Photosensitive composition, cured product and method for producing same, display element, and imaging element

Abstract

The purpose of the present invention is to provide: a photosensitive composition that undergoes little increase in viscosity even after a given period of time has elapsed, has exceptional storage stability, does not solidify when a coating slit nozzle or the like is used, and can be applied even after a given period of time has elapsed (has excellent coating properties over time); a cured film formed from the photosensitive composition; a method for producing the cured film; a display element provided with the cured film; and an imaging element provided with the cured film. The present invention relates to a photosensitive composition for forming an optical member, the photosensitive composition containing particles (A), a radically polymerizable compound (B), a photoradical generator (C), and a dehydrating agent (D), the dehydrating agent (D) containing an orthoester compound.

Description

Photosensitive composition, cured product and method for producing the same, display element, and imaging element

[0001] The present invention relates to a photosensitive composition, a cured product and a method for producing the same, a display element, and an imaging element, and more particularly to a technique for forming an optical member for a display element or an imaging element.

[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 imaging elements in imaging devices such as cameras. Solid-state imaging elements are provided with hemispherical condenser lenses (hereinafter also referred to as "microlenses") or intralayer lenses to collect light onto light-receiving elements (photodiodes) and improve sensor sensitivity. Furthermore, display elements such as organic EL elements have adopted a structure in which microlenses are provided on the light-emitting side of each pixel in order to improve light extraction efficiency and adjust the viewing angle (see, for example, Patent Document 1). Lenses for solid-state imaging elements and display elements have also recently been formed by photolithography using photosensitive compositions.

[0003] Known examples of the photosensitive composition include a film-forming composition containing inorganic particles, a polysilane compound, a polymerizable monomer, and a curing accelerator such as a dehydrating agent (see, for example, Patent Document 2).

[0004] JP 2020-101659 A JP 2007-131714 A

[0005] The inventors have found that photosensitive compositions containing particles increase in viscosity over time and have poor storage stability. Furthermore, when using a coating device such as a slit nozzle, the slit nozzle is repeatedly used in the cycle of coating, leaving the composition undisturbed, coating, and leaving the composition undisturbed. However, after a certain period of time, the photosensitive composition in the coating device solidifies and adheres to the tip of the nozzle, resulting in poor coating performance.

[0006] The present invention aims to provide a photosensitive composition that exhibits excellent storage stability with little increase in viscosity even after a certain period of time, that does not solidify when using a coating slit nozzle or the like, and that can be applied even after a certain period of time has passed (good applicability over time); a cured film formed from the photosensitive composition and a method for producing the same; a display element including the cured film; and an imaging element including the cured film.

[0007] As a result of extensive research into solving the above problems, the present inventors have found that the above object can be achieved by using a photosensitive composition having the following constitution, and have thus completed the present invention.

[0008] In one embodiment, the present invention relates to a photosensitive composition for forming an optical member, comprising particles (A), a radical polymerizable compound (B), a photoradical generator (C), and a dehydrating agent (D), wherein the dehydrating agent (D) comprises an orthoester compound.

[0009] In another embodiment, the present invention relates to a photosensitive composition for forming an optical member, the photosensitive composition comprising particles (A), a radical polymerizable compound (B), and a photoradical generator (C), wherein the amount of water contained in the photosensitive composition is less than 2000 ppm.

[0010] In another embodiment, the present invention relates to a method for producing a cured product, the method comprising: applying the photosensitive composition onto a substrate; irradiating the photosensitive composition applied onto the substrate with radiation; developing the photosensitive composition after irradiation with radiation; and heating the developed photosensitive composition at a temperature of 100°C or less to cure it.

[0011] In another embodiment, the present invention relates to a cured product formed by curing the photosensitive composition, and a display element and an imaging element including the cured film.

[0012] The photosensitive composition of the present invention exhibits excellent storage stability with little increase in viscosity even after a certain period of time, and when using a coating slit nozzle or the like, the photosensitive composition does not solidify and can be applied even after a certain period of time has passed (i.e., has good coatability over time). The reason for this is presumed to be as follows: When a photosensitive composition containing particles is exposed to the atmosphere for a certain period of time, moisture in the atmosphere acts on the particles in the photosensitive composition, promoting aggregation, which is thought to result in an increase in viscosity of the photosensitive composition and poor coatability over time and poor coatability over time and poor coatability over time and poor coatability over time. However, in the present invention, by incorporating an orthoester compound into the photosensitive composition, it is possible to capture moisture that has penetrated into the photosensitive composition, and it is thought that even a photosensitive composition containing particles exhibits little increase in viscosity and excellent coatability over time and excellent coatability over time and good coatability over time and good coatability over time and good coatability over time.

[0013] Furthermore, according to the photosensitive composition of another embodiment, the amount of water contained in the photosensitive composition is less than 2000 ppm, which is thought to make it difficult for the particle components in the composition to aggregate, resulting in good long-term coatability.

[0014] The method for producing a cured film of the present invention uses a photosensitive composition that exhibits little increase in viscosity even after a certain period of time and has excellent long-term coatability and storage stability, and therefore can produce a high-quality cured film even after a certain period of time has passed.

[0015] The display element and the imaging element of the present invention are of high quality because they include the cured film.

[0016] 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 "to" means that the numerical values ​​described before and after "to" are included as the lower and upper limits. A "structural unit" refers to a unit that mainly constitutes the main chain structure, and at least two or more units are contained in the main chain structure.

[0017] In this specification, the term "hydrocarbon group" includes chain hydrocarbon groups, alicyclic hydrocarbon groups, and aromatic hydrocarbon groups. The term "chain hydrocarbon group" refers to a straight-chain hydrocarbon group or a branched hydrocarbon group that does not contain a cyclic structure in the main chain and is composed only of a chain structure. However, it may be saturated or unsaturated. The term "alicyclic hydrocarbon group" refers to a hydrocarbon group that contains only an alicyclic hydrocarbon structure as a ring structure and does not contain an aromatic ring structure. However, it does not necessarily have to be composed only of an alicyclic hydrocarbon structure, and it also includes groups that have a chain structure as part of it. The term "aromatic hydrocarbon group" refers to a hydrocarbon group that contains an aromatic ring structure as a ring structure. However, it does not necessarily have to be composed only of an aromatic ring structure, and it may contain a chain structure or an alicyclic hydrocarbon structure as part of it. The ring structures of the alicyclic hydrocarbon group and the aromatic hydrocarbon group may have a substituent consisting of a hydrocarbon structure.

[0018] In this specification, "(meth)acrylo" is intended to encompass "acrylo" and "methacrylo", "(meth)acrylic" is intended to encompass "acrylic" and "methacrylic", and "(meth)acrylate" is intended to encompass "acrylate" and "methacrylate".

[0019] <Photosensitive Composition> The photosensitive composition according to this embodiment (hereinafter also referred to as "the composition") is a composition containing particles (A), a radical polymerizable compound (B), a photoradical generator (C), and a dehydrating agent (D), wherein the dehydrating agent (D) contains an orthoester compound (hereinafter also referred to as the composition (1)), and a photosensitive composition for forming an optical member, which contains particles (A), a radical polymerizable compound (B), and a photoradical generator (C), and wherein the water content in the photosensitive composition is less than 2000 ppm (hereinafter also referred to as the composition (2)).

[0020] The photosensitive composition is a photosensitive composition for forming optical elements for display elements such as organic EL elements and imaging elements. Optical elements formed from this composition are used, for example, to increase the light extraction efficiency of display elements or to improve sensor sensitivity by collecting light on light-receiving elements (photodiodes) in solid-state imaging devices. The optical element preferably includes a planarizing film or a pattern formed by repeatedly arranging lenses. The lenses constituting the pattern may have a hemispherical, cylindrical, or truncated conical shape. The shape of the lenses as viewed from above may be circular, polygonal, or the like, and each may have a curved surface such as a sphere, or a cylindrical or truncated conical shape. The lenses are formed from the photosensitive composition of the present invention, and another transparent material layer, such as a low-refractive index material layer, may be formed in the gap between the lenses. The planarizing film is formed on a substrate to planarize the surface of the substrate on which a semiconductor element or the like is formed. The pattern is a microscopic light collector (lens or trapezoidal / rectangular pattern) or interlayer lens provided in a display element or a solid-state imaging element (e.g., a CCD image sensor or a CMOS image sensor). In a display element such as an organic EL element, the pattern is provided in each pixel for the purpose of improving the light extraction efficiency of each pixel and adjusting the viewing angle, and in a solid-state imaging element, the pattern is provided for the purpose of collecting light in a light-receiving element to improve sensor sensitivity. The composition is preferably a photosensitive composition for forming a planarizing film or a photosensitive composition for forming a pattern. Each component contained in the photosensitive composition will be described below.

[0021] <Particles (A)> The particles (A) can be selected according to 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 particles (A) may be either inorganic particles or organic particles, and pigment particles can also be used.

[0022] The inorganic particles are not particularly limited, and examples thereof include particulate substances 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, palladium sulfide, etc. Among these, from the viewpoint of particle stability, at least one type of particle selected from the group consisting of zirconium oxide, titanium oxide, and barium titanate is preferred, and zirconium oxide particles are particularly preferred in terms of high dispersion stability.

[0023] The organic particles are not particularly limited and include, for example, particles made of polymer compounds such as polystyrene, polyolefin resins such as polyethylene and polypropylene, and acrylic resins. Organic particles also include transparent particles, opaque particles, colored particles, and hollow particles.

[0024] The pigment particles may be either organic or inorganic. Examples of the pigment include organic or inorganic pigments such as carbon black, graphite, activated carbon, carbon fiber, carbon nanotubes, carbon microcoils, carbon nanohorns, carbon aerogel, fullerene, aniline black, Pigment Black 7, titanium black, lactam black, perylene black, chromium oxide green, Milori blue, cobalt green, cobalt blue, manganese-based pigments, ferrocyanide, phosphate ultramarine, Prussian blue, ultramarine, cerulean blue, pyridian, emerald green, lead sulfate, yellow lead, zinc yellow, red iron oxide (red iron (III)), 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.

[0025] The shape of the particles (A) is not particularly limited, but examples thereof include spherical, granular, plate-like, and columnar shapes.

