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

Abstract

The purpose of the present invention is to provide: a photosensitive composition which has excellent storage stability even after a certain period of time due to little increase in viscosity; a cured film formed from the photosensitive composition; a method for producing the cured film; a display element comprising the cured film; when a coating slit nozzle or the like is used, the photosensitive composition does not solidify, and can be coated even after a certain period of time (good coating performance over time). The present invention relates to a photosensitive composition for forming an optical member, the photosensitive composition comprising particles (A), a radical polymerizable compound (B), a light radical generator (C), and a dehydrating agent (D), the dehydrating agent (D) comprising an ortho-ester compound.

Description

TECHNICAL FIELD

[0001] The present application relates to a photosensitive composition, a hardened product and a manufacturing method thereof, a display element, and an imaging element, and particularly to a technology for forming an optical member for a display element or an imaging element. BACKGROUND

[0002] Various image sensors such as a charge-coupled device (CCD) image sensor or a complementary metal-oxide-semiconductor (CMOS) image sensor are used as a solid-state imaging element in an imaging device such as a camera. In the solid-state imaging element, a hemispherical condenser lens (hereinafter, also referred to as "microlens") or an in-layer lens is provided to condense light into a light-receiving element (photodiode) to increase the sensor sensitivity. In addition, in a display element such as an organic electroluminescence (EL) element, a structure in which a microlens is provided on the light-exiting side of each pixel is adopted for the purpose of improving light extraction efficiency or adjusting the viewing angle (for example, refer to Patent Document 1). In recent years, the lens of the solid-state imaging element or the display element is also formed by photolithography using a photosensitive composition.

[0003] As the photosensitive composition, for example, a film-forming composition containing inorganic particles, a polysilane compound, a polymerizable monomer, and a hardening accelerator such as a dehydrating agent is known (for example, refer to Patent Document 2).

[0004] PRIOR ART DOCUMENTS

[0005] PATENT DOCUMENTS

[0006] Patent Document 1: Japanese Patent Laid-Open No. 2020-101659

[0007] Patent Document 2: Japanese Patent Laid-Open No. 2007-131714 SUMMARY

[0008] PROBLEMS TO BE SOLVED BY THE INVENTION

[0009] The present inventors and others have conducted research, and as a result, it has been found that in a photosensitive composition in which particles are dispersed, the viscosity sometimes increases with time and the storage stability is poor. In addition, when a coating mechanism such as a coating slit nozzle is used, the slit nozzle is repeatedly used in a manner of coating, standing, coating, and standing, but after a certain period of time, a part of the photosensitive composition inside the coating mechanism is solidified and adheres to the tip end of the nozzle to cause coating failure.

[0010] The present application relates to a photosensitive composition, a hardened film formed from the photosensitive composition, a method for producing the hardened film, a display element including the hardened film, and an imaging element including the hardened film, in which the photosensitive composition has less viscosity increase even after a certain period of time, is excellent in storage stability, and does not solidify even when a coating slot nozzle or the like is used, and can be coated even after a certain period of time (good in coating stability over time).

[0011] Technical means for solving the problem

[0012] The present inventors have made intensive studies in order to solve the problem, and as a result, have found that the object can be achieved by forming a photosensitive composition having the following structure, thereby completing the present application.

[0013] The present application relates to a photosensitive composition for forming an optical member,

[0014] The photosensitive composition contains a particle (A), a radical polymerizable compound (B), a photoradical generator (C), and a dehydrating agent (D),

[0015] The dehydrating agent (D) contains a primary ester compound.

[0016] The present application relates to a photosensitive composition for forming an optical member,

[0017] The photosensitive composition contains a particle (A), a radical polymerizable compound (B), and a photoradical generator (C),

[0018] The amount of moisture contained in the photosensitive composition is less than 2000 ppm.

[0019] The present application relates to a method for producing a hardened product, including:

[0020] A step of applying the photosensitive composition on a substrate;

[0021] A step of irradiating the photosensitive composition applied on the substrate with a radiation;

[0022] A step of developing the photosensitive composition after the irradiation with the radiation; and

[0023] A step of heating the photosensitive composition after the development at a temperature of 100°C or lower to harden the photosensitive composition.

[0024] The present application relates to a

[0025] A hardened product formed by hardening the photosensitive composition, a display element including the hardened film, and an imaging element.

[0026] Effects of the Invention

[0027] The photosensitive composition according to the present application is less in viscosity increase even after a certain period of time and is excellent in storage stability, and in the case of using a coating slit nozzle or the like, the photosensitive composition does not solidify, and can be coated even after a certain period of time (i.e., is good in chronologically coating property). The reason is presumed as follows. It is considered that the photosensitive composition in which particles are disposed, if exposed to the atmosphere for a certain period of time, moisture in the atmosphere acts on the particles in the photosensitive composition to accelerate agglomeration, as a result, the viscosity of the photosensitive composition increases, and the chronologically coating property or the storage stability is poor, but in the present application, by disposing a primary ester compound in the photosensitive composition, the moisture intruding into the photosensitive composition can be captured, and even for the photosensitive composition in which particles are disposed, the viscosity increase is less, and the chronologically coating property or the storage stability is excellent.

[0028] In addition, the photosensitive composition according to another embodiment is less in the amount of moisture contained in the photosensitive composition than 2000 ppm, and it is considered that the particle component in the composition is less likely to agglomerate, and the chronologically coating property becomes good.

[0029] In the method for producing a hardened film of the present application, since the photosensitive composition which is less in viscosity increase even after a certain period of time and is excellent in chronologically coating property or storage stability is used, a high-quality hardened film can be produced even after a certain period of time.

[0030] The display element and the imaging element of the present application are high-quality since they include the hardened film. DETAILED DESCRIPTION

[0031] Hereinafter, the embodiments of the present application are described in detail, but the present application is not limited to these embodiments. In addition, in the present specification, the numerical range written with "to" includes the numerical values written before and after "to" as lower limit values and upper limit values. The so-called "structural unit" is a unit mainly constituting the main chain structure, and refers to a unit including two or more units in the main chain structure.

[0032] In the present specification, "hydrocarbon group" has the meaning including chain hydrocarbon group, alicyclic hydrocarbon group, and aromatic hydrocarbon group. The "chain hydrocarbon group" means straight-chain hydrocarbon group and branched-chain hydrocarbon group which are composed of only chain structure without ring structure in the main chain. Among them, it can be saturated or unsaturated. The "alicyclic hydrocarbon group" means a hydrocarbon group which contains only a structure of alicyclic hydrocarbon as a ring structure without aromatic ring structure. Among them, it need not be composed of only the structure of alicyclic hydrocarbon, and a group having a chain structure in a part thereof is also included. The "aromatic hydrocarbon group" means a hydrocarbon group which contains an aromatic ring structure as a ring structure. Among them, it need not be composed of only the aromatic ring structure, and a chain structure or a structure of alicyclic hydrocarbon can be included in a part thereof. In addition, the ring structure of the alicyclic hydrocarbon group and the aromatic hydrocarbon group can also have a substituent group containing a hydrocarbon structure.

[0033] In the present specification, "(meth)acryl-" has the meaning including "acryl-" and "methacryl-", and "(meth)acrylic acid group" has the meaning including "acrylic acid group" and "methacrylic acid group". "(Meth)acrylate" has the meaning including "acrylate" and "methacrylate".

[0034] Photosensitive composition

[0035] The photosensitive composition of the present embodiment (hereinafter, also simply referred to as "the present composition") is

[0036] A composition (hereinafter, also referred to as the present composition (1)) containing a particle (A), a radical polymerizable compound (B), a photoradical generator (C), and a dehydrating agent (D), and the dehydrating agent (D) contains a primary ester compound; and

[0037] A photosensitive composition for forming an optical member containing a particle (A), a radical polymerizable compound (B), and a photoradical generator (C), and the amount of moisture contained in the photosensitive composition is less than 2000 ppm (hereinafter, also referred to as the present composition (2)).

