH was further adjusted to 8 with t-butylamine, and then concentrated using the same ultrafiltration module until the solid content concentration reached 20%. At a solid content concentration of 20%, a rutile-type titanium dioxide hydrosol was obtained, coated with 15% SiO2 and 15% SnO2 relative to TiO2. (3) Solvent replacement of hydrosol with propylene glycol monomethyl ether The coated titanium dioxide hydrosol obtained in (2) above was diluted with propylene glycol monomethyl ether to a TiO2 concentration of 5%, and the solution was passed through the same ultrafiltration module while supplying an amount of propylene glycol monomethyl ether equal to the amount filtered. Finally, the supply of propylene glycol monomethyl ether was stopped to obtain a titania particle dispersion (A-4) with a water content of 1% or less, a solid content concentration of 20%, and coated with 15% SiO2 and 15% SnO2 relative to the TiO2. The average particle size of the particles in the titania particle dispersion (A-4) was 36 nm.

[0148] [Preparation Example 5] Barium titanate particle dispersion (A-5) In a perfluoroalkoxyalkane (PFA) container, 100 parts by mass of barium titanate (manufactured by Sigma-Aldrich, primary particle size less than 100 nm) was added to 11 parts by mass of Marbon AC-F3 (polyoxyethylene secondary alkyl ether) manufactured by Matsumoto Oil & Fat Pharmaceutical Co., Ltd., and 192 parts by mass of propylene glycol monomethyl ether. Further, 900 parts by mass of zirconia beads with a particle size of 0.1 mm (manufactured by Nikkatoh Co., Ltd.) were added, and the mixture was shaken for 1 hour using paint conditioner (manufactured by REDDEVIL) to disperse the barium titanate nanoparticles in the propylene glycol monomethyl ether. After that, the zirconia beads were removed to obtain barium titanate particle dispersion (A-5). The average particle size of the particles in the barium titanate particle dispersion (A-5) was 50 nm.

[0149] <Synthesis of polymerizable compound (B-3)> [Synthesis Example 2] 440 parts by mass of a 50% by mass sodium hydroxide aqueous solution / dichloromethane (mass ratio = 1 / 1) were mixed with 13.9 g (0.12 mol) of 3-ethyl-3-hydroxymethyloxetane, 15.2 g (0.1 mol) of p-vinylbenzyl chloride, and 2.1 g of tetrabutylammonium bromide as an interlayer transfer catalyst. The mixture was stirred at room temperature under a nitrogen atmosphere for 6 hours. The salts produced from the reaction mixture were then removed using a glass filter, and the residue was washed thoroughly with dichloromethane. The resulting filtrate was subjected to three separate liquid-liquid purifications using dichloromethane and distilled water, and then extracted with dichloromethane. Next, a small amount of activated carbon was added to the dichloromethane layer to remove the color, and the mixture was dried over magnesium sulfate. The solvent was then removed by distillation under reduced pressure concentration. The crude product obtained was purified by silica gel chromatography (ethyl acetate / n-hexane = 1 / 3) to obtain 17.2 g of 3-[(4-vinylbenzyl)oxymethyl]-3-ethyloxetane (polymerizable compound (B-3)).