[0026] The average particle size of the particles (A) is not particularly limited, but from the viewpoint of obtaining a cured film having 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. From the viewpoint of dispersion stability, the average particle size of the particles (A) is, for example, 1 nm or more, preferably 2 nm or more. The average particle size in the present invention means the D50 particle size (median size, which is the particle size showing the 50% integrated value of the integrated distribution curve) measured by dynamic light scattering, and can be measured, for example, using a MicrotracWave II-EX150 manufactured by MicrotracBell.

[0027] From the viewpoint of dispersion stability of the particles in a solvent, the particles (A) are preferably particles coated with a surface coating agent, and more preferably inorganic particles (hereinafter also referred to as "coated particles") coated with a compound having an acidic group (hereinafter also referred to as "specific coating agent"). Here, the 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 specific coating agent.

[0028] Examples of the acidic group possessed by the specific coating agent include a carboxy group, a phenolic hydroxyl group, a sulfo group, a phosphate group, and a phosphonate group. From the viewpoint of improving the dispersibility of the particles in a solvent and alkaline developability, among these, a carboxy group or a phenolic hydroxyl group is preferred, and a carboxy group is particularly preferred. In terms of excellent alkaline developability and suppression of development residues, the coated particles are preferably particles of at least one selected from the group consisting of zirconium oxide, titanium oxide, and barium titanate, the surface of which is coated with a carboxy group-containing compound, and more preferably zirconium oxide particles the surface of which is coated with a carboxy group-containing compound.

[0029] The specific coating agent may be a low molecular weight compound (i.e., a compound having no molecular weight distribution) or a polymer. The specific 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.

[0030] The monocarboxylic acid used as the specific coating agent includes a compound represented by the following formula (2): 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 atoms selected from the group consisting of oxygen atoms, sulfur atoms, and nitrogen atoms.

[0031] In the above formula (2), R ３ Examples of the monovalent hydrocarbon group having 4 or more carbon atoms represented by R include a chain hydrocarbon group, an alicyclic hydrocarbon group, and an aromatic hydrocarbon group. ３ When the monovalent hydrocarbon group represented by R 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. ３ Of these, the monovalent hydrocarbon group represented by R is preferably a chain hydrocarbon group, and more preferably an alkyl group or an alkenyl group. ３ From the viewpoint of enhancing the dispersibility of the particles (A), the number of carbon atoms in R is preferably 6 or more, more preferably 7 or more. ３ The number of carbon atoms in R is preferably 30 or less, and more preferably 20 or less. ３ is a monovalent halogenated hydrocarbon group having 4 or more carbon atoms, R ３ Examples of the halogen atom contained in include a fluorine atom and a chlorine atom.

[0032] R ３ When R is a monovalent group having one or more atoms selected from the group consisting of oxygen, sulfur, and nitrogen atoms, examples of the monovalent group include a hydrocarbon group having one or more atoms selected from the group consisting of -O-, -S-, and -NH- between the carbon-carbon bond, and a hydrocarbon group in which any hydrogen atom has been substituted with one or more atoms selected from the group consisting of a hydroxyl group, a thiol group, and an amino group. Of these, a hydrocarbon group having -O- between the carbon-carbon bond is preferred. ３ is a monovalent group having one or more atoms selected from the group consisting of oxygen atoms, sulfur atoms, and nitrogen atoms, R ３The number of carbon atoms in the group 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).

[0033] Specific examples of the compound represented by the above formula (2) include R ３ is a monovalent hydrocarbon group, examples of which 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.

[0034] R ３ is a monovalent group having one or more atoms selected from the group consisting of an oxygen atom, a sulfur atom, and a nitrogen atom, examples of the monocarboxylic acid include methoxyacetic acid, ethoxyacetic acid, 3-ethoxypropionic acid, 2-methoxyethoxyacetic acid, glyoxylic acid, pyruvic acid, hydroxybenzoic acid, thioglycolic acid, 2-[2-(2-methoxyethoxy)]ethoxyacetic acid, oxovaleric acid, asparagine, glutamine, methionine, glycolic acid, lactic acid, 2-hydroxyisobutyric acid, hydroxystearic acid, and salicylic acid.

[0035] As the carboxyl group-containing polymer, a polymer containing a structural unit having a carboxyl group can be preferably used. Specific examples of the carboxyl group-containing polymer as the specific coating agent include the same polymers as those exemplified as specific examples of the binder resin (G) described below.

[0036] As the surface coating agent, compounds other than the specific coating agent (hereinafter also referred to as "other coating agents") may be used alone or in combination with the specific 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 the unsaturated carbon-carbon bond-containing compound include silane compounds having a carbon-carbon unsaturated bond, among the compounds exemplified as the alkoxysilyl group-containing compound. In addition, compounds having a basic group can also be used as the surface coating agent.

[0037] When the specific coating agent is used in combination with other coating agents, the proportion of the other coating agents used is preferably 50% by mass or less, more preferably 40% by mass or less, based on the total amount of the surface coating agents used to coat the particles (A).

[0038] When the particles (A) are coated particles, the production method is not particularly limited and they can be produced by contacting treated particles with a surface coating agent according to a known method. In this case, the coated particles may be produced by a top-down method or a bottom-up method. Furthermore, the coated particles may be produced in a gas phase or a liquid phase. For example, the coated particles can be obtained by contacting treated particles with a surface coating agent, preferably in the presence of water. Alternatively, the treated particles and the surface coating agent may be mixed in an organic solvent, preferably in the presence of a dispersant, and then stirred using beads to obtain the coated particles. The temperature and pressure when contacting the treated particles with the surface coating agent can be appropriately set depending on the production method employed. When contacting the treated particles with the surface coating agent, the ratio of the treated particles to the surface coating agent can be, for example, 0.5 to 20 parts by mass of the surface coating agent per 100 parts by mass of the treated particles, and preferably 1 to 20 parts by mass of the surface coating agent per 100 parts by mass of the treated particles.

[0039] Furthermore, as the particles (A), titanium oxide particles whose surfaces are coated with an inorganic oxide of silicon, zinc, tin, zirconium, aluminum, or the like (inorganic oxide-coated titanium oxide particles) as described in JP-A Nos. 2013-008428 and 2009-179678 can also be suitably used.

[0040] The present composition may contain one type of the particles (A) or a combination of two or more types.

[0041] The lower limit of the content of particles (A) in the composition (total content when multiple types are contained) is preferably 10 mass%, more preferably 15 mass%, even more preferably 35 mass%, even more preferably 45 mass%, and particularly preferably 55 mass%, based on the total amount of solids contained in the composition (i.e., components other than the solvent), from the viewpoint of increasing the refractive index of the resulting cured product. Also, the upper limit of the content of particles (A) is preferably 95 mass%, more preferably 90 mass%, based on the total amount of solids contained in the composition, from the viewpoint of ensuring the stability of the dispersion.

[0042] <Radical polymerizable compound (B)> Examples of the radical polymerizable compound (B) include a monofunctional polymerizable compound (B1) and a polyfunctional polymerizable compound (B2). The radical polymerizable compound (B) is a compound that can generate a polymer by reacting multiple polymerizable compounds (B) with each other when the composition is irradiated with radiation.

[0043] As the monofunctional polymerizable compound (B1), a compound having one radical polymerizable group can be preferably used, for example, (meth)acryloyl group-containing compounds, chain vinyl compounds, aromatic vinyl compounds, maleimide compounds, etc. Specific examples of (meth)acryloyl group-containing compounds include unsaturated carboxylic acids, unsaturated carboxylic anhydrides, (meth)acrylic acid esters having a chain structure, (meth)acrylic acid esters having an alicyclic structure, (meth)acrylic acid esters having an aromatic ring structure, (meth)acrylamide compounds, chain vinyl compounds, and compounds having a phosphate group and a (meth)acryloyl group, etc. These compounds are preferably used in terms of good polymerizability and relatively high plasticity. As the monofunctional polymerizable compound (B1), a (meth)acryloyl group-containing compound can be preferably used in terms of achieving a high refractive index and transparency.

[0044] Examples of the unsaturated carboxylic acid include (meth)acrylic acid, crotonic acid, maleic acid, itaconic acid, and fumaric acid; examples of the unsaturated carboxylic acid anhydride include maleic anhydride, itaconic anhydride, and citraconic anhydride.

[0045] Examples of the (meth)acrylic acid ester having the chain structure include (meth)acrylic acid alkyl esters, (meth)acrylic acid hydroxyalkyl esters, (meth)acrylic acid alkoxyalkyl esters, (meth)acrylic acid polyoxyalkylene esters, (meth)acrylic acid alkoxypolyoxyalkylene esters, (meth)acrylic acid polyoxycarbonyl alkylene esters, (meth)acrylic acid alkoxypolyoxycarbonyl alkylene esters, and mono(meth)acryloyloxyalkyl esters of dicarboxylic acids.

[0046] Examples of the (meth)acrylic acid alkyl esters 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, and n-stearyl (meth)acrylate; examples of the (meth)acrylic acid hydroxyalkyl esters include 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 3-hydroxypropyl (meth)acrylate, and 4-hydroxybutyl (meth)acrylate; examples of the (meth)acrylic acid alkoxyalkyl esters include methoxyethyl (meth)acrylate, ethoxyethyl (meth)acrylate, and propoxyethyl (meth)acrylate; Examples of the (meth)acrylic acid polyoxyalkylene esters and (meth)acrylic acid alkoxypolyoxyalkylene esters 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), and the like; examples of the (meth)acrylic acid polyoxycarbonyl alkylene esters include ω-carboxy-polycaprolactone mono(meth)acrylate, and the like; examples of the mono(meth)acryloyloxyalkyl esters of dicarboxylic acids include mono(2-(meth)acryloyloxyethyl) succinate and mono(2-(meth)acryloyloxyethyl) phthalate.

[0047] Examples of the (meth)acrylic acid ester having an alicyclic structure include cyclohexyl (meth)acrylate, 2-methylcyclohexyl (meth)acrylate, 4-butylcyclohexyl (meth)acrylate, 4-hydroxymethylcyclohexyl (meth)acrylate, tricyclo[5.2.1.0](meth)acrylate, and 2-methylcyclohexyl (meth)acrylate. ２，６] decan-8-yl, (meth)acrylic acid tricyclo[5.2.1.0 ２，５ ] decan-8-yloxyethyl, isobornyl (meth)acrylate, and the like.

[0048] Examples of the (meth)acrylic acid ester having an 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.