[0038] The photosensitive composition is a photosensitive composition for forming an optical member for a display element such as an organic EL element or an imaging element. The optical member formed from the present composition improves light extraction efficiency in a display element, for example, or concentrates light into a light-receiving element (photodiode) in a solid-state imaging device to improve sensor sensitivity. As the optical member, a pattern formed by repeating arrangement of a planarization film or a lens can be cited. As the shape of the lens constituting the pattern, a semispherical shape, a cylindrical shape, a frustum of a cone shape, or the like can be cited. As the shape viewed from the upper surface of the lens, a circular shape, a polygonal shape, or the like can be cited, each of which can be a shape having a curved surface like a spherical shape or a trapezoidal shape like a frustum of a cone. The lens is formed from the photosensitive composition of the present application, and another transparent material layer such as a low-refractive material layer can be formed in the gap between the lenses. The planarization film is formed on a substrate in order to planarize the surface of the substrate on which a semiconductor element or the like is formed. The pattern is a minute condensing body (lens or trapezoidal / rectangular pattern) or an interlayer lens provided in a display element or a solid-state imaging element (for example, a CCD image sensor, a CMOS image sensor). In a display element such as an organic EL element, it is provided in each pixel for the purpose of improving light extraction efficiency of each pixel or adjusting the viewing angle, and in a solid-state imaging element, it is provided for the purpose of concentrating light into a light-receiving element to improve sensor sensitivity. The present composition is preferably a photosensitive composition for planarization film formation or a photosensitive composition for pattern formation. Hereinafter, each component contained in the photosensitive composition will be described.

[0039] <Particle (A)>

[0040] The particle (A) can use a particle corresponding to the purpose of addition such as refractive index adjustment, and in the present application, it is preferable to use a particle that can achieve high refractive index of the obtained hardened product. As the particle (A), either an inorganic particle or an organic particle can be used, and a pigment particle can also be used.

[0041] As the inorganic particle, there is no particular limitation, and for example, particle-like substances such as zirconium oxide, titanium oxide, aluminum oxide, silver oxide, zinc oxide, barium titanate, silicon dioxide (including silicon dioxide, hollow silicon dioxide), cerium oxide, silicon nitride, palladium sulfide, or the like can be cited. Among these, from the viewpoint of stability of the particle, it is preferable to select at least one particle from the group consisting of zirconium oxide, titanium oxide, and barium titanate, and from the aspect of high stability of the dispersion, zirconium oxide particles are particularly preferable.

[0042] As the organic particle, there is no particular limitation, and for example, particles containing a polyolefin-based resin such as polystyrene, polyethylene, or polypropylene, an acrylic resin, or the like, or a high molecular compound can be cited. In addition, transparent particles, opaque particles, colored particles, and hollow particles are also contained in the organic particle.

[0043] In addition, as the pigment particles, either of an organic pigment or an inorganic pigment can be used. As the pigment, for example, carbon black, graphite, activated carbon, carbon fiber, carbon nanotube, carbon micro coil, carbon nanohorn, carbon aerogel, fullerene, aniline black, pigment black 7, titanium black, lactam black, perylene black, chromium oxide green, Milori blue, cobalt green, cobalt blue, manganese group, ferrocyanide, phosphate ultramarine, deep blue, ultramarine, cerulean blue, viridian, emerald green, lead sulfate, yellow lead, zinc yellow, Bengala (red iron (III) oxide), cadmium red, umber, lake pigment, barium sulfate, calcium carbonate, hydrous magnesium silicate (talc), magnesium carbonate, calcium sulfate, diatomite, mica, silica, or the like organic pigment or inorganic pigment can be listed. Among these, perylene black is preferable.

[0044] As for the shape of the particles (A), for example, a spherical shape, a granular shape, a plate shape, a columnar shape, or the like can be listed.

[0045] In addition, the average particle diameter of the particles (A) is not particularly limited, and from the viewpoint of obtaining a hardened film with high surface planarity and transparency, it is preferable to be 100 nm or less, more preferable to be 50 nm or less, and further preferable to be 30 nm or less. In addition, from the viewpoint of dispersion stability, the average particle diameter of the particles (A) is, for example, 1 nm or more, and preferably 2 nm or more. The average particle diameter in the present application means a D50 particle diameter (a median diameter indicating a cumulative value of 50% of a cumulative distribution curve) in measurement using a dynamic light scattering method, and for example, a Microtrac Wave II-EX150 manufactured by Microtrac Bell Co. can be used for measurement.

[0046] As the particles (A), from the aspect of dispersion stability of the particles in a solvent, it is preferable that the particles are covered with a surface coating agent, and more preferable that the inorganic particles are covered with a compound having an acidic group (hereinafter, also referred to as "specific coating agent") (hereinafter, also referred to as "coated particles"). Here, the inorganic particles covered with the specific coating agent are a specific coating agent-particle complex obtained by surface treatment of the particles with a surface coating agent containing the specific coating agent.

[0047] As the acidic group possessed by the specific coating agent, there can be mentioned a carboxyl group, a phenolic hydroxyl group, a sulfo group, a phosphoric acid group, a phosphonic acid group, and the like. Of these, from the viewpoint of imparting good dispersibility of the particles in a solvent and good alkali developability, a carboxyl group or a phenolic hydroxyl group is preferable, and a carboxyl group is particularly preferable. From the viewpoint of excellent alkali developability and the ability to suppress development residue, as the coated particles, a particle whose surface is coated with a carboxyl group-containing compound selected from at least one of the group consisting of zirconium oxide, titanium oxide, and barium titanate is preferable, and a zirconium oxide particle whose surface is coated with a carboxyl group-containing compound is more preferable.

[0048] The specific coating agent can be a low-molecular compound (i.e., a compound having no molecular weight distribution) or a polymer. The specific coating agent is preferably a carboxyl group-containing compound, and more preferably a moncarboxylic acid or a carboxyl group-containing polymer is used as the carboxyl group-containing compound.

[0049] The moncarboxylic acid used as the specific coating agent can be exemplified by a compound represented by the following formula (2).

[0050] R 3 -COOH … (2)

[0051] (In formula (2), R 3 is a monovalent hydrocarbon group or a halogenated hydrocarbon group having 4 or more carbon atoms, or has one or more monovalent groups selected from the group consisting of an oxygen atom, a sulfur atom, and a nitrogen atom)

[0052] In formula (2), the monovalent hydrocarbon group having 4 or more carbon atoms represented by R 3 may be exemplified by a chain hydrocarbon group, an alicyclic hydrocarbon group, and an aromatic hydrocarbon group. In addition, in the case where the monovalent hydrocarbon group represented by R 3 is a chain hydrocarbon group or an alicyclic hydrocarbon group, it can be either saturated or unsaturated, and in the case of a chain hydrocarbon group, it can be either linear or branched. Of these, the monovalent hydrocarbon group represented by R 3 is preferably a chain hydrocarbon group, and more preferably an alkyl group or an alkenyl group. From the viewpoint of improving the dispersibility of the particles (A), the carbon number of R 3 is preferably 6 or more, and more preferably 7 or more. In addition, from the viewpoint of ease of coating, the carbon number of R 3 is preferably 30 or less, and more preferably 20 or less. In the case where R 3 is a monovalent halogenated hydrocarbon group having 4 or more carbon atoms, as the halogen atom possessed by R 3 , there can be mentioned a fluorine atom, a chlorine atom, and the like.

[0053] In the case where R 3In the case of having one or more monovalent groups selected from the group consisting of an oxygen atom, a sulfur atom, and a nitrogen atom, as the monovalent group, a group containing one or more groups selected from the group consisting of -O-, -S-, and -NH- between carbon-carbon bonds of a hydrocarbon group, a group in which any hydrogen atom possessed by a hydrocarbon group is substituted with one or more groups selected from the group consisting of a hydroxyl group, a thiol group, and an amino group can be exemplified. Among these, a group containing -O- between carbon-carbon bonds of a hydrocarbon group is preferable. In R 3 In the case of having one or more monovalent groups selected from the group consisting of an oxygen atom, a sulfur atom, and a nitrogen atom, from the viewpoint of improving the dispersibility of the particles (A), R 3 The carbon number of R is preferably 2 or more, more preferably 2 to 15, and further preferably 2 to 8.