[0150] <Preparation of photosensitive composition> The types and abbreviations of the particles (A), radical polymerizable compounds (B), radical polymerization initiators (C), photoacid generators (E), solvents (F), binder resins (G), surfactants (H), and adhesion promoters (I) used in the preparation of the photosensitive composition are shown below. <(A) Particle> A-1~A-5: Particle dispersions obtained according to preparation examples 1~5 (A-1)~(A-5) <(B) Radical polymerizable compounds> B-1: A mixture of dipentaerythritol pentaacrylate and dipentaerythritol hexaacrylate (product name: KAYARAD DPHA, manufactured by Nippon Kayaku Co., Ltd.) B-2:3-Phenoxybenzyl acrylate (product name: Light Acrylate POB-A, manufactured by Kyoeisha Chemical Co., Ltd.) B-3: 3-[(4-vinylbenzyl)oxymethyl]-3-ethyloxetane obtained in Synthesis Example 2 (C) Photoradical Generator C-1: NCI-930 (Product name, manufactured by ADEKA Corporation) <(E) Photoacid Generator> E-1: Triphenylsulfonium hexafluoroantimonate <(F) Solvent> F-1: Propylene glycol monomethyl ether acetate F-2: Propylene glycol monomethyl ether F-3:3-Methoxybutylacetate F-4: Diethylene glycol ethyl methyl ether F-5: Diacetone alcohol F-6: Dipropylene glycol methyl ether acetate <(G) Binder resin> G-1: Binder resin (G-1) obtained by synthesis example 1 <(H) Surfactants> H-1: Polyether-modified silicone additive (Product name: DOWSIL™ SH28 Paint Additive, manufactured by Toray Dow Corning Corporation) <(I) Adhesion enhancer> I-1:3-Glycidoxypropyltrimethoxysilane I-2:3-Methacryloxypropyltrimethoxysilane (Product name: Sylace S710, manufactured by Chisso Corporation)

[0151] [Example 1] Preparation of a photosensitive composition A photosensitive composition (S) was prepared by adding 100.0 parts by mass (solid content) of zirconia particle dispersion (A-1) as particles (A), 10.0 parts by mass (solid content) of binder resin (G-1), 10.0 parts by mass (solid content) of polymerizable compound (B-1) and 15.0 parts by mass of polymerizable compound (B-2) as polymerizable compounds (B), 4.0 parts by mass of photoradical generator (C) (C-1), and 0.05 parts by mass of surfactant (H) (H-1). Furthermore, solvent (F) consisting of (F-1) and (F-2) in a 50:50 (mass ratio) ratio was added to achieve a solid content concentration of 40.0% by mass, and the mixture was stirred. The mixture was then filtered using a 0.5 μm filter. The photosensitive composition (S) was then left to stand in a sealed, humidified environment for a certain period of time to adjust the moisture content, thereby obtaining a photosensitive composition (S-1) with a moisture content of 2103 ppm.

[0152] <Measuring moisture content> The water content in the photosensitive composition was measured using a Mitsubishi Chemical Analytical Corporation CA-100 coulometric titration moisture meter. Aquamicron TMAX / CXU was used as the titration reagent. Three measurements were repeated, and the average value was calculated as the water content of the photosensitive composition.

[0153] [Examples 2 and 3] Adjustment of the moisture content of the photosensitive composition By varying the time spent leaving the photosensitive composition (S) in a sealed, humidified environment, the amount of water absorbed by the photosensitive composition was adjusted, resulting in photosensitive compositions with different water content. The water content of the photosensitive composition (S-2) in Example 2 was 3054 ppm, and the water content of the photosensitive composition (S-3) in Example 3 was 4119 ppm.

[0154] [Examples 4-15] The particle dispersion, binder resin, polymerizable compound, photoradical generator, photoacid generator, surfactant, adhesion aid, and solvent were mixed in the proportions shown in Table 1, and the photosensitive compositions (S-4) to (S-15) of Examples 4 to 15 were prepared in the same manner as the photosensitive composition of Example 1. In Table 1, "-" indicates that the corresponding component was not used. Also, in Table 1, the % in the solvent column represents the mass ratio of each component. For example, Example 2 indicates that a mixed solvent of (F-1) and (F-2) in a mass ratio of 50:50 was used, and Example 5 indicates that (F-1) was used alone.