[0049] Examples of the (meth)acrylamide compound include (meth)acryloylmorpholine, N-(2-hydroxyethyl)(meth)acrylamide, N-vinyl-2-pyrrolidone, and N-vinyl-ε-caprolactam.

[0050] Examples of the chain vinyl compounds include propene, butene, pentene, hexene, etc. Examples of the 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, vinylnaphthalene, etc. Examples of the maleimide compounds include N-methylmaleimide, N-cyclohexylmaleimide, N-phenylmaleimide, N-(p-methylphenyl)maleimide, etc.

[0051] Examples of the compound having a phosphate group and a (meth)acryloyl group include 2-hydroxyethyl methacrylic acid phosphate (CAS number: 52628-03-2), beta-(2-furyl)acrylamido phosphate (CAS number: 16655-99-5), bis(2-methylacryloxyethyl)phosphate (CAS number: 32435-46-4), polyethylene glycol methacrylate phosphate (CAS number: 35705-94-3), bis(2-(acryloyloxy)ethyl)phosphate (CAS number: 40074-34-8), and 10-(2-methacryloyloxy group)monodecyl phosphate (CAS number: 85590-00-7).

[0052] Further specific examples of the monofunctional polymerizable compound (B1) include compounds represented by the following formulae (b1-1) to (b1-28). (In formulas (b1-1) to (b1-28), R ２０ is a hydrogen atom or a methyl group. ２１ is a monovalent hydrocarbon group having 1 to 20 carbon atoms, and n is an integer from 0 to 10.

[0053] As the polyfunctional polymerizable compound (B2), a compound having two or more radically polymerizable groups can be preferably used, and examples thereof include a polyfunctional (meth)acryloyl group-containing compound, a polyfunctional aromatic vinyl compound, and a polyfunctional chain vinyl compound.

[0054] Specific examples of the polyfunctional (meth)acryloyl group-containing compound include bifunctional (meth)acrylic acid esters and trifunctional or higher functional (meth)acrylic acid esters. Specific examples of these include bifunctional (meth)acrylic acid esters such as 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, and tetraethylene glycol di(meth)acrylate.

[0055] Examples of trifunctional or higher functional (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, and carboxy group-containing polybasic acid-modified (meth)acrylic oligomers, as well as polyfunctional urethane acrylate compounds obtained by reacting a compound having a linear alkylene group and an alicyclic structure and having two or more isocyanate groups with a compound having one or more hydroxy groups in the molecule and three, four, or five (meth)acryloyloxy groups.

[0056] Examples of the polyfunctional aromatic vinyl compounds include 1,3-divinylbenzene, 1,4-divinylbenzene, etc. Examples of the polyfunctional chain vinyl compounds include 1,5-hexadiene, 1,6-heptadiene, 1,7-octadiene, etc.

[0057] Further specific examples of the polyfunctional polymerizable compound (B2) include compounds represented by the following formulas (b2-29) to (b2-53). (In formulas (b2-29) to (b2-53), R ２０ is a hydrogen atom or a methyl group. m and n are each independently an integer of 0 to 10. x, y, and z are each independently an integer of 0 to 3, provided that 1≦x+y+z≦3 is satisfied.

[0058] As the polyfunctional polymerizable compound (B2), from the viewpoints of increasing the refractive index and transparency, among the above, a (meth)acryloyl group-containing compound can be preferably used.

[0059] The radical polymerizable compound (B) may also be a polymerizable compound (B3) having both a radical polymerizable group and a cationically polymerizable group, and is preferably used in combination with the monofunctional polymerizable compound (B1) or the polyfunctional polymerizable compound (B2). Examples of the cationically polymerizable group include an epoxy group, an oxetanyl group, and a vinyl ether group.

[0060] The polymerizable compound (B3) having both a radical polymerizable group and a cationically polymerizable group is preferably a compound having a vinyl group or a (meth)acryloyl group as the radical polymerizable group and an epoxy group or an oxetanyl group as the cationically polymerizable group. Examples of the polymerizable compound (B3) include glycidyl (meth)acrylate, 3,4-epoxycyclohexyl (meth)acrylate, 3,4-epoxycyclohexylmethyl (meth)acrylate, 2-(3,4-epoxycyclohexyl)ethyl (meth)acrylate, 3,4-epoxytricyclo[5.2.1.0] ２，６] decyl (meth)acrylate, 2-hydroxyethyl methacrylate [3,4-epoxytricyclo(5.2.1.0 ２，６ ) decan-9-yl], methacrylic acid [3,4-epoxytricyclo(5.2.1.0 ２，６ ) decan-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-vinylbenzyl glycidyl ether, m-vinylbenzyl glycidyl ether, p-vinylbenzyl glycidyl ether, 3-[(4-vinylbenzyl)oxymethyl]-3-ethyloxetane, and the like, with 3-[(4-vinylbenzyl)oxymethyl]-3-ethyloxetane being preferred.

[0061] The present composition may contain one or a combination of two or more of the radical polymerizable compounds (B).

[0062] 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, based on the total amount of the monofunctional polymerizable compound (B1) and the polyfunctional polymerizable compound (B2). The content of the monofunctional polymerizable compound (B1) is preferably 100% by mass or less, more preferably 90% by mass or less, more preferably 80% by mass or less, and even more preferably 70% by mass or less, based on the total amount of the monofunctional polymerizable compound (B1) and the polyfunctional polymerizable compound (B2).

[0063] Furthermore, when the radical polymerizable compound (B) contains the polymerizable compound (B3), the content thereof in the radical polymerizable compound (B) is preferably 50 mass% or less, and more preferably 30 mass% or less.

[0064] The lower limit of the content of the radical polymerizable compound (B) in the composition (the total content when multiple types of the polymerizable compounds (B1) to (B3) are included) is preferably 5 parts by mass, more preferably 10 parts by mass, and even more preferably 20 parts by mass, relative to 100 parts by mass of the particles (A). The upper limit of the content of the radical polymerizable compound (B) is preferably 350 parts by mass, more preferably 200 parts by mass, even more preferably 100 parts by mass, even more preferably 50 parts by mass, even more preferably 45 parts by mass, and particularly preferably 35 parts by mass, relative to 100 parts by mass of the particles (A). By ensuring that the content of the radical polymerizable compound (B) in the composition falls within the above range, the refractive index can be increased, the sensitivity of the composition can be improved, and a cured product having good heat resistance and chemical resistance can be obtained.

[0065] <Cationically polymerizable compound (B4) having no radically polymerizable group but having a cationically polymerizable group> In the present invention, a cationically polymerizable compound (B4) having no radically polymerizable group but having a cationically polymerizable group can be used. As the cationically polymerizable compound (B4), a compound having an epoxy group (oxiranyl group) or a compound having an oxetanyl group (oxetane compound) is preferred. The cationically polymerizable compound (B4) may have one or more cationically polymerizable groups, and preferably has 1 to 3 cationically polymerizable groups.

[0066] Examples of the compound having an epoxy group include an alicyclic compound having an epoxy group (alicyclic epoxy compound), an aromatic compound having an epoxy group (aromatic epoxy compound), and an acyclic compound having an epoxy group (acyclic epoxy compound), and alicyclic epoxy compounds are preferred. Examples of the alicyclic epoxy compound include 3',4'-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate, 3,4-epoxycyclohexylalkyl(meth)acrylate (e.g., 3,4-epoxycyclohexylmethyl(meth)acrylate), (3,3',4,4'-diepoxy)bicyclohexyl, hydrogenated bisphenol A epoxy resin, and hydrogenated bisphenol F epoxy resin.

[0067] Examples of the oxetane compound include 3-ethyl-3-hydroxymethyloxetane (trade name Aron Oxetane OXT-101, manufactured by Toagosei Co., Ltd.), 1,4-bis[(3-ethyl-3-oxetanyl)methoxymethyl]benzene (OXT-121, manufactured by Toagosei Co., Ltd.), 3-ethyl-3-(phenoxymethyl)oxetane (OXT-211, manufactured by Toagosei Co., Ltd.), di(1-ethyl-(3-oxetanyl))methyl ether (OXT-221, manufactured by Toagosei Co., Ltd.), and 3-ethyl-3-(2-ethylhexyloxymethyl)oxetane (OXT-212, manufactured by Toagosei Co., Ltd.).

[0068] Compounds having both an epoxy group and an oxetanyl group can also be used, such as 3-ethyl-3-(2,3-epoxypropoxymethyl)oxetane.

[0069] When the composition contains the cationically polymerizable compound (B4), the lower limit of the content of the cationically polymerizable compound (B4) (the total content when multiple types are contained) is preferably 5 parts by mass, more preferably 10 parts by mass, and even more preferably 20 parts by mass, relative to 100 parts by mass of the particles (A). The upper limit of the content of the cationically polymerizable compound (B4) is preferably 100 parts by mass, more preferably 80 parts by mass, and even more preferably 60 parts by mass, relative to 100 parts by mass of the particles (A). By setting the content of the cationically polymerizable compound (B4) in the composition within the above range, the refractive index can be increased, the sensitivity of the composition can be improved, and a cured product having good heat resistance and chemical resistance can be obtained.

[0070] As the radical polymerizable compound (B), the polymerizable compounds (B1) to (B4) can be used in appropriate combination. Among these, polymerizable compounds having an alkylene oxide chain such as an ethylene oxide chain or a propylene oxide chain, and polymerizable compounds having an acidic group are preferred from the viewpoints of bending resistance and dispersibility.

[0071] <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 radically polymerizable compound (B) can be preferably used. The photopolymerization initiator to be used is not particularly limited, but examples thereof include O-acyloxime compounds, acetophenone compounds, biimidazole compounds, and acylphosphine oxide compounds.

[0072] Examples of O-acyloxime compounds include 1,2-octanedione 1-[4-(phenylthio)-2-(O-benzoyloxime)], ethanone-1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]-1-(O-acetyloxime), 1-(9-ethyl-6-benzoyl-9H-carbazol-3-yl)-octan-1-one oxime-O-acetate, 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]-ethan-1-one oxime-O-benzoate, 1-[9-n-butyl-6-(2-ethylbenzoyl)-9H- -carbazol-3-yl]-ethan-1-one oxime-O-benzoate, ethanone-1-[9-ethyl-6-(2-methyl-4-tetrahydrofuranylbenzoyl)-9.H.-carbazol-3-yl]-1-(O-acetyloxime), ethanone-1-[9-ethyl-6-(2-methyl-4-tetrahydropyranylbenzoyl)-9.H.-carbazol-3-yl]-1-(O-acetyloxime), ethanone-1-[9-ethyl-6-(2-methyl-5-tetrahydrofuranylbenzoyl)-9.H.-carbazol-3-yl]-1-(O-acetyloxime), ethanone-1-[9-ethyl-6-{2-methyl-4-(2,2-dimethyl-1,3-dioxolanyl)methoxybenzoyl}-9.H. -carbazol-3-yl]-1-(O-acetyloxime), etc. Commercially available products include, for example, ADEKA ARCLES N-1919T, NCI-831E, NCI-930, and NCI-730 (all manufactured by ADEKA Corporation), and IRGACURE OXE01, OXE2, OXE3, and OXE4 (all manufactured by BASF).