[0054] As a specific example of the compound represented by the formula (2), as R 3 As a monocarboxylic acid in which R is a monovalent hydrocarbon group, 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 can be exemplified.

[0055] As R 3 As a monocarboxylic acid in which R is a monovalent group selected from the group consisting of an oxygen atom, a sulfur atom, and a nitrogen atom, methoxyacetic acid, ethoxyacetic acid, 3-ethoxypropionic acid, 2-methoxyethoxyacetic acid, glyoxylic acid, pyruvic acid, hydroxybenzoic acid, thio glycolic acid, 2-[2-(2-methoxyethoxy)]ethoxyacetic acid, oxovaleric acid, asparagine, glutamine, methionine, glycolic acid, lactic acid, 2-hydroxyisobutyric acid, hydroxystearic acid, and salicylic acid can be exemplified.

[0056] As the carboxyl group-containing polymer, a polymer containing a structural unit having a carboxyl group can be preferably used. As a specific example of the carboxyl group-containing polymer as the specific coating agent, the same polymers as exemplified as specific examples of the binder resin (G) to be described later can be exemplified.

[0057] As the surface coating agent, a compound other than the specific coating agent (hereinafter, also referred to as "other coating agent") can be used alone, or can be used in combination with the specific coating agent. As the other coating agent, for example, alkoxy titanium, alkoxysilane group-containing compound, unsaturated carbon-carbon bond-containing compound, and the like can be exemplified. As the alkoxy titanium, tetra-n-butoxy titanium, tetra-t-butoxy titanium, tetraethoxy titanium, and the like can be exemplified. As the alkoxysilane group-containing compound, vinyltrimethoxysilane, vinyltriethoxysilane, 3-(meth)acryloyloxypropyltrimethoxysilane, 3-(meth)acryloyloxypropyltriethoxysilane, N-(2-aminoethyl)-3-aminopropylmethyldimethoxysilane, N-(2-aminoethyl)-3-aminopropyltrimethoxysilane, p-styryltrimethoxysilane, p-styryltriethoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, and the like can be exemplified. As the unsaturated carbon-carbon bond-containing compound, a silane compound having a carbon-carbon unsaturated bond among the compounds exemplified as the alkoxysilane group-containing compound can be exemplified. In addition, as the surface coating agent, a compound having a basic group can be used.

[0058] In the case where the specific coating agent is used in combination with the other coating agent, the use ratio of the other coating agent with respect to the total amount of the surface coating agent used in the coating of the particles (A) is preferably 50% by mass or less, more preferably 40% by mass or less.

[0059] In the case where the particles (A) are coated particles, the method for producing the same is not particularly limited, and the coated particles can be produced by bringing the treated particles into contact with the surface coating agent according to a known method. At this time, the coated particles can be produced by a top-down method, or can be produced by a bottom-up method. In addition, the coated particles can be produced in a gas phase, or can be produced in a liquid phase. For example, the coated particles can be obtained by bringing the treated particles into contact with the surface coating agent, preferably in the presence of water. In addition, the coated particles can be obtained by mixing the treated particles with the surface coating agent, preferably in the presence of a dispersant, in an organic solvent, and stirring the mixture using beads. The temperature or pressure at the time of bringing the treated particles into contact with the surface coating agent can be appropriately set according to the production method to be employed. At the time of bringing the treated particles into contact with the surface coating agent, the ratio of the treated particles to the surface coating agent can be, for example, 100 parts by mass of the treated particles to 0.5 parts by mass to 20 parts by mass of the surface coating agent, and is preferably 100 parts by mass of the treated particles to 1 part by mass to 20 parts by mass of the surface coating agent.

[0060] In addition, as the particle (A), it is also possible to use, as appropriate, a titanium oxide particle (inorganic oxide-coated titanium oxide particle) in which the surface is covered with an inorganic oxide such as silicon, zinc, tin, zirconium, aluminum, or the like, as described in Japanese Patent Application Publication No. 2013-008428 or Japanese Patent Application Publication No. 2009-179678.

[0061] The present composition can contain one or a combination of two or more of the particles (A).

[0062] From the viewpoint of achieving high refractive index of the obtained hardened product, the lower limit value of the content ratio of the particle (A) in the present composition (the total content ratio in the case of containing a plurality of kinds) with respect to the total amount of the solid components (i.e., components other than the solvent) contained in the present composition is preferably 10% by mass, more preferably 15% by mass, further preferably 35% by mass, further more preferably 45% by mass, and particularly preferably 55% by mass. In addition, from the viewpoint of ensuring the stability of the dispersion liquid, the upper limit value of the content ratio of the particle (A) with respect to the total amount of the solid components contained in the present composition is preferably 95% by mass, more preferably 90% by mass.

[0063] <Free Radical Polymerizable Compound (B)>

[0064] As the free radical polymerizable compound (B), monofunctional polymerizable compounds (B1), polyfunctional polymerizable compounds (B2) can be exemplified. The so-called free radical polymerizable compound (B) is a compound that can generate a polymer by the reaction of a plurality of polymerizable compounds (B) with each other in association with the irradiation of the present composition with a radiation.

[0065] As the monofunctional polymerizable compound (B1), a compound having one free radical polymerizable group can be preferably used, and, for example, (meth)acryl group-containing compounds, chain vinyl compounds, aromatic vinyl compounds, maleimide compounds, and the like can be exemplified. As specific examples of the (meth)acryl group-containing compounds, unsaturated carboxylic acids, unsaturated carboxylic anhydrides, (meth)acrylates containing a chain structure, (meth)acrylates having an alicyclic structure, (meth)acrylates having an aromatic ring structure, (meth)acrylamide compounds, chain vinyl compounds, compounds having a phosphoric acid group and a (meth)acryl group, and the like can be exemplified. These compounds can be preferably used from the viewpoint of good polymerizability or the viewpoint of relatively high plasticizing property. As the monofunctional polymerizable compound (B1), from the viewpoint of achieving high refractive index or the viewpoint of transparency, (meth)acryl group-containing compounds can be preferably used.

[0066] As the unsaturated carboxylic acid, (meth)acrylic acid, crotonic acid, maleic acid, itaconic acid, fumaric acid, and the like can be exemplified; as the unsaturated carboxylic anhydride, maleic anhydride, itaconic anhydride, citraconic anhydride, and the like can be exemplified.

[0067] As the (meth)acrylic acid alkyl ester, there can be mentioned methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, isopropyl (meth)acrylate, butyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, isodecyl (meth)acrylate, n-lauryl (meth)acrylate, n-stearyl (meth)acrylate, and the like;

[0068] As the (meth)acrylic acid alkyl ester, there can be mentioned methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, isopropyl (meth)acrylate, butyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, isodecyl (meth)acrylate, n-lauryl (meth)acrylate, n-stearyl (meth)acrylate, and the like;

[0069] As the (meth)acrylic acid alkyl ester, there can be mentioned methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, isopropyl (meth)acrylate, butyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, isodecyl (meth)acrylate, n-lauryl (meth)acrylate, n-stearyl (meth)acrylate, and the like;

[0070] As the (meth)acrylic acid alkyl ester, there can be mentioned methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, isopropyl (meth)acrylate, butyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, isodecyl (meth)acrylate, n-lauryl (meth)acrylate, n-stearyl (meth)acrylate, and the like;

[0071] As the (meth)acrylic acid alkyl ester, there can be mentioned methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, isopropyl (meth)acrylate, butyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, isodecyl (meth)acrylate, n-lauryl (meth)acrylate, n-stearyl (meth)acrylate, and the like;

[0072] As the (meth)acrylic acid alkyl ester, there can be mentioned methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, isopropyl (meth)acrylate, butyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, isodecyl (meth)acrylate, n-lauryl (meth)acrylate, n-stearyl (meth)acrylate, and the like;

[0073] As the (meth)acrylic acid alkyl ester, there can be mentioned methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, isopropyl (meth)acrylate, butyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, isodecyl (meth)acrylate, n-lauryl (meth)acrylate, n-stearyl (meth)acrylate, and the like;

[0074] As the (meth)acrylic acid alkyl ester, there can be mentioned methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, isopropyl (meth)acrylate, butyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, isodecyl (meth)acrylate, n-lauryl (meth)acrylate, n-stearyl (meth)acrylate, and the like;2,6 ] decan-8-yl ester, (meth)acrylic acid tricyclo[5.2.1.0 2,5 ] decan-8-yloxyethyl ester, isobornyl (meth)acrylate, and the like.