[0155] [Comparative Examples 1-3] Adjustment of the moisture content of photosensitive compositions Separately from the photosensitive composition (S-1) obtained in Example 1, a photosensitive composition (S-1) was prepared. Molecular sieves were added to this photosensitive composition (S-1), and the mixture was left to stand in a sealed environment to adjust the moisture content. The molecular sieves were then removed by filtration to obtain photosensitive compositions (SC-1) to (SC-3) with different moisture content. The moisture content of photosensitive composition (SC-1) was 1459 ppm, the moisture content of photosensitive composition (SC-2) was 976 ppm, and the moisture content of photosensitive composition (SC-3) was 510 ppm.

[0156] <Method for fabricating a film-deposited substrate> A photosensitive composition was rotary coated onto a silicon wafer having a silicon oxide film. The wafer was then pre-baked at 85°C for 60 seconds using a hot plate, followed by cooling at 25°C for 30 seconds to form a 3 μm thick coating. Next, the wafer was exposed using a Canon MPA through a predetermined mask and allowed to stand at 25°C for 60 seconds. Finally, it was developed for 60 seconds in an alkaline developer (2.38% by mass tetramethylammonium hydroxide aqueous solution) heated to 23°C, followed by rinsing with ultrapure water for 60 seconds to prepare a film-deposited substrate. While substrate preparation is typically carried out under 50% humidity, in Example 16, the substrate was prepared under 55% humidity, and in Example 17, under 45% humidity, using the photosensitive composition from Example 1.

[0157] <Evaluation of residual film rate during development> The residual film rate after development was evaluated by measuring the film thickness after development and calculating the ratio to the film thickness after exposure (film thickness after development ÷ film thickness after exposure × 100 (%)). The film thickness after exposure and development was measured using a non-contact film thickness gauge. The evaluation results for the residual film rate after development are shown in Table 1.

[0158] [Table 1]

[0159] As shown in Table 1, each photosensitive composition in Examples 1 to 17 exhibited high residual film rates and high sensitivity during development. In contrast, Comparative Examples 1 to 3 exhibited low residual film rates and reduced sensitivity. When the residual film rate during development is low, there is a problem of large variations in film thickness due to development, resulting in in-plane film thickness variations and unstable light extraction efficiency.

[0160] Next, we will describe Examples 18-22 and Comparative Example 4. The compounds used in these examples and comparative examples are as follows.

[0161] <(A) Particle> A-2, A-4: Particle dispersions obtained according to Preparation Example 2 and Preparation Example 4 (A-2), (A-4) <(B) Radical polymerizable compounds> B-4: α-Acryloyloxy-ω-carboxymethyl-polyethylene glycol B-5:4'-(6-acryloyloxyhexyloxy)biphenyl-4-carboxylic acid (CAS number: 134903-88-1) B-6: 2-Methyl-2-acrylate-2-hydroxyethyl phosphate (CAS number: 52628-03-2) B-7: 2-(2-ethoxyethoxy)ethyl acrylate (CAS number: 7328-17-8) B-8: α-Acryloyl-ω-(Acryloyloxy)poly(oxyethylene) (CAS number: 26570-48-9) B-9: Tripropylene glycol diacrylate (CAS number: 42978-66-5) B-10: α,α'-[propane-2,2-diylbis(4,1-phenylene)]bis[ω-(methacryloyloxy)poly(oxyethylene)] (CAS number: 41637-38-1) B-11: 3-Ethyl-3-(2,3-Epoxypropoxymethyl)oxetane (CAS No.: 15957-34-3) B-12:3,3'-[oxybis(methylene)]bis(3-ethyloxetane) (CAS number: 18934-00-4) (C) Photoradical Generator C-2: Irgacure OXE-01 (BASF) C-3: Irgacure OXE-02 (BASF) <(E) Photoacid Generator> E-2: Diphenyl[4-(phenylthio)phenyl]sulfonium hexafluorophosphate E-3: 4-Isobutylphenyl-4'-Toluyliodohexafluorophosphate <(F) Solvent> F-1: Propylene glycol monomethyl ether acetate F-2: Propylene glycol monomethyl ether F-3:3-Methoxybutylacetate F-5: Diacetone alcohol <(H) Surfactants> H-2: BYK-310 (manufactured by BYK) H-3: BYK-313 (manufactured by BYK) H-4: BYK-320 (manufactured by BYK) H-5: BYK-331 (Manufactured by BYK) <(I) Adhesion enhancer> I-3:β-(3,4-epoxycyclohexyl)ethyltrimethoxysilane (CAS number: 3388-04-3) I-4:β-(3,4-epoxycyclohexyl)ethyltriethoxysilane <(J) Sensitizer> J-1: 4-(dimethylamino)benzoate ethyl (CAS number: 10287-53-3) J-2:9,10-Dibutoxyanthracene (CAS number: 76275-14-4)