[0073] 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-yl-phenyl)-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. Commercially available products include Irgacure 369, 369E, 379EG, 651, 184, and 907 (all manufactured by BASF).

[0074] Examples of the biimidazole compound 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, and 2,2'-bis(2,4,6-trichlorophenyl)-4,4',5,5'-tetraphenyl-1,2'-biimidazole.

[0075] Examples of the acylphosphine oxide compound include 2,4,6-trimethylbenzoyl-diphenylphosphine oxide and phenylbis(2,4,6-trimethylbenzoyl)phosphine oxide.

[0076] The present composition may contain one or a combination of two or more of the above photoradical generators (C).

[0077] The lower limit of the content of the photoradical generator (C) in the composition (the total content when multiple types are contained) is preferably 0.5 parts by mass, more preferably 1 part by mass, relative to 100 parts by mass of the particles (A) contained in the 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, relative to 100 parts by mass of the particles (A) contained in the 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.

[0078] <Dehydrating Agent (D)> The composition (1) contains a dehydrating agent (D), and the dehydrating agent (D) includes an orthoester compound. The orthoester compound is a compound having three groups "-OR １ ” (However, R １ is a monovalent hydrocarbon group) bonded to the same carbon atom, and is a compound represented by the general formula: R ２ -C(OR １ ) ３ where R ２ is a hydrogen atom or a monovalent organic group. The orthoester compound is hydrolyzed to an ester. By incorporating such an orthoester compound into the photosensitive composition, the water absorption action of the orthoester compound can improve the long-term coatability and storage stability of the photosensitive composition. In addition, orthoester compounds are preferred in that they are stable and hydrophobic in alkaline developers and have little effect on exposed areas (e.g., on sensitivity).

[0079] The group "-OR" contained in the orthoester compound １ Examples of the group "-OR" include a methoxy group, an ethoxy group, an n-propoxy group, an i-propoxy group, an n-butoxy group, an i-butoxy group, a tert-butoxy group, an n-pentoxy group, a phenoxy group, and a methylphenyloxy group. １ " is preferably an alkoxy group, more preferably an alkoxy group having 1 to 4 carbon atoms. １" are the same or different groups.

[0080] R ２ Examples of R include a hydrogen atom, a monovalent chain hydrocarbon group, a halogenated chain hydrocarbon group in which at least one hydrogen atom of the chain hydrocarbon group is substituted with a halogen atom, and a monovalent aromatic ring group. ２ is preferably a hydrogen atom, a monovalent chain hydrocarbon group, or a monovalent aromatic ring group, and specific examples thereof include a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an alkenyl group having 2 to 20 carbon atoms, and an aryl group having 6 to 20 carbon atoms.

[0081] Among the above orthoester compounds, compounds represented by the following formula (1) can be preferably used: ２１ -C-(OR １１ ) ３ ...(1) (In formula (1), R １１ is an alkyl group having 1 to 4 carbon atoms or a phenyl group, and R ２１ is a hydrogen atom, a monovalent chain hydrocarbon group having 1 to 4 carbon atoms, or a monovalent aromatic ring group having 6 to 12 carbon atoms. １１ are the same or different.)

[0082] In the above formula (1), R １１ The alkyl group of R may be linear or branched. １１ is preferably a methyl group, an ethyl group or a phenyl group, more preferably a methyl group or an ethyl group.

[0083] R ２１ The chain hydrocarbon group R is preferably a chain or branched alkyl group having 1 to 4 carbon atoms. ２１ Examples of the aromatic ring group of R include a phenyl group, a methylphenyl group, a dimethylphenyl group, an ethylphenyl group, and a naphthyl group. In addition, the chain hydrocarbon group or aromatic ring group may have at least one hydrogen atom substituted with a halogen atom. ２１ is preferably a monovalent aromatic ring group, and particularly preferably a phenyl group, in that it is highly effective in improving the coating properties over time and the storage stability.

[0084] Specific examples of the orthoester compound include triethyl orthochloroacetate, trimethyl orthoformate, triethyl orthoformate, tripropyl orthoformate, triisopropyl orthoformate, tributyl orthoformate, diethylphenyl orthoformate, trimethyl orthoacetate, triethyl orthoacetate, triethyl orthodichloroacetate, trimethyl orthobutyrate, triethyl orthobutyrate, trimethyl orthopropionate, triethyl orthopropionate, trimethyl orthovalerate, triethyl orthovalerate, trimethyl orthoisobutyrate, orthoisobutyrate, Among these, one or more selected from the group consisting of methyl orthoacetate, triethyl orthoacetate, trimethyl orthobenzoate, and triethyl orthobenzoate are preferred, one or more selected from the group consisting of triethyl orthoacetate, trimethyl orthobenzoate, and triethyl orthobenzoate are more preferred, and one or more selected from the group consisting of trimethyl orthobenzoate and triethyl orthobenzoate are even more preferred.

[0085] As the orthoester compound, a compound having an aromatic ring group can be preferably used from the viewpoint of long-term coating property and storage stability. Specific examples of the compound having an aromatic ring group include those represented by the above formula (1) where R １１ and R ２１ In particular, compounds in which at least one group is an aromatic ring-containing group are exemplified.

[0086] Specific examples of orthoester compounds having an aromatic ring group include trimethyl orthobenzoate, triethyl orthobenzoate, diethylphenyl orthoformate, etc. Among these, trimethyl orthobenzoate and triethyl orthobenzoate are particularly preferred because of their high effect of improving coating properties over time and storage stability.

[0087] The boiling point of the orthoester compound is not particularly limited, but is preferably 105° C. or higher at 1 atmosphere, more preferably 110° C. or higher, and even more preferably 115° C. or higher. Note that when the boiling point of the orthoester compound is high, even if the photosensitive composition is allowed to remain in a coating device or the like for a certain period of time, the orthoester compound can be prevented from volatilizing during that period, and the effect of incorporating the orthoester compound can be maintained, which is preferable.

[0088] Specific examples of orthoester compounds having a boiling point of 105°C or higher at 1 atmosphere include triethyl orthoformate (boiling point 145°C), tripropyl orthoformate (boiling point 198°C), tributyl orthoformate (boiling point 247°C), trimethyl orthoacetate (boiling point 108°C), triethyl orthoacetate (boiling point 145°C), triethyl orthodichloroacetate (boiling point 195°C), trimethyl orthobutyrate (boiling point 146°C), trimethyl orthopropionate (boiling point 128°C), triethyl orthopropionate (boiling point 158°C), trimethyl orthovalerate (boiling point 164°C), trimethyl orthobenzoate (boiling point 115°C), and triethyl orthobenzoate (boiling point 240°C). Of these, trimethyl orthobenzoate (boiling point 115°C / 3.3 kPa) and triethyl orthobenzoate (boiling point 240°C) are preferred. In this specification, the boiling point is a value at 1 atmosphere.

[0089] The dehydrating agent (D) may contain one or a combination of two or more of the above-mentioned orthoester compounds, or may contain a known dehydrating agent other than an orthoester compound, but preferably consists solely of an orthoester compound.

[0090] The lower limit of the content of the dehydrating agent (D) in the composition is preferably 1 part by mass, more preferably 3 parts by mass, and even more preferably 5 parts by mass, relative to 100 parts by mass of the particles (A) contained in the composition. The upper limit of the content of the dehydrating agent (D) is preferably 40 parts by mass, more preferably 30 parts by mass, and even more preferably 25 parts by mass, relative to 100 parts by mass of the particles (A) contained in the composition. By setting the content of the dehydrating agent (D) within the above range, a photosensitive composition having excellent long-term coatability and storage stability can be obtained, which is preferable.

[0091] The present composition (1) may contain components other than the particles (A), radical polymerizable compound (B), photoradical generator (C), and dehydrating agent (D). Examples of these other components include a photoacid generator (E), a solvent (F), a binder resin (G), a surfactant (H), and an adhesion aid (I). The present composition (2) may contain components other than the particles (A), radical polymerizable compound (B), and photoradical generator (C). Examples of these other components include the dehydrating agent (D), photoacid generator (E), a solvent (F), a binder resin (G), a surfactant (H), an adhesion aid (I), and a sensitizer (J).

[0092] <Photoacid Generator (E)> The photoacid generator (E) refers to a compound that generates an acid upon irradiation with light or other radiation. Examples of radiation include ultraviolet light, far ultraviolet light, X-rays, and charged particle beams. The generation of this acid can initiate cationic polymerization of a cationically polymerizable compound. Therefore, when the radical polymerizable compound (B) contains a polymerizable compound (B3), it is preferable that the radical polymerizable compound (B) contains a photoacid generator (E).

[0093] Examples of the photoacid generator (E) include oxime sulfonate compounds, sulfonimide compounds, halogen-containing compounds, diazomethane compounds, sulfone compounds, sulfonate ester compounds, carboxylate ester compounds, and onium salts. Specific examples of these compounds include those described in JP-A-2020-026515. Among these, onium salts are preferred.

[0094] Examples of the onium salt include diphenyliodonium salt, triphenylsulfonium salt, sulfonium salt, benzothiazonium salt, and tetrahydrothiophenium salt. Examples of the diphenyliodonium salt include diphenyliodonium tetrafluoroborate and 4-isobutylphenyl-4'-tolyliodohexafluorophosphate. Examples of the triphenylsulfonium salt include triphenylsulfonium trifluoromethanesulfonate, triphenylsulfonium hexafluoroantimonate, triphenylsulfonium hexafluorophosphate, triphenylsulfonium tetrakis(pentafluorophenyl)borate, and diphenyl[4-(phenylthio)phenyl]sulfonium hexafluorophosphate. Among these, triphenylsulfonium hexafluoroantimonate and diphenyl[4-(phenylthio)phenyl]sulfonium hexafluorophosphate are preferred.