[0075] As the (meth)acrylate having an aromatic ring structure, there can be mentioned 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-phenyloxyethyl (meth)acrylate, 2-hydroxy-3-phenoxypropyl (meth)acrylate, polyvinyl oxy nonyl phenyl (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 (Chemical Abstracts Service) No. 134903-88-1), and the like.

[0076] As the (meth)acrylamide compound, there can be mentioned (meth)acryloylmorpholine, N-(2-hydroxyethyl) (meth)acrylamide, N-vinyl-2-pyrrolidone, N-vinyl-ε-caprolactam, and the like.

[0077] As the chain vinyl compound, there can be mentioned propylene, butylene, pentene, hexene, and the like. As the aromatic vinyl compound, there can be mentioned styrene, methylstyrene, α-methylstyrene, t-butoxy styrene, o-hydroxystyrene, m-hydroxystyrene, p-hydroxystyrene, o-vinylbenzoic acid, m-vinylbenzoic acid, p-vinylbenzoic acid, vinyl naphthalene, and the like. As the maleimide compound, there can be mentioned N-methylmaleimide, N-cyclohexylmaleimide, N-phenylmaleimide, N-(p-methylphenyl)maleimide, and the like.

[0078] As the compound having a phosphoric acid group and a (meth)acryloyl group, there can be mentioned 2-hydroxyethyl methacrylate phosphate (CAS No. 52628-03-2), β-(2-furyl)acrylamide phosphate (CAS No. 16655-99-5), bis(2-methacryloyloxyethyl) phosphate (CAS No. 32435-46-4), polyethylene glycol methacrylate phosphate (CAS No. 35705-94-3), bis(2-(acryloyloxy)ethyl) phosphate (CAS No. 40074-34-8), 10-(2-methacryloyloxy)monodecyl phosphate (CAS No. 85590-00-7), and the like.

[0079] As further specific examples of the monofunctional polymerizable compound (Bl), compounds represented by the following formulae (bl-1) to (bl-28), and the like can be given.

[0080] [Chem. 1]

[0081]

[0082] [Chem. 2]

[0083]

[0084] (In formulae (bl-1) to (bl-28), R 20 is a hydrogen atom or a methyl group; R 21 is a monovalent hydrocarbon group having a carbon number of 1 to 20; and n is an integer of 0 to 10)

[0085] As the multifunctional polymerizable compound (B2), a compound having two or more radical polymerizable groups can be preferably used, and for example, a multifunctional (meth)acryl group-containing compound, a multifunctional aromatic vinyl compound, a multifunctional chain vinyl compound, and the like can be given.

[0086] As specific examples of the multifunctional (meth)acryl group-containing compound, a difunctional (meth)acrylate, a (meth)acrylate having a functionality of three or more, and the like can be given. As specific examples of the difunctional (meth)acrylate, for example, 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, ethylene oxide (EO) modified neopentyl glycol di(meth)acrylate, propylene oxide (PO) modified neopentyl glycol di(meth)acrylate, bisphenol A di(meth)acrylate, EO modified bisphenol A di(meth)acrylate, PO modified bisphenol A di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, 1,9-nonanediol di(meth)acrylate, 1,10-decanediol di(meth)acrylate, diethylene glycol di(meth)acrylate, tetraethylene glycol di(meth)acrylate, and the like can be given.

[0087] As the (meth)acrylate ester having three or more functionalities, for example, in addition to trimethylolpropane tri(meth)acrylate, oxirane-modified trimethylolpropane tri(meth)acrylate, pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, dipentaerythritol penta(meth)acrylate, dipentaerythritol hexa(meth)acrylate, oxirane-modified dipentaerythritol hexa(meth)acrylate, tris(2-(meth)acryloyloxyethyl) phosphate, succinic acid-modified pentaerythritol tri(meth)acrylate, succinic acid-modified dipentaerythritol penta(meth)acrylate, tris(2-(meth)acryloyloxyethyl) isocyanurate, (meth)acrylic acid oligomer modified with a carboxyl-containing polybasic acid, a compound having a linear alkylene group and an alicyclic structure and having two or more isocyanate groups, and a compound having one or more hydroxyl groups in the molecule and having three, four, or five (meth)acryloyloxy groups, and the like can be exemplified. The (meth)acrylate ester having three or more functionalities is not particularly limited and can be appropriately selected depending on the intended purpose.

[0088] As the multifunctional aromatic vinyl compound, 1,3-divinylbenzene, 1,4-divinylbenzene, and the like can be exemplified. As the multifunctional chain vinyl compound, 1,5-hexadiene, 1,6-heptadiene, 1,7-octadiene, and the like can be exemplified.

[0089] As further specific examples of the multifunctional polymerizable compound (B2), compounds represented by the following formulae (b2-29) to (b2-53), and the like can be exemplified.

[0090] [Chemical Formula 3]

[0091]

[0092] [Chemical Formula 4]

[0093]

[0094] [Chemical Formula 5]

[0095]

[0096] (In formulae (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; and 1 ≤ x + y + z ≤ 3 is satisfied)

[0097] As the multifunctional polymerizable compound (B2), from the viewpoint of achieving a high refractive index or the viewpoint of transparency, a (meth)acryloyl group-containing compound can also be preferably used.

[0098] Further, as the radically polymerizable compound (B), a polymerizable compound (B3) having both a radically polymerizable group and a cationically polymerizable group can be exemplified, and it is preferable to be used in combination with the monofunctional polymerizable compound (B1) or the multifunctional polymerizable compound (B2). As the cationically polymerizable group, an epoxy group, an oxetanyl group, or a vinyl ether group can be exemplified.