[0162] [Example 18] Preparation of a photosensitive composition 10.0 parts by mass (on a solid content basis) of zirconia particle dispersion (A-2) as particles (A), 16.0 parts by mass of polymerizable compound (B-4) and 16.0 parts by mass of polymerizable compound (B-7) as polymerizable compounds (B), 3.0 parts by mass of photoradical generator (C-2), 0.02 parts by mass of photoacid generator (E-2), 0.01 parts by mass of sensitizer (J-1), 6.0 parts by mass of adhesion aid (I-3), and 1.0 part by mass of surfactant (H-2). After adding solvent (F-3) to achieve a solid content concentration of 40.0% by mass, the mixture was stirred, filtered using a 0.5 μm filter, and the water content was adjusted in the same manner as in Example 1 to prepare the photosensitive composition of Example 18.

[0163] [Examples 19-22] The particle dispersion, polymerizable compound, photoradical generator, photoacid generator, sensitizer, surfactant, adhesion aid, and solvent were mixed in the proportions shown in Table 2, and the photosensitive compositions of Examples 19 to 22 were prepared in the same manner as the photosensitive composition of Example 18. In Table 2, "-" indicates that the corresponding component was not used. Also, in Table 2, the % in the solvent column represents the mass ratio of each component.

[0164] [Comparative Example 4] Adjustment of the moisture content of the photosensitive composition Separately from the photosensitive composition of Example 18, a molecular sieve was added to the photosensitive composition, and the mixture was left to stand in a sealed environment to adjust the moisture content. The molecular sieve was then removed by filtration to obtain a photosensitive composition of Comparative Example 4 with a different moisture content. The moisture content of the photosensitive composition of Comparative Example 4 was 988 ppm.

[0165] [Table 2]

[0166] As shown in Table 2, each photosensitive composition in Examples 18-22 exhibited high residual film rates and high sensitivity during development. In contrast, Comparative Example 4 showed low residual film rates and reduced sensitivity. When the residual film rate during development is low, there is a problem of large variations in film thickness due to development, resulting in in-plane film thickness variations and unstable light extraction efficiency.

Claims

1. A photosensitive composition for forming an optical component, comprising particles (A), a radical polymerizable compound (B), and a photoradical generator (C), The amount of water contained in the above photosensitive composition is 2000 ppm by mass or more. A photosensitive composition for forming optical components.

2. The photosensitive composition according to claim 1, wherein the above-mentioned particle (A) is at least one particle selected from the group consisting of zirconium oxide, titanium oxide, barium titanate, and silica.

3. The photosensitive composition according to claim 1, wherein the optical component is a component that improves the light extraction efficiency in a display element.

4. A cured product obtained by curing the photosensitive composition according to any one of claims 1 to 3.

5. A step of applying a photosensitive composition for forming an optical component, comprising particles (A), a radical polymerizable compound (B), and a photoradical generator (C), onto a substrate, The process includes irradiating a photosensitive composition coated on the above substrate with radiation. The amount of water contained in the photosensitive composition during the radiation irradiation process is 2000 ppm by mass or more. A method for manufacturing a cured product.

6. A display element comprising the cured product described in claim 4.

7. An image sensor comprising the cured product described in claim 4.

Images