[0095] The present composition may contain one or more of the above photoacid generators (E) in combination.

[0096] When the composition contains a photoacid generator (E), the lower limit of the content of the photoacid generator (E) (the total content when multiple types are contained) is preferably 0.1 parts by mass, more preferably 0.2 parts by mass, even more preferably 0.5 parts by mass, and even more preferably 1 part by mass, relative to 100 parts by mass of the particles (A) contained in the composition. The upper limit of the content of the photoacid generator (E) is preferably 10 parts by mass, more preferably 5 parts by mass, relative to 100 parts by mass of the particles (A) contained in the composition. By setting the content of the photoacid generator (E) within the above range, a photosensitive composition exhibiting good curability can be obtained.

[0097] When a photoacid generator (E) is used in the present composition, the above-mentioned polymerizable compound (B3), adhesion aids (I) having a cationically polymerizable group such as an oxiranyl group or an oxetanyl group, and polymerizable compound (B4) can be used. Furthermore, when a photoacid generator (E) is used in the present composition, a sensitizer (J) can be used to improve sensitivity.

[0098] <Solvent (F)> The present composition is preferably a liquid composition in which the particles (A), the radical polymerizable compound (B), the photoradical generator (C), the dehydrating agent (D), and other components blended as necessary are dissolved or dispersed in a solvent. As the solvent (F), an organic solvent that dissolves the particles (A), the radical polymerizable compound (B), the photoradical generator (C), and the dehydrating agent (D) and does not react with the other components is preferred.

[0099] Specific examples of the solvent (F) include 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, dimethylene 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.

[0100] From the viewpoint of long-term coating properties, the solvent (F) preferably contains a solvent having a high boiling point (for example, 160° C. or higher).

[0101] <Binder Resin (G)> The binder resin (G) is preferably a polymer having an acidic group. Examples of the acidic group include a carboxy group, a phenolic hydroxyl group, and a fluorinated hydroxyalkyl group. The binder resin is preferably an alkali-soluble resin. Here, "alkali-soluble" refers to a polymer that can be dissolved or swelled in a 2.38% by mass aqueous solution of tetramethylammonium hydroxide (TMAH) at 25°C. The fluorinated hydroalkyl group refers to a group in which any hydrogen atom bonded to a carbon in a hydroxyalkyl group is substituted with a fluorine atom.

[0102] As the binder resin (G), a polymer having an ethylenically unsaturated monomer as a constituent unit can be preferably used. Examples of the ethylenically unsaturated monomer constituting the polymer include the same compounds as those exemplified as the monofunctional polymerizable compound (B1), and preferably contain a carboxyl group-containing compound. In this case, the binder resin (G) preferably contains structural units derived from the carboxyl group-containing compound in an amount of 5% by mass or more, more preferably 10% by mass or more, and even more preferably 20% by mass or more, based on the total structural units constituting the binder resin (G).

[0103] When the binder resin (G) is a polymer containing an ethylenically unsaturated monomer as a constituent unit, the polymer can be produced, for example, by a known method such as radical polymerization using the above-mentioned ethylenically unsaturated monomer in an appropriate solvent in the presence of a polymerization initiator. Examples of the polymerization initiator include azo compounds such as 2,2'-azobis(isobutyronitrile), 2,2'-azobis(2,4-dimethylvaleronitrile), and 2,2'-azobis(isobutyrate)dimethyl. The proportion of the 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 the polymerization solvent include alcohols, ethers, ketones, esters, and hydrocarbons, and specific examples include those listed above for the solvent (F). The amount of the polymerization solvent used is preferably such that the total amount of the monomers used in the reaction is 0.1 to 60% by mass relative to the total amount of the reaction solution. In the polymerization, the reaction temperature is usually 30° C. to 180° C. The reaction time varies depending on the types of polymerization initiator and monomer and the reaction temperature, but is usually 0.5 to 10 hours.

[0104] Examples of the binder resin (G) include polymers containing ethylenically unsaturated monomers as structural units, as well as phenolic hydroxyl group-containing polymers such as novolak resins, phenol-xylylene glycol condensation resins, cresol-xylylene glycol condensation resins, and phenol-dicyclopentadiene condensation resins. Furthermore, alkali-soluble polyorganosiloxanes, alkali-soluble polyimides, alkali-soluble polybenzoxazoles, and the like may also be used as the binder resin (G). Specific examples of alkali-soluble polyorganosiloxanes include the polymers described in WO 2017 / 188047 and WO 2017 / 169763. Specific examples of alkali-soluble polyimides and polybenzoxazoles include the polymers described in WO 2017 / 169763 and WO 2017 / 159876.

[0105] By including a binder resin (G) in the present composition, alkaline developability can be improved, but the surface smoothness of the resulting cured product tends to decrease. Therefore, the presence or absence of the binder resin (G) and the amount of the binder resin (G) to be included can be determined depending on the intended use of the resulting cured product. Specifically, in applications where the resulting cured product requires surface smoothness, it is preferable not to use the binder resin (G), and in applications where improved alkaline developability is required, it is preferable to use the binder resin (G).

[0106] The present composition may contain one or more of the above binder resins (G).

[0107] When the present composition contains a binder resin (G), the content ratio of the binder resin (G) (the total content ratio when multiple types of binder resins (G) are contained) 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 the particles (A) contained in the present composition.

[0108] <Surfactant (H)> The surfactant (H) can be used to improve the coatability of the composition (i.e., to improve wetting and spreading properties and reduce coating unevenness). Examples of the surfactant (H) include fluorine-based surfactants, silicone-based surfactants, and nonionic surfactants.

[0109] Specific examples of the surfactant (H) include fluorine-based surfactants, such as Megafac F-171, F-172, F-173, F-251, F-430, F-554, and F-563 (manufactured by DIC Corporation); Fluorad FC430 and FC431 (manufactured by Sumitomo 3M Limited); Asahiguard AG710, Surflon S-382, SC-101, SC-102, SC-103, SC-104, SC-105, SC-106, and S-611 (manufactured by AGC Seimi Chemical Co., Ltd.); and Polyflow No. 75 and No. 95 (manufactured by Kyoeisha Chemical Co., Ltd.); FTX-218 (manufactured by Neos Co., Ltd.); F-Top EF301, EF303, and EF352 (manufactured by Shin-Akita Kasei Co., Ltd.).

[0110] Examples of silicone surfactants include the following trade 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, and L-700. 1, L-7002 (manufactured by Toray Dow Corning Silicone Co., Ltd.); organosiloxane polymer KP341 (manufactured by Shin-Etsu Chemical Co., Ltd.); BYK-300, 306, 310, 313, 320, 330, 331, 335, 341, 344, 370, 340, and 345 (manufactured by BYK Japan KK).

[0111] 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.

[0112] The present composition may contain one or more of the surfactants (H) described above.

[0113] When a surfactant (H) is blended in the present composition, the content of the surfactant (H) (the total content when multiple types are included) relative to 100 parts by mass of the particles (A) contained in the present composition 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, even more 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.

[0114] <Adhesion Aid (I)> The adhesion aid (I) is a component that improves the adhesion between the obtained cured film and the substrate. As the adhesion aid (I), a functional silane coupling agent having a reactive functional group such as a carboxy group, a methacryloyl group, a vinyl group, an isocyanate group, or an oxiranyl group is preferred.

[0115] Examples of the functional silane coupling agent include trimethoxysilylbenzoic acid, γ-methacryloxypropyltrimethoxysilane, vinyltriacetoxysilane, vinyltrimethoxysilane, γ-isocyanatopropyltriethoxysilane, γ-glycidoxypropyltrimethoxysilane, β-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, and β-(3,4-epoxycyclohexyl)ethyltriethoxysilane.

[0116] The present composition may contain one or a combination of two or more of the adhesion aids (I).

[0117] When the present composition contains an adhesion aid (I), the content ratio of the adhesion aid (I) (the total content ratio when multiple types of adhesion aids (I) are contained) relative to 100 parts by mass of the particles (A) contained in the present composition is preferably 1 part by mass or more and 60 parts by mass or less, more preferably 1 part by mass or more and 50 parts by mass or less, even more preferably 1 part by mass or more and 35 parts by mass or less, still more preferably 1 part by mass or more and 15 parts by mass or less, and particularly preferably 3 parts by mass or more and 10 parts by mass or less.

[0118] <Sensitizer (J)> In the present invention, a sensitizer 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-dimethylaminoethyl benzoate, 2-ethylhexyl 4-dimethylaminobenzoate, 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 sensitizer include 9,10-dimethoxyanthracene, 9,10-dibutoxyanthracene, 2-ethyl-9,10-dimethoxyanthracene, 9,10-diethoxyanthracene, and 2-ethyl-9,10-diethoxyanthracene.

[0119] When the present composition contains a sensitizer (J), the content of the sensitizer (J) (the total content when multiple types of sensitizers (J) are contained) 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 still more preferably 0.05 parts by mass or more and 3 parts by mass or less, relative to 100 parts by mass of the particles (A) contained in the present composition.

[0120] In addition to the above, other components include, for example, a polymerization inhibitor, an antioxidant, a softener, a plasticizer, an ultraviolet absorber, etc. The blending ratio of these components is appropriately selected depending on each component within a range that does not impair the effects of the present disclosure.

[0121] The present composition (1) can be obtained by mixing the above-mentioned particles (A), radical polymerizable compound (B), photoradical generator (C), dehydrating agent (D), and other components that are optionally blended, in a predetermined ratio, and the present composition (2) can be obtained by mixing the above-mentioned particles (A), radical polymerizable compound (B), photoradical generator (C), and other components that are optionally blended, in a predetermined ratio. The composition obtained by mixing the respective components may be filtered, for example, with a filter having a pore size of 0.5 μm or less.

[0122] The solids concentration of the 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 taking into consideration viscosity, volatility, and the like. The solids concentration of the composition is preferably in the range of 3 to 60 mass%. A solids concentration of 3 mass% or more is preferred in that a sufficient coating thickness can be ensured when the composition is applied to a substrate. Furthermore, a solids concentration of 60 mass% or less is preferred in that the coating thickness does not become too large, and furthermore, the viscosity of the composition can be appropriately increased, ensuring good coatability. The solids concentration of the composition is more preferably 5 to 55 mass%, and even more preferably 10 to 50 mass%.