[0099] As the polymerizable compound (B3) having both a radically polymerizable group and a cationically polymerizable group, a compound having a vinyl group or a (meth)acryloyl group as the radically polymerizable group and having an epoxy group or an oxetanyl group as the cationically polymerizable group is preferable. As the polymerizable compound (B3), (meth)acrylic acid glycidyl ester, (meth)acrylic acid 3,4-epoxycyclohexyl ester, (meth)acrylic acid 3,4-epoxycyclohexylmethyl ester, (meth)acrylic acid 2-(3,4-epoxycyclohexyl)ethyl ester, (meth)acrylic acid 3,4-epoxytricyclo[5.2.1.02'6]decyl ester, 2-hydroxyethyl [3,4-epoxytricyclo(5.2.1.02'6)dec-9-yl] methyl acrylate, [3,4-epoxytricyclo(5.2.1.02'6)dec-9-yl] methyl acrylate, (meth)acrylic acid (3-methyloxetan-3-yl)methyl ester, (meth)acrylic acid (3-ethyloxetan-3-yl) ester, (meth)acrylic acid (3-ethyloxetan-3-yl)methyl ester, (meth)acrylic acid (oxetan-3-yl)methyl ester, 3-(meth)acryloyloxy methyl-3-ethyloxetane, o-vinylbenzyl glycidyl ether, m-vinylbenzyl glycidyl ether, p-vinylbenzyl glycidyl ether, 3-[(4-vinylbenzyl)oxymethyl]-3-ethyloxetane, and the like can be exemplified, and 3-[(4-vinylbenzyl)oxymethyl]-3-ethyloxetane is preferable. 2,6 ]cyclohexyl ester, (meth)acrylic acid 3,4-epoxycyclohexylmethyl ester, (meth)acrylic acid 2-(3,4-epoxycyclohexyl)ethyl ester, (meth)acrylic acid 3,4-epoxytricyclo[5.2.1.02'6]decyl ester, 2-hydroxyethyl [3,4-epoxytricyclo(5.2.1.02'6)dec-9-yl] methyl acrylate, [3,4-epoxytricyclo(5.2.1.02'6)dec-9-yl] methyl acrylate, (meth)acrylic acid (3-methyloxetan-3-yl)methyl ester, (meth)acrylic acid (3-ethyloxetan-3-yl) ester, (meth)acrylic acid (3-ethyloxetan-3-yl)methyl ester, (meth)acrylic acid (oxetan-3-yl)methyl ester, 3-(meth)acryloyloxy methyl-3-ethyloxetane, o-vinylbenzyl glycidyl ether, m-vinylbenzyl glycidyl ether, p-vinylbenzyl glycidyl ether, 3-[(4-vinylbenzyl)oxymethyl]-3-ethyloxetane, and the like can be exemplified, and 3-[(4-vinylbenzyl)oxymethyl]-3-ethyloxetane is preferable. 2,6 ]cyclohexyl ester, (meth)acrylic acid 3,4-epoxycyclohexylmethyl ester, (meth)acrylic acid 2-(3,4-epoxycyclohexyl)ethyl ester, (meth)acrylic acid 3,4-epoxytricyclo[5.2.1.02'6]decyl ester, 2-hydroxyethyl [3,4-epoxytricyclo(5.2.1.02'6)dec-9-yl] methyl acrylate, [3,4-epoxytricyclo(5.2.1.02'6)dec-9-yl] methyl acrylate, (meth)acrylic acid (3-methyloxetan-3-yl)methyl ester, (meth)acrylic acid (3-ethyloxetan-3-yl) ester, (meth)acrylic acid (3-ethyloxetan-3-yl)methyl ester, (meth)acrylic acid (oxetan-3-yl)methyl ester, 3-(meth)acryloyloxy methyl-3-ethyloxetane, o-vinylbenzyl glycidyl ether, m-vinylbenzyl glycidyl ether, p-vinylbenzyl glycidyl ether, 3-[(4-vinylbenzyl)oxymethyl]-3-ethyloxetane, and the like can be exemplified, and 3-[(4-vinylbenzyl)oxymethyl]-3-ethyloxetane is preferable. 2,6 ]cyclohexyl ester, (meth)acrylic acid 3,4-epoxycyclohexylmethyl ester, (meth)acrylic acid 2-(3,4-epoxycyclohexyl)ethyl ester, (meth)acrylic acid 3,4-epoxytricyclo[5.2.1.02'6]decyl ester, 2-hydroxyethyl [3,4-epoxytricyclo(5.2.1.02'6)dec-9-yl] methyl acrylate, [3,4-epoxytricyclo(5.2.1.02'6)dec-9-yl] methyl acrylate, (meth)acrylic acid (3-methyloxetan-3-yl)methyl ester, (meth)acrylic acid (3-ethyloxetan-3-yl) ester, (meth)acrylic acid (3-ethyloxetan-3-yl)methyl ester, (meth)acrylic acid (oxetan-3-yl)methyl ester, 3-(meth)acryloyloxy methyl-3-ethyloxetane, o-vinylbenzyl glycidyl ether, m-vinylbenzyl glycidyl ether, p-vinylbenzyl glycidyl ether, 3-[(4-vinylbenzyl)oxymethyl]-3-ethyloxetane, and the like can be exemplified, and 3-[(4-vinylbenzyl)oxymethyl]-3-ethyloxetane is preferable.

[0100] The present composition can contain one or a combination of two or more of the radically polymerizable compound (B).

[0101] In the case where the radical polymerizable compound (B) contains both the monofunctional polymerizable compound (Bl) and the multifunctional polymerizable compound (B2), the content of the monofunctional polymerizable compound (Bl) is preferably 20% by mass or more, more preferably 30% by mass or more, and still more preferably 40% by mass or more, relative to the total amount of the monofunctional polymerizable compound (Bl) and the multifunctional polymerizable compound (B2). In addition, the content of the monofunctional polymerizable compound (Bl) is preferably 100% by mass or less, preferably 90% by mass or less, more preferably 80% by mass or less, and still more preferably 70% by mass or less, relative to the total amount of the monofunctional polymerizable compound (Bl) and the multifunctional polymerizable compound (B2).

[0102] In addition, in the case where the radical polymerizable compound (B) contains the polymerizable compound (B3), the content thereof is preferably 50% by mass or less, and more preferably 30% by mass or less, in the radical polymerizable compound (B).

[0103] The lower limit of the content ratio of the radical polymerizable compound (B) in the present composition (the total content ratio in the case where a plurality of the polymerizable compounds (Bl) to (B3) are contained) is preferably 5 parts by mass, more preferably 10 parts by mass, and still more preferably 20 parts by mass, relative to 100 parts by mass of the particles (A). In addition, the upper limit of the content ratio of the radical polymerizable compound (B) is preferably 350 parts by mass, more preferably 200 parts by mass, still more preferably 100 parts by mass, yet more preferably 50 parts by mass, yet more preferably 45 parts by mass, and particularly preferably 35 parts by mass, relative to 100 parts by mass of the particles (A). By setting the content ratio of the radical polymerizable compound (B) in the present composition to the above range, the refractive index can be increased, the sensitivity of the present composition can be made good, and a hardened product having good heat resistance and chemical resistance can be obtained.

[0104] < Cationic polymerizable compound (B4) not having a radical polymerizable group and having a cationic polymerizable group >

[0105] In the present application, a cationic polymerizable compound (B4) not having a radical polymerizable group and having a cationic polymerizable group can be used. As the cationic polymerizable compound (B4), a compound having an epoxy group (oxetanyl group) or a compound having an oxetanyl group (oxetane compound) is preferable. The cationic polymerizable compound (B4) can have one or more cationic polymerizable groups, and preferably one to three.

[0106] As the compound having an epoxy group, an alicyclic compound having an epoxy group (alicyclic epoxy compound), an aromatic compound having an epoxy group (aromatic epoxy compound), a non-cyclic compound having an epoxy group (non-cyclic epoxy compound), and the like can be exemplified, and an alicyclic epoxy compound is preferable. As the alicyclic epoxy compound, 3',4'-epoxycyclohexylmethyl-3,4-epoxycyclohexane carboxylate, (meth)acrylic acid 3,4-epoxycyclohexylalkyl ester (e.g., (meth)acrylic acid 3,4-epoxycyclohexylmethyl ester, and the like), (3,3',4,4'-dihydroxy)bis cyclohexyl ester, hydrogenated bisphenol A type epoxy resin, hydrogenated bisphenol F type epoxy resin, and the like can be exemplified.

[0107] As the oxetane compound, 3-ethyl-3-hydroxymethyloxetane (trade name: Aron Oxetane OXT-101 manufactured by Toagosei Co., Ltd., and the like), 1,4-bis[(3-ethyl-3-oxetanyl)methoxymethyl]benzene (trade name: Aron Oxetane OXT-121 manufactured by Toagosei Co., Ltd., and the like), 3-ethyl-3-(phenoxy-methyl)oxetane (trade name: Aron Oxetane OXT-211 manufactured by Toagosei Co., Ltd., and the like), di(1-ethyl-(3-oxetanyl))methyl ether (trade name: Aron Oxetane OXT-221 manufactured by Toagosei Co., Ltd., and the like), 3-ethyl-3-(2-ethylhexyloxymethyl)oxetane (trade name: Aron Oxetane OXT-212 manufactured by Toagosei Co., Ltd., and the like), and the like can be exemplified.

[0108] In addition, a compound having both an epoxy group and an oxetanyl group can also be used. As the compound, 3-ethyl-3-(2,3-epoxypropyloxymethyl)oxetane can be exemplified.