[0123] The water content of the present composition (2) is less than 2000 ppm, preferably 1500 ppm or less, more preferably 1200 ppm or less, and even more preferably 1000 ppm or less. When the water content is within the above range, stable coating properties can be obtained. The water content in the composition can be measured by the method described in the Examples. Furthermore, the water content of the present composition (1) is preferably within the above range.

[0124] <<Method for Producing a Cured Product>> A cured product can be produced by using the photosensitive composition prepared as described above. This composition is particularly suitable as a negative pattern-forming material in which a pattern (i.e., the portion formed by the photosensitive composition) is obtained by exposing a portion of a film formed by the photosensitive composition to light and dissolving the unexposed portion in an alkaline developer, and then curing the pattern by heat treatment.

[0125] The cured product of the present disclosure is produced, for example, by a method including the following steps (I) to (IV): (I) a step of applying the present composition onto a substrate; (II) a step of irradiating the present composition applied onto the substrate with radiation; (III) a step of developing the present composition after irradiation; and (IV) a step of heating the present composition after development at a temperature of 100°C or less to cure it. Each step (steps (I) to (IV)) in the production method of the present disclosure will be described below.

[0126] <Step (I): Coating Step> Step (I) is a step of forming a coating film on a substrate by coating the present composition on the substrate. Examples of the substrate include glass substrates, silicon wafers, plastic substrates, plastic films, and substrates having colored resists, overcoats, anti-reflection films, various metal thin films, sealing films, etc. formed on their surfaces. 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. These substrates may be previously provided with various elements (for example, light-receiving elements such as photodiodes, and light-emitting elements such as organic light-emitting diodes).

[0127] The composition can be applied by any suitable method, such as spraying, roll coating, rotary coating (spin coating), slit die coating, bar coating, ink jetting, etc. Of these, spin coating, bar coating, and slit die coating are preferred.

[0128] After the composition is applied to a substrate, the composition may be preheated (prebaked) for the purpose of preventing dripping, etc. The prebaking conditions can be appropriately set depending on the type and use ratio of each component. The prebaking conditions can be, for example, 60 to 100°C for about 30 seconds to 10 minutes. From the viewpoint of applicability to organic EL devices, the prebaking temperature is preferably 60 to 90°C. The thickness of the coating film formed after prebaking is preferably 0.1 to 20 μm, more preferably 0.2 to 15 μm.

[0129] <Step (II): Exposure Step> Step (II) is a step of irradiating at least a portion of the coating film formed in step (I) with radiation. This radiation exposure causes a curing reaction to proceed in the exposed area. In step (II), the radiation exposure to 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.

[0130] Examples of radiation to be irradiated onto the coating film include ultraviolet rays, far ultraviolet rays, X-rays, charged particle rays, etc. Examples of ultraviolet rays include g-rays (wavelength 436 nm), i-rays (wavelength 365 nm), KrF excimer laser light (wavelength 248 nm), etc. Examples of X-rays include synchrotron radiation, etc. Examples of charged particle rays include electron beams, etc. Among these, ultraviolet rays are preferred as the radiation to be irradiated onto the coating film, and ultraviolet rays with a wavelength of 200 nm or more and 380 nm or less are more preferred. Examples of light sources to be used include low-pressure mercury lamps, high-pressure mercury lamps, deuterium lamps, metal halide lamps, argon resonance lamps, xenon lamps, excimer lasers, etc. The radiation exposure dose is 500 J / m ２ ~5,000 J / m ２ (50~500mJ / cm２ ) is preferred.

[0131] <Step (III): Development Step> Step (III) is a step of forming a pattern on the substrate by developing the coating film irradiated with radiation in step (II). This development step removes unexposed areas of the coating film formed on the substrate, allowing a pattern consisting of exposed areas to be formed on the substrate.

[0132] Examples of the developer 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, an aqueous solution obtained by adding an appropriate amount of a water-soluble organic solvent such as methanol or ethanol or a surfactant to an aqueous alkali solution, or by adding a small amount of various organic solvents capable of dissolving the present composition, may be used as the developer.

[0133] As the developing method, for example, a suitable method such as a puddle method, a dipping method, a swing immersion method, a shower method, etc. can be used. The developing time may be adjusted appropriately depending on the composition of the present composition. The developing time is, for example, 20 to 120 seconds.

[0134] <Step (IV): Heating Step> Step (IV) is a step of heating the developed pattern at 100°C or less. The heat treatment in step (IV) further promotes curing, and a cured product exhibiting good heat resistance and chemical resistance can be obtained. The heat treatment can be performed using a heating device such as an oven or a hot plate. When obtaining microlenses as the cured product, hemispherical microlenses may be obtained by thermally flowing the developed pattern through the heat treatment in step (IV).

[0135] 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 devices. 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 appropriately set 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. Furthermore, 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 heating treatment is performed multiple times may be used.

[0136] 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 a "post-exposure step"). Irradiation with radiation in the post-exposure step (hereinafter also referred to as "post-exposure") can further improve heat resistance, chemical resistance, etc., and produce a cured product with higher reliability. The type of radiation and exposure conditions in the post-exposure can be the same as those in step (II). The conditions for the post-exposure, such as the wavelength and dose of irradiation light and the light source, may be the same as or different from those in step (II).

[0137] <<Cured Film>> The cured film of the present invention can be formed by curing the photosensitive composition. This composition can provide a cured product with a high refractive index, specifically, a cured product with a refractive index of 1.60 or more at a wavelength of 550 nm. This composition can also provide a cured film with a high refractive index, preferably 1.68 or more, more preferably 1.70 or more at a wavelength of 550 nm.

[0138] The present composition has high solubility in an alkaline developer and excellent storage stability and long-term application properties. Therefore, by subjecting the composition to exposure treatment and development treatment, a cured product having a desired pattern shape can be obtained, and the same cured product can be obtained even after a certain period of time has passed.

[0139] The cured film is suitable as an optical component for a display device or an imaging device. The optical component is preferably a component for improving the light extraction efficiency of a display device (a component for adjusting the path of light) or a component for adjusting the path of light to focus it on a light-receiving element (photodiode) included in an imaging device such as a camera.

[0140] <Display element> The display element of the present invention includes a cured film formed from the photosensitive composition. Examples of the display element include a liquid crystal display element, an organic EL display element, and a micro LED (Light Emitting Diode) display element.

[0141] The imaging element of the present invention includes a cured film formed from the photosensitive composition described above. The cured film of the present invention is preferably used as an optical path adjusting member that adjusts the path of light to focus it on a light receiving element (photodiode) included in the imaging element of a camera or the like.

[0142] The present invention will be described in more detail below with reference to examples, but the present invention is not limited to these examples. In the examples and comparative examples, "parts" and "%" are by mass unless otherwise specified. In these examples, the weight average molecular weight (Mw) of the polymer (binder resin) was measured by the following method.

[0143] [Weight-average molecular weight (Mw)] The Mw of a polymer (binder resin) is a polystyrene-equivalent value measured by the following method and conditions: Measurement method: gel permeation chromatography (GPC) method Apparatus: GPC-101 manufactured by Showa Denko K.K. GPC column: GPC-KF-801, GPC-KF-802, GPC-KF-803, and GPC-KF-804 manufactured by Shimadzu GLC Corporation combined together Mobile phase: tetrahydrofuran Column temperature: 40°C Flow rate: 1.0 mL / min Sample concentration: 1.0 mass% Sample injection amount: 100 μL Detector: differential refractometer Standard material: monodisperse polystyrene

[0144] [Average Particle Diameter] The average particle diameter of the particles is the D50 particle diameter (median diameter, which is the particle diameter showing the 50% integrated value of the integrated distribution curve) measured by dynamic light scattering, and was measured using MicrotracWave II-EX150 manufactured by MicrotracBell.

[0145] Synthesis of Binder Resin (G-1) [Synthesis Example 1] A flask equipped with a condenser and a stirrer was charged with 100 parts by weight of propylene glycol monomethyl ether acetate and purged with nitrogen. The flask was heated to 80°C, and a mixed solution of 100 parts by weight of propylene glycol monomethyl ether acetate, 15 parts by weight of methacrylic acid, 15 parts by weight of styrene, 5 parts by weight of benzyl methacrylate, 15 parts by weight of 2-hydroxyethyl methacrylate, 23 parts by weight of 2-ethylhexyl methacrylate, 12 parts by weight of N-phenylmaleimide, 15 parts by weight of mono(2-acryloyloxyethyl) succinate, and 6 parts by weight of 2,2'-azobis(2,4-dimethylvaleronitrile) was added dropwise over 1 hour at the same temperature. This temperature was maintained and polymerization was carried out for 2 hours. Thereafter, the temperature of the reaction solution was raised to 100°C, and polymerization was carried out for another 1 hour to obtain a binder resin solution (solids concentration: 33% by weight). The resulting binder resin solution had an Mw of 12,200. This binder resin solution is referred to as "binder resin (G-1)."

[0146] <Preparation of Particle Dispersion> [Preparation Example 1] Zirconia Particle Dispersion (A-1) 782 g of a 2-ethylhexanoate zirconium mineral spirit solution (manufactured by Daiichi Kigenso Kagaku Kogyo 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 during the reaction at 180°C was 1.03 MPa. The solution after the reaction was removed, and the precipitate that had accumulated at the bottom was filtered out, washed with acetone, and then dried. 100 g of the dried precipitate was dispersed in 800 mL of toluene, resulting in a cloudy white solution. Next, as a purification step, the solution was again filtered using quantitative filter paper (manufactured by Advantec Toyo Co., Ltd., No. 5C) to remove coarse particles and the like from the precipitate. The filtrate was then concentrated under reduced pressure, and the toluene was removed to recover white zirconium oxide particles. 10 g of the zirconium oxide particles obtained above were dispersed in 90 g of toluene to obtain a transparent dispersion. 1.5 g of 3-methacryloxypropyltrimethoxysilane (KBM-503, manufactured by Shin-Etsu Chemical Co., Ltd.) was added as a surface coating agent to the obtained transparent dispersion, and the mixture was heated to reflux at 90°C for 1 hour. Next, n-hexane was added to the dispersion after refluxing to aggregate the dispersed particles, making the dispersion cloudy. The aggregated particles were separated from the cloudy liquid using filter paper and then heated and dried at room temperature to prepare zirconium oxide particles surface-treated with 2-ethylhexanoic acid and 3-methacryloxypropyltrimethoxysilane. The average particle diameter of the obtained coated zirconium oxide particles was measured and found to be 12 nm. Furthermore, propylene glycol monomethyl ether (PGME) was added to the white powder and the mixture was stirred to obtain a zirconia particle dispersion containing 80 mass% coated zirconia particles (referred to as "zirconia particle dispersion (A-1)"). The average particle size of the aggregated particles in the zirconia particle dispersion (A-1) was 12 nm.