[0109] In the case where the present composition contains the cationically polymerizable compound (B4), the lower limit value of the content ratio (in the case of containing a plurality, the total content ratio) of the cationically polymerizable compound (B4) with respect to 100 parts by mass of the particles (A) is preferably 5 parts by mass, more preferably 10 parts by mass, and further preferably 20 parts by mass. In addition, the upper limit of the content ratio of the cationically polymerizable compound (B4) with respect to 100 parts by mass of the particles (A) is preferably 100 parts by mass, more preferably 80 parts by mass, and further preferably 60 parts by mass. By setting the content ratio of the cationically polymerizable compound (B4) in the present composition to the range, the refractive index can be increased, the sensitivity of the present composition can be made good, and in addition, a hardened product having good heat resistance and chemical resistance can be obtained.

[0110] As the radical polymerizable compound (B), the polymerizable compounds (B1) to (B4) can be suitably used in combination. Among these, from the viewpoint of the flexibility or the dispersibility, a polymerizable compound having an alkylene oxide chain such as an ethylene oxide chain or a propylene oxide chain, a polymerizable compound having an acidic group is preferred.

[0111] <Photoradical Generator (C)>

[0112] As the photoradical generator (C), a photoradical polymerization initiator which can generate radicals by being subjected to radiation and initiate the polymerization of the radical polymerizable compound (B) can be preferably used. As the photopolymerization initiator used, there is no particular limitation, and for example, O-acyloxime compounds, phenylacetone compounds, bisimidazole compounds, acyloxyphosphine compounds, and the like can be exemplified.

[0113] As the O-acyl oxime compound, for example, 1,2-octanedione 1-[4-(phenylthio)-2-(O-benzoyl oxime)], ethanone-1-〔9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl〕-1-(O-acetyl oxime), 1-(9-ethyl-6-benzoyl-9.H.-carbazol-3-yl)-octan-1-one oxime-O-acetic acid ester, 1-〔9-ethyl-6-(2-methylbenzoyl)-9.H.-carbazol-3-yl〕-ethan-1-one oxime-O-benzoic acid ester, 1-〔9-n-butyl-6-(2-ethylbenzoyl)-9.H.-carbazol-3-yl〕-ethan-1-one oxime-O-benzoic acid ester, ethanone-1-[9-ethyl-6-(2-methyl-4-tetrahydrofurylbenzoyl)-9.H.-carbazol-3-yl]-1-(O-acetyl oxime), ethanone-1-〔9-ethyl-6-(2-methyl-4-tetrahydropyranylbenzoyl)-9.H.-carbazol-3-yl〕-1-(O-acetyl oxime), ethanone-1-〔9-ethyl-6-(2-methyl-5-tetrahydrofurylbenzoyl)-9.H.-carbazol-3-yl〕-1-(O-acetyl oxime), ethanone-1-〔9-ethyl-6-{2-methyl-4-(2,2-dimethyl-1,3-dioxolanyl)methoxybenzoyl}-9.H.-carbazol-3-yl〕-1-(O-acetyl oxime), and the like can be exemplified. In addition, as the commercially available products, for example, ADEKA ARKLS N-1919T, ADEKA ARKLS NCI-831E, ADEKA ARKLS NCI-930, ADEKA ARKLS NCI-730 (manufactured by ADEKA KK), Irgacure OXE01, Irgacure OXE2, Irgacure OXE3, Irgacure OXE4 (manufactured by BASF), and the like can be exemplified.

[0114] As the acetophenone compound, for example, an α-amino ketone compound, an α-hydroxy ketone compound, or the like can be exemplified. As the α-amino ketone compound, for example, 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)-butan-1-one, 2-dimethylamino-2-(4-methylbenzyl)-1-(4-morpholin-4-yl-phenyl)-butan-1-one, 2-methyl-1-(4-methylthiophenyl)-2-morpholinopropan-1-one, or the like can be exemplified. As the α-hydroxy ketone compound, for example, 1-phenyl-2-hydroxy-2-methylpropan-1-one, 1-(4-isopropylphenyl)-2-hydroxy-2-methylpropan-1-one, 4-(2-hydroxyethoxy)phenyl-(2-hydroxy-2-propyl)ketone, 1-hydroxycyclohexyl phenyl ketone, or the like can be exemplified. Further, as the commercially available product, for example, Irgacure 369, Irgacure 369E, Irgacure 379EG, Irgacure 651, Irgacure 184, Irgacure 907 (all manufactured by BASF Corporation), or the like can be exemplified.

[0115] As the bisimidazole compound, for example, 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetraphenyl-1,2'-bisimidazole, 2,2'-bis(2,4-dichlorophenyl)-4,4',5,5'-tetraphenyl-1,2'-bisimidazole, or 2,2'-bis(2,4,6-trichlorophenyl)-4,4',5,5'-tetraphenyl-1,2'-bisimidazole, or the like can be exemplified.

[0116] As the acylphosphine oxide compound, for example, 2,4,6-trimethylbenzoyl-diphenylphosphine oxide, phenyl bis(2,4,6-trimethylbenzoyl)phosphine oxide, or the like can be exemplified.

[0117] The present composition can contain one or a combination of two or more of the photoradical generator (C).

[0118] The lower limit value of the content ratio (in the case of containing a plurality, the total content ratio) of the photoradical generator (C) in the present composition with respect to 100 parts by mass of the particles (A) contained in the present composition is preferably 0.5 parts by mass, more preferably 1 part by mass. Further, the upper limit value of the content ratio of the photoradical generator (C) with respect to 100 parts by mass of the particles (A) contained in the present composition is preferably 40 parts by mass, more preferably 30 parts by mass, further preferably 15 parts by mass, further more preferably 10 parts by mass, particularly preferably 5 parts by mass. By setting the content ratio of the photoradical generator (C) to the range, a photosensitive composition which exhibits good hardenability and transparency can be produced.

[0119] <Dehydrating agent (D)>

[0120] The present composition (1) contains a dehydrating agent (D) which comprises a proto-ester compound. The proto-ester compound is a compound having three groups "-OR 1 " (wherein R 1 is a monovalent hydrocarbon group) bonded to the same carbon, and is represented by the general formula: R 2 -C(OR 1 )3. Here, R 2 is a hydrogen atom or a monovalent organic group. The proto-ester compound is hydrolyzed to become an ester. By including such a proto-ester compound in the photosensitive composition, the proto-ester compound's water absorption can be utilized to improve the photosensitive composition's coating properties over time or storage stability. In addition, the proto-ester compound is preferable in terms of being stable to an alkali developer and being hydrophobic, and having less influence (e.g., on sensitivity) on the exposed portion.

[0121] As the group "-OR 1 " possessed by the proto-ester compound, for example, methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, isobutoxy, t-butoxy, n-pentoxy, phenoxy, methylphenyloxy, and the like can be given. Among these, the group "-OR 1 " possessed by the proto-ester compound is preferably an alkoxy group, and more preferably an alkoxy group having 1 to 4 carbons. Furthermore, the three groups "-OR 1 " possessed by the proto-ester compound are the same or different groups.

[0122] As R 2 , for example, 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, a monovalent aromatic ring group, and the like can be given. Among these, R 2 is preferably a hydrogen atom, a monovalent chain hydrocarbon group, or a monovalent aromatic ring group, and specifically, a hydrogen atom, an alkyl group having 1 to 20 carbons, an alkenyl group having 2 to 20 carbons, an aryl group having 6 to 20 carbons can be given.

[0123] As the proto-ester compound, the following compound represented by Formula (1) can be preferably used.

[0124] R 21 -C-(OR 11 )3... (1)

[0125] (In Formula (1), R 11 is an alkyl group having 1 to 4 carbons or a phenyl group, R 21 is a hydrogen atom, a monovalent chain hydrocarbon group having 1 to 4 carbons, or a monovalent aromatic ring group having 6 to 12 carbons; and the three R 11 are the same or different)

[0126] In Formula (1), R11 The alkyl group can be either straight-chain or branched. Regarding aspects where the impact on sensitivity is less significant, R... 11 Preferably, it is methyl, ethyl, or phenyl, more preferably methyl or ethyl.