[0147] [Preparation Example 2] Zirconia particle dispersion (A-2) A zirconia particle dispersion (A-2) was prepared in the same manner as in Preparation Example 1, except that the solvent (PGME) in the particle dispersion (A-1) was changed to propylene glycol monomethyl ether acetate (PGMEA). The average particle size of the particles in the zirconia particle dispersion (A-2) was 12 nm.

[0148] 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 solid contents of the zirconium dioxide particles, the dispersant, and the binder resin (G-1) and the amount of the solvent in the dispersion were as follows: Note that the amount of solvent below is the total amount including the amount of the dispersant used when preparing the particle dispersion (A-3) and the amount of the solvent contained in the binder resin (G-1). Zirconium dioxide particles (manufactured by Daiichi Kigenso Kagaku Kogyo Co., Ltd., UEP) 100.00 parts by mass Dispersant (manufactured by BYK-Chemie, DISPERBYK-111) 6.67 parts by mass / solids equivalent Binder resin (G-1) 6.67 parts by mass / solids equivalent Solvent (PGMEA) 138.51 parts by mass The above components were thoroughly stirred to obtain a mixed liquid (referred to as mixed liquid Lqb). Next, 20 g of zirconia beads having a diameter of 0.3 mm and 10 g of mixed liquid Lqb were used, and a dispersion treatment was carried out for 6 hours at 25 to 45 ° C. using a paint shaker. After the dispersion treatment was completed, the beads and dispersion were separated using a filter to prepare a zirconia dispersion (A-3) having a total solids content of 45% by mass. The average particle diameter of the particles in the zirconia particle dispersion (A-3) was 38 nm.

[0149] Preparation Example 4 Titania Particle Dispersion (A-4) (1) Preparation of Rutile Titanium Oxide Hydrosol In a 1 L glass beaker, TiO ２ 240 g of a 25% titanium oxychloride aqueous solution (TiO ２ 60 g as ZrO ２ 5 g of 35% zirconium oxychloride powder (ZrO ２The solution was called Solution A. 1 kg of water and 1.8 g of SnO were added to a 2 L flask equipped with a stirring means and a reflux condenser. ２ 20 g of 30% stannic chloride aqueous solution (SnO ２ The mixture was charged with 6 g of ammonium hydroxide (as a base), heated with stirring, and when the temperature reached 60°C, solution A was added dropwise over 15 minutes while maintaining the temperature at 60°C. After the addition was complete, the mixture was heated to boiling and the boiling state was maintained under reflux for 3 hours. The mixture was then cooled to 40°C, the pH was adjusted to 7.0 with a 28% aqueous ammonia solution, filtered, and washed to obtain a cake. Water and 36% hydrochloric acid were added to the cake and stirred to adjust the pH to 1.3, and TiO ２ At a concentration of 20%, TiO ２ In contrast, SnO ２ 10% as ZrO ２ (2) Hydrosol Coating Treatment: In a 2 L glass beaker, the TiO 3 obtained in (1) above was added, and 300 g of titanium oxide hydrosol containing 3% as a titanium dioxide was prepared. ２ 200g of 20% titanium oxide hydrosol (TiO ２ 40 g of TiO ２ The solution was diluted to a concentration of 4%, and 5.2 g of 3-glycidoxypropyltrimethoxysilane (organosilane KBM-403, manufactured by Shin-Etsu Chemical Co., Ltd.) was added to the solution while stirring. This solution was called Solution B. In another 5 L glass beaker, SiO ２ 40 g of 10% sodium silicate aqueous solution (SiO ２ A mixture of 4 g of SnO and 2 g of 48% aqueous sodium hydroxide solution was added and diluted with ion-exchanged water to a total amount of 1200 g. Solution B was added dropwise to this solution over 15 minutes while stirring. The pH after the addition was 10. Next, SnO was added to this mixed solution. ２ 20 g of 30% stannic chloride aqueous solution (SnO ２ 6 g of SiO 2 was added dropwise over 15 minutes while maintaining the pH at 10, simultaneously with a 48% aqueous solution of sodium hydroxide. ２ 20 g of 10% sodium silicate aqueous solution (SiO ２The mixture was heated to 80°C, adjusted to pH 8 with 1% hydrochloric acid, and aged at the same temperature for 120 minutes. The mixture was cooled to 20°C and adjusted to pH 3 with a 10% aqueous citric acid solution. This liquid was passed through an ultrafiltration module (Microza SLP-1053, manufactured by Asahi Kasei Chemicals Corp.) while replenishing with ion-exchanged water in an amount equal to the amount of filtration, and TiO ２ At a concentration of 3%, the electrical conductivity is 3 x 10 －３ The electrolyte content was reduced to 0.25 S / cm or less. At this stage, the citric acid used as a pH adjuster was removed and no longer remained. The pH was then adjusted to 8 with t-butylamine, and the same ultrafiltration module was used to concentrate the solution to a solids concentration of 20%. At a solids concentration of 20%, TiO ２ In contrast, SiO ２ 15% as SnO ２ (3) Solvent substitution of hydrosol with propylene glycol monomethyl ether The coated titanium oxide hydrosol obtained in (2) above was substituted with propylene glycol monomethyl ether to obtain a rutile titanium oxide hydrosol coated with 15% TiO. ２ The solution was diluted to a concentration of 5%, and passed through the same ultrafiltration module while supplying propylene glycol monomethyl ether in the same amount as the filtration volume. Finally, the supply of propylene glycol monomethyl ether was stopped, and the solution was filtered to a moisture content of 1% or less and a solid content of 20%. ２ In contrast, SiO ２ 15% as SnO ２ As a result, a titania particle dispersion liquid (A-4) coated with 15% of the titania particles was obtained. The average particle diameter of the particles in the titania particle dispersion liquid (A-4) was 36 nm.

[0150] [Preparation Example 5] Barium titanate particle dispersion (A-5) To a perfluoroalkoxyalkane (PFA) container, 100 parts by weight of barium titanate (Sigma-Aldrich, primary particle diameter less than 100 nm), 11 parts by weight of MARBON AC-F3 (polyoxyethylene secondary alkyl ether) manufactured by Matsumoto Yushi Seiyaku Co., Ltd., and 192 parts by weight of propylene glycol monomethyl ether were added, and 900 parts by weight of zirconia beads (manufactured by Nikkato Corporation) having a particle size of 0.1 mm were added. The mixture was shaken for 1 hour using a paint conditioner (manufactured by REDDEVIL Co., Ltd.) to disperse the barium titanate nanoparticles in the propylene glycol monomethyl ether. The zirconia beads were then removed to obtain a barium titanate particle dispersion (A-5). The average particle size of the particles in the barium titanate particle dispersion (A-5) was 50 nm.

[0151] [Preparation Example 6] Perylene Black Particle Dispersion (A-6) Perylene black particle dispersion (A-6) was prepared by treating with a bead mill using 12 parts by mass of C.I. Pigment Black 788 as a perylene black-based black pigment, 6 parts by mass (solid content concentration: 40% by mass) of BYK-LPN21116 (manufactured by BYK) as a dispersant, 4 parts by mass (solid content concentration: 33% by mass) of binder resin (G-1), and 78 parts by mass of PGMEA as a solvent. The average particle diameter of the particles in perylene black particle dispersion (A-6) was 42 nm.

[0152] Synthesis of Polymerizable Compound (B-3) Synthesis Example 2 To 440 parts by mass of a 50% by mass aqueous sodium hydroxide solution / dichloromethane (mass ratio = 1 / 1), 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 a phase transfer catalyst were added, and the mixture was stirred at room temperature under a nitrogen atmosphere for 6 hours. The resulting salt was then removed from the reaction solution using a glass filter, and the residue was washed with sufficient dichloromethane. The resulting filtrate was purified by separation three times using dichloromethane and distilled water, and then extracted with dichloromethane. A small amount of activated carbon was then added to the dichloromethane layer to remove coloration, followed by drying over magnesium sulfate and further concentration under reduced pressure to remove the solvent. The obtained crude product 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)).

[0153] <Preparation of Photosensitive Composition> The types and abbreviations of the particles (A), radical polymerizable compound (B), radical polymerization initiator (C), dehydrating agent (D), photoacid generator (E), solvent (F), binder resin (G), surfactant (H), and adhesion aid (I) used in the preparation of the photosensitive composition are shown below. <(A) Particles> A-1 to A-6: Particle dispersions (A-1) to (A-6) obtained in Preparation Examples 1 to 6 <(B) Radically Polymerizable Compound> B-1: Mixture of dipentaerythritol pentaacrylate and dipentaerythritol hexaacrylate (trade name: KAYARAD DPHA, manufactured by Nippon Kayaku Co., Ltd.) B-2: 3-phenoxybenzyl acrylate (trade 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 (trade name, manufactured by ADEKA Corporation) <(D) Dehydrating Agent> D-1: Methyl orthoformate D-2: Methyl orthoacetate D-3: Triethyl orthoacetate D-4: trimethyl orthobenzoate D-5: triethyl orthobenzoate D-6: acetic anhydride <(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-methoxybutyl acetate 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 in Synthesis Example 1 <(H) Surfactant> H-1: polyether-modified silicone additive (trade name: DOWSIL™ SH28 Paint Additive, manufactured by Dow Corning Toray Co., Ltd.) <(I) Adhesion Aid> I-1: 3-glycidoxypropyltrimethoxysilane I-2: 3-methacryloxypropyltrimethoxysilane (trade name: Sila-Ace S710, manufactured by Chisso Corporation)

[0154] Example 1 Preparation of Photosensitive Composition A photosensitive composition (S-1) was prepared by adding 100.0 parts by mass (solids content equivalent) of zirconia particle dispersion (A-1) as particles (A), 10.0 parts by mass (solids content equivalent) of binder resin (G-1) as polymerizable compounds (B), 10.0 parts by mass 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 (C-1) as photoradical generator (C), 10.0 parts by mass of (D-1) as dehydrating agent (D), and 0.05 parts by mass of (H-1) as surfactant (H), and further adding (F-1) and (F-2) in a 50:50 (mass ratio) as solvent (F) so that the solids concentration was 40.0 mass%. The mixture was stirred and then filtered using a 0.5 μm filter.