[0127] R 21 The chain-like hydrocarbon group is preferably a chain-like or branched alkyl group having 1 to 4 carbon atoms. As R 21 Aromatic cyclic groups, for example, include phenyl, methylphenyl, dimethylphenyl, ethylphenyl, naphthyl, etc. Alternatively, they can be groups formed by substituting at least one hydrogen atom of the chain-like hydrocarbon group or aromatic cyclic group with a halogen atom. Regarding the high improvement in coating properties or storage stability over time, R... 21 Preferably, it is a monovalent aromatic cyclic group, and particularly preferably phenyl.

[0128] Specific examples of orthoester compounds include: triethyl orthochloroacetate, trimethyl orthoformate, triethyl orthoformate, tripropyl orthoformate, triisopropyl orthoformate, tributyl orthoformate, diethylphenyl orthoformate, trimethyl orthoacetate, triethyl orthoacetate, triethyl orthochloroacetate, trimethyl orthobutyrate, triethyl orthobutyrate, trimethyl orthopropionate, triethyl orthopropionate, trimethyl orthovalerate, triethyl orthovalerate, trimethyl orthoisobutyrate, and trimethyl orthobenzoate. The esters include trimethyl orthoacetate, triethyl orthobenzoate, etc., preferably one or more selected from the group consisting of methyl orthoacetate, triethyl orthoacetate, trimethyl orthobenzoate, and triethyl orthobenzoate, more preferably one or more selected from the group consisting of triethyl orthoacetate, trimethyl orthobenzoate, and triethyl orthobenzoate, and even more preferably one or more selected from the group consisting of trimethyl orthobenzoate and triethyl orthobenzoate.

[0129] From the viewpoint of coating properties over time or storage stability, compounds having aromatic ring groups are preferred as orthoester compounds. Specific examples of compounds having aromatic ring groups include R in formula (1). 11 and R 21 Compounds in which at least one group is an aromatic ring.

[0130] Specific examples of orthoester compounds having aromatic ring groups include trimethyl orthobenzoate, triethyl orthobenzoate, and diethylphenyl orthoformate. Among these, trimethyl orthobenzoate and triethyl orthobenzoate are particularly preferred in terms of their superior improvement in coating properties and storage stability over time.

[0131] The boiling point of the orthoester compound is not particularly limited, and is preferably 105°C or higher, more preferably 110°C or higher, and further preferably 115°C or higher at 1 atm. In addition, in the case where the orthoester compound has a high boiling point, even if the photosensitive composition is allowed to stand in a coating mechanism or the like for a certain period of time, the orthoester compound can be inhibited from volatilizing during the period, and the effect of the orthoester compound can be maintained, and thus is preferred.

[0132] Specific examples of the orthoester compound having a boiling point of 105°C or higher at 1 atm 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 orthopentanoate (boiling point: 164°C), trimethyl orthobenzoate (boiling point: 115°C), triethyl orthobenzoate (boiling point: 240°C), and the like, among which trimethyl orthobenzoate (boiling point: 115°C / 3.3 kPa) and triethyl orthobenzoate (boiling point: 240°C) are preferred. In the present specification, the boiling point is a value at 1 atm.

[0133] The dehydrating agent (D) can contain one or a combination of two or more of the orthoester compounds, and in addition, a known dehydrating agent other than the orthoester compound can be contained, and it is preferred that only the orthoester compound be contained.

[0134] The lower limit value of the content ratio of the dehydrating agent (D) in the present composition is preferably 1 part by mass, more preferably 3 parts by mass, and further preferably 5 parts by mass, relative to 100 parts by mass of the particles (A) contained in the present composition. In addition, the upper limit value of the content ratio of the dehydrating agent (D) is preferably 40 parts by mass, more preferably 30 parts by mass, and further preferably 25 parts by mass, relative to 100 parts by mass of the particles (A) contained in the present composition. By setting the content ratio of the dehydrating agent (D) to the above range, a photosensitive composition having excellent coating properties over time and storage stability can be produced, and thus is preferred.

[0135] In the present composition (1), components other than the particle (A), the radical polymerizable compound (B), the photo radical generator (C), and the dehydrating agent (D) can be contained. As the other components, for example, a photo acid generator (E), a solvent (F), a binder resin (G), a surfactant (H), a close contact aid (I), and the like can be exemplified. In addition, in the present composition (2), components other than the particle (A), the radical polymerizable compound (B), and the photo radical generator (C) can be contained. As the other components, for example, the dehydrating agent (D), the photo acid generator (E), the solvent (F), the binder resin (G), the surfactant (H), the close contact aid (I), a sensitizer (J), and the like can be exemplified.

[0136] <Photo acid generator (E)>

[0137] The photo acid generator (E) refers to a compound that generates an acid by irradiation of light or other radiation. As the radiation, for example, ultraviolet rays, far ultraviolet rays, X-rays, charged particle beams, and the like can be exemplified. By the generation of the acid, the cationic polymerization of the cationic polymerizable compound can be started. Therefore, in the case where the radical polymerizable compound (B) contains the polymerizable compound (B3), it is preferable to include the photo acid generator (E).

[0138] As the photo acid generator (E), for example, an oxime sulfonate compound, a sulfimide compound, a halogen-containing compound, a diazomethane compound, a sulfone compound, a sulfonate compound, a carboxylate compound, an onium salt, and the like can be exemplified. As specific examples of these compounds, for example, the compounds described in Japanese Patent Application Publication No. 2020-026515 can be exemplified. Among these, the onium salt is preferable.

[0139] As the onium salt, diphenyliodonium salts, triphenylsulfonium salts, sulfonium salts, benzothiazolium salts, tetrahydrothiophenium salts, and the like can be exemplified. As the diphenyliodonium salt, for example, diphenyliodonium tetrafluoroborate, 4-isobutylphenyl-4'-tolylcarbonyliodoniurn hexafluorophosphate can be exemplified. As the triphenylsulfonium salt, for example, triphenylsulfonium triflate, triphenylsulfonium hexafluoroantimonate, triphenylsulfonium hexafluorophosphate, triphenylsulfonium tetrakis(pentafluorophenyl)borate, diphenyl[4-(phenylthio)phenyl]sulfonium hexafluorophosphate, and the like can be exemplified. Among these, triphenylsulfonium hexafluoroantimonate, diphenyl[4-(phenylthio)phenyl]sulfonium hexafluorophosphate are preferable.

[0140] The present composition can contain one or a combination of two or more of the photo acid generators (E).

[0141] In the case where the present composition contains the photoacid generator (E), the lower limit value of the contained proportion (the total contained proportion in the case of containing a plurality) of the photoacid generator (E) with respect to 100 parts by mass of the particles (A) contained in the present composition is preferably 0.1 part by mass, more preferably 0.2 part by mass, further preferably 0.5 part by mass, and further more preferably 1 part by mass. In addition, the upper limit value of the contained proportion of the photoacid generator (E) with respect to 100 parts by mass of the particles (A) contained in the present composition is preferably 10 parts by mass, more preferably 5 parts by mass. By setting the contained proportion of the photoacid generator (E) to the range, a photosensitive composition which exhibits good hardenability can be produced.

[0142] In the case where the present composition uses the photoacid generator (E), the polymerizable compound (B3), or a compound having a cationically polymerizable group such as an oxiranyl group or an oxetanyl group in the adhesion aid (I), a polymerizable compound (B4) can be used. In addition, in the case where the present composition uses the photoacid generator (E), a sensitizer (J) can be used in order to improve the sensitivity.

[0143] <Solvent (F)>

[0144] 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 as necessary are dissolved or dispersed in a solvent. As the solvent (F), an organic solvent which dissolves the particles (A), the radical polymerizable compound (B), the photoradical generator (C), and the dehydrating agent (D) and does not react with each component is preferred.

[0145] As specific examples of the solvent (F), for example, alcohols such as methanol, ethanol, isopropanol, butanol, octanol, diacetone alcohol, and the like; 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, 3-methoxypropyl methyl acetate, 3-ethoxypropyl ethyl acetate, and the like; ethers such as ethylene glycol monobutyl ether, propylene glycol monomethyl ether, ethylene glycol diethylene glycol monomethyl ether, ethylene glycol diethylene glycol ethyl methyl ether, dimethyleneglycol dimethyl ether, diethylene glycol dimethyl ether, diethylene glycol ethyl methyl ether, and the like; amides such as dimethylformamide, N,N-dimethylacetamide, N-methylpyrrolidone, and the like; ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclopentanone, cyclohexanone, and the like; and aromatic hydrocarbons such as benzene, toluene, xylene, ethylbenzene, and the like are exemplified. Among these, as the solvent (F), at least one selected from the group consisting of alcohols, ethers, and esters is preferred, and 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 is more preferred.

[0146] As the solvent (F), from the viewpoint of the coating property over time, a solvent containing a solvent having a high boiling point (for example, 160°C or higher) is preferred.

[0147] <Adhesive Resin (G)>

[0148] The adhesive resin (G) is preferably a polymer having an acidic group. As the acidic group, a carboxyl group, a phenolic hydroxyl group, a fluorinated hydroxyl alkyl group, and the like can be exemplified. The adhesive resin is preferably an alkali-soluble resin. Here, the "alkali-soluble" means a polymer capable of being dissolved or swelled in a 2.38 mass% concentration aqueous solution of tetramethylammonium hydroxide (TMAH) at 25°C. The fluorinated hydroxyl alkyl group means a group in which any hydrogen atom bonded to carbon of a hydroxyl alkyl group is replaced with a fluorine atom.

[0149] As the adhesive resin (G), a polymer having an ethylenic unsaturated monomer as a constituent unit can be preferably used. As the ethylenic unsaturated monomer constituting the polymer, the same compounds as exemplified as the monofunctional polymerizable compound (B1) can be exemplified, and a compound containing a carboxyl group is preferred. In this case, the adhesive resin (G) preferably has 5 mass% or more of a structural unit derived from the compound containing a carboxyl group, more preferably 10 mass% or more, and further preferably 20 mass% or more, with respect to the total structural units constituting the adhesive resin (G).

[0150] In the case where the adhesive resin (G) is a polymer having an ethylenic unsaturated monomer as a constituent unit, the polymer can be produced, for example, using the ethylenic unsaturated monomer, in the presence of a polymerization initiator or the like, in a suitable solvent, according to a known method such as radical polymerization. As the polymerization initiator, azo compounds such as 2,2'-azobis(isobutyronitrile), 2,2'-azobis(2,4-dimethylvaleronitrile), and dimethyl 2,2'-azobis(isobutyrate) can be exemplified. The use ratio of the polymerization initiator is preferably 0.01 mass part to 30 mass parts with respect to 100 mass parts of the total amount of the monomers used in the reaction. As the polymerization solvent, alcohols, ethers, ketones, esters, hydrocarbons, and the like can be exemplified, specifically, the solvents exemplified in the solvent (F) can be exemplified. The amount of the polymerization solvent used is preferably an amount such that the total amount of the monomers used in the reaction is 0.1 mass% to 60 mass% with respect to the entire 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 kind of the polymerization initiator and the monomer or the reaction temperature, and is usually 0.5 hours to 10 hours.

[0151] As the binder resin (G), in addition to the polymer having ethylenic unsaturated monomer as a constituent unit, for example, a polymer having a phenolic hydroxyl group such as a novolak resin, a phenol-xylenol condensation resin, a cresol-xylenol condensation resin, a phenol-dicyclopentadiene condensation resin, and the like can be exemplified. In addition, as the binder resin (G), an alkali-soluble polyorganosiloxane, an alkali-soluble polyimide, an alkali-soluble polybenzoxazole, and the like can be used. As specific examples of the alkali-soluble polyorganosiloxane, for example, the polymers described in International Publication No. 2017 / 188047, International Publication No. 2017 / 169763, and the like can be exemplified. As specific examples of the alkali-soluble polyimide and polybenzoxazole, for example, the polymers described in International Publication No. 2017 / 169763, International Publication No. 2017 / 159876, and the like can be exemplified.

[0152] By containing the binder resin (G) in the present composition, improvement of alkali developability can be achieved, on the other hand, there is a tendency that the surface planarity of the obtained hardened product decreases. Therefore, depending on the purpose of use of the obtained hardened product, it can be determined whether or not to formulate the binder resin (G), and the formulation amount thereof. Specifically, in the use in which the surface planarity of the obtained hardened product is required, it is preferable not to use the binder resin (G), and in the use in which improvement of alkali developability is required, it is preferable to use the binder resin (G).

[0153] The present composition can contain one or a combination of two or more of the binder resin (G).

[0154] In the case where the present composition contains the binder resin (G), the content ratio (in the case of containing a plurality, the total content ratio) of the binder resin (G) with respect to 100 parts by mass of the particles (A) contained in the present composition 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.

[0155] <SURFACE ACTIVE AGENT (H)>

[0156] The surface active agent (H) can be used for improving the coatability (wet spreadability or reduction of coating unevenness) of the present composition. As the surface active agent (H), for example, a fluorine-based surface active agent, a silicone-based surface active agent, a nonionic surface active agent can be exemplified.

[0157] As specific examples of the surfactant (H), as a fluorine-based surfactant, the following trade names can be listed: Megafac F-171, Megafac F-172, Megafac F-173, Megafac F-251, Megafac F-430, F-554, F-563 (manufactured by DIC Corporation); Fluorad FC430, Fluorad FC431 (manufactured by Sumitomo 3M Limited); Asahi Guard AG710, Surflon S-382, Surflon SC-101, Surflon SC-102, Surflon SC-103, Surflon SC-104, Surflon SC-105, Surflon SC-106, Surflon S-611 (manufactured by AGC Seimi Chemical Co., Ltd.); Polyflow No. 75, Polyflow No. 95 (manufactured by Kyoeisha Chemical Co., Ltd.); FTX-218 (manufactured by NEOS Corporation); Eftop EF301, Eftop EF303, Eftop EF352 (manufactured by New Afton Chemical Co., Ltd.), and the like.

[0158] As a silicone-based surfactant, the following trade names can be listed: SH200-100cs, SH-28PA, SH-30PA, SH-89PA, SH-190, SH-8400, FLUID, SH-193, SZ-6032, SF-8428, DC-57, DC-190, PAINTAD 19, FZ-2101, FZ-77, FZ-2118, L-7001, L-7002 (manufactured by Toray Dow Corning Silicone Co., Ltd.); organosiloxane polymer KP341 (manufactured by Shin-Etsu Chemical Co., Ltd.); BYK-300, BYK-306, BYK-310, BYK-313, BYK-320, BYK-330, BYK-331, BYK-335, BYK-341, BYK-344, BYK-370, BYK-340, BYK-345 (manufactured by BYK-Chemie Japan K.K.).

[0159] As the nonionic surfactant, for example, polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene oleyl ether, polyoxyethylene n-octylphenyl ether, polyoxyethylene n-nonylphenyl ether, polyethylene glycol dilaurate, polyethylene glycol distearate, or the like can be exemplified.

[0160] The present composition can contain one or a combination of two or more of the surfactants (H).

[0161] In the case where the surfactant (H) is formulated in the present composition, the content ratio (in the case of containing a plurality, the total content ratio) of the surfactant (H) 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, further preferably 0.01 parts by mass or more and 3 parts by mass or less, further more preferably 0.01 parts by mass or more and 1.5 parts by mass or less, particularly preferably 0.02 parts by mass or more and 1.2 parts by mass or less, with respect to 100 parts by mass of the particles (A) contained in the present composition.

[0162] <Adhesion aid (I)>

[0163] The adhesion aid (I) is a component for improving the adhesion of the obtained hardened film to the substrate. As the adhesion aid (I), a functional silane coupling agent having a reactive functional group such as a carboxyl group