[0155] [Examples 2 to 21, Comparative Examples 1 and 2] Preparation of Photosensitive Compositions (S-2) to (S-24) Photosensitive compositions (S-2) to (S-24) were prepared in the same manner as photosensitive composition (S-1), with the particle dispersion, binder resin, radical polymerizable compound, photoradical generator, dehydrating agent, surfactant, adhesion aid, and solvent mixed in the ratios shown in Table 1. In Table 1, "-" indicates that the corresponding component was not used. In Table 1, the percentage in the solvent column indicates the mass ratio of each component. For example, Example 2 indicates that a mixed solvent of (F-1) and (F-2) in a 50:50 (mass ratio) was used, and Example 10 indicates that (F-1) was used alone.

[0156]

[0157] <Method for evaluating application properties over time (syringe clogging)> A 10 mL clear syringe (PSY-10E, manufactured by Musashi Engineering Co., Ltd.) was fitted with an SUS needle (SNA-20G-B, manufactured by Musashi Engineering Co., Ltd., inner diameter × needle outer diameter (φmm): 0.61 × 0.91). 5 g of each of the photosensitive compositions (S-1 to 24) was placed in the clear syringe, which was then quickly capped with a syringe head cap (HC-10C, manufactured by Musashi Engineering Co., Ltd.). The photosensitive composition came out of the SUS needle, but stopped after about 20 seconds. The clear syringe was left to stand, and after a certain period of time, the syringe head cap was removed. If the photosensitive composition passed through, it was judged as "no syringe clogging"; if the photosensitive composition did not pass through, it was judged as "syringe clogging." Evaluation was performed according to the following criteria: A: Syringe clogging did not occur even after 100 minutes or more had passed. B: The syringe did not clog in less than 80 minutes, but clogged after 80 to 100 minutes. C: The syringe did not clog in less than 60 minutes, but clogged after 60 to 80 minutes. D: The syringe did not clog in less than 20 minutes, but clogged after 20 to 60 minutes. E: Clogged after less than 20 minutes.

[0158] <Evaluation of Storage Stability (Rate of Viscosity Change)> The viscosity of each of the photosensitive compositions (S-1 to 24) was measured immediately after preparation using an E-type viscometer (initial viscosity). The photosensitive compositions were then stored at 25°C for one month, and the viscosity was measured again (viscosity after storage). The rate of viscosity change was calculated using the following formula and evaluated according to the following criteria. A: Viscosity change rate is less than 2% B: Viscosity change rate is 2% or more but less than 5% C: Viscosity change rate is 5% or more but less than 10% D: Viscosity change rate is 10% or more

[0159] <Evaluation of Storage Stability (Change in Resolution)> The resolution of each of the photosensitive compositions (S-1 to 24) immediately after preparation was measured according to the following method (initial resolution). The photosensitive compositions were then stored at 25°C for one month, and the resolution was measured again (resolution after storage). The change in resolution was calculated using the following formula and evaluated according to the following criteria: Resolution change (μm) = (initial resolution) - (resolution after storage) (Resolution Evaluation Method) Each of the photosensitive compositions (S-1 to 24) was applied to a 6-inch glass wafer using a spinner, and then prebaked on a hot plate at 85°C for 60 seconds to form a coating film with a thickness of 3.0 μm. Using a high-pressure mercury lamp (SUSS), a cumulative irradiation dose of 100 mJ / cm was measured through a photomask with a 20 μm hole. ２ The substrate was exposed to light so that the image was clear, and puddle development was carried out using a 2.38% TMAH aqueous solution (developer temperature: 25°C) for 60 seconds, followed by rinsing with water. The substrate was heated in a clean oven at 85°C for 60 minutes to form a cured film on the 6-inch glass wafer. The bottom width inside the resulting hole was confirmed using an optical microscope to evaluate the resolution. A: Resolution change of less than 1 μm B: Resolution change of 1 μm or more but less than 3 μm C: Resolution change of 3 μm or more but less than 5 μm D: Resolution change of 5 μm or more

[0160] Table 2 shows the evaluation results for the photosensitive compositions (S-1 to 24) prepared in the Examples and Comparative Examples.

[0161]

[0162] As shown in Table 2, the photosensitive compositions of Examples 1 to 21 were evaluated as being good in both applicability over time and storage stability. In contrast, the syringes of Comparative Examples 1 to 3 clogged within 60 minutes, making application impossible. The compositions also had poor storage stability.

[0163] Next, a description will be given of Examples 22 to 26 and Comparative Example 4. The compounds used in these Examples and Comparative Examples are as follows. <(A) Particles> A-2, A-4: Particle dispersions (A-2) and (A-4) obtained in Preparation Examples 2 and 4. <(B) Radically 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-acrylic acid-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 number: 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 (manufactured by BASF) C-3: Irgacure OXE-02 (manufactured by BASF) <(D) Dehydrating Agent> D-4: Trimethyl orthobenzoate <(E) Photoacid Generator> E-2: Diphenyl[4-(phenylthio)phenyl]sulfonium hexafluorophosphate E-3: 4-isobutylphenyl-4'-toluyl iodohexafluorophosphate <(F) Solvent> F-1: Propylene glycol monomethyl ether acetate F-2: Propylene glycol monomethyl ether F-3: 3-methoxybutyl acetate F-5: Diacetone alcohol <(H) Surfactant> 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 aid> 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)ethylbenzoate (CAS number: 10287-53-3) J-2: 9,10-dibutoxyanthracene (CAS number: 76275-14-4),

[0164] Example 22 Preparation of Photosensitive Composition Photosensitive composition (S-25) was prepared by adding 10.0 parts by mass (solids content equivalent) 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 (C-2) as photoradical generator (C), 0.02 parts by mass of (E-2) as photoacid generator, 0.01 parts by mass of (J-1) as sensitizer, 1.0 part by mass of (D-4) as dehydrating agent (D), 6.0 parts by mass of (I-3) as adhesion aid (I), and 1.0 part by mass of (H-2) as surfactant (H), and further adding (F-3) as solvent (F) so that the solids concentration was 40.0% by mass. The mixture was stirred and then filtered using a 0.5 μm filter.

[0165] [Examples 23 to 26, Comparative Example 4] Preparation of Photosensitive Compositions (S-26) to (S-30) Photosensitive compositions (S-26) to (S-30) were prepared in the same manner as photosensitive composition (S-25) by mixing the particle dispersion, polymerizable compound, photoradical generator, photoacid generator, sensitizer, dehydrating agent, surfactant, adhesion aid, and solvent in the ratios shown in Table 3. In Table 3, "-" indicates that the corresponding component was not used. In Table 3, the percentage in the solvent column indicates the mass ratio of each component.

[0166]

[0167] Table 4 shows the evaluation results for the photosensitive compositions (S-25 to 30) prepared in the Examples and Comparative Examples.

[0168]

[0169] As shown in Table 4, the photosensitive compositions of Examples 22 to 26 were evaluated as being good in both the long-term coatability and the storage stability. In contrast, Comparative Example 4 was inferior to the Examples in the long-term coatability and the storage stability.

[0170] The correlation between the water content in the compositions of Examples 1 to 26 and Comparative Examples 1 to 4 and the applicability over time (syringe clogging) was evaluated, and the results are shown in Table 5. The water content was measured as follows.

[0171] <Evaluation of Moisture Content> The moisture content of each of the photosensitive compositions (S-1 to 30) was measured using a coulometric moisture meter CA-100 manufactured by Mitsubishi Chemical Analytical Corporation. Aquamicron TMAX / CXU was used as the titration reagent. The measurement was repeated three times, and the average value was calculated as the moisture content of each photosensitive composition.

[0172]

[0173] The results in Table 5 show that in Comparative Examples 1 to 4, in which the water content was 2000 ppm or more, the particle components in the composition were prone to aggregation, resulting in poor long-term applicability. On the other hand, when the water content was less than 2000 ppm, aggregation was less likely, and the long-term applicability was better than in the Comparative Examples. In particular, when the water content was less than 1000 ppm, the particle components in the composition were less likely to aggregate, and the long-term applicability was good, with no problems at all.

Claims

1. A photosensitive composition for forming an optical member, comprising particles (A), a radical polymerizable compound (B), a photoradical generator (C), and a dehydrating agent (D), wherein the dehydrating agent (D) comprises an orthoester compound.

2. The photosensitive composition according to claim 1, wherein the dehydrating agent (D) comprises an orthoester compound having a boiling point of 105° C. or higher.

3. The photosensitive composition according to claim 1, wherein the orthoester compound is a compound represented by the following formula (1): ２１ -C-(OR １１ ) ３ ...(1) (In formula (1), R １１ is an alkyl group having 1 to 4 carbon atoms or a phenyl group, R ２１ is a hydrogen atom, a monovalent chain hydrocarbon group having 1 to 4 carbon atoms, or a monovalent aromatic ring group having 6 to 12 carbon atoms. １１ are the same or different.) 4. The photosensitive composition according to claim 1, wherein said orthoester compound has an aromatic ring group.

5. The photosensitive composition according to claim 1, wherein the particles (A) are inorganic particles coated with a compound having an acidic group.

6. The photosensitive composition according to claim 5, wherein the inorganic particles are at least one type of particles selected from the group consisting of zirconium oxide, titanium oxide, barium titanate and silica.

7. The photosensitive composition according to claim 1, wherein the water content in said photosensitive composition is less than 2000 ppm.

8. The photosensitive composition according to claim 1, wherein the optical member is a member for improving the light extraction efficiency in a display element.

9. A cured product obtained by curing the photosensitive composition according to any one of claims 1 to 8.

10. A method for producing a cured product, comprising the steps of: applying the photosensitive composition according to any one of claims 1 to 8 onto a substrate; irradiating the photosensitive composition applied onto the substrate with radiation; developing the photosensitive composition after irradiation with radiation; and heating the developed photosensitive composition at a temperature of 100°C or less to cure it.

11. A display device comprising the cured product according to claim 9.

12. An imaging device comprising the cured product according to claim 9.

13. 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 moisture contained in the photosensitive composition is less than 2000 ppm.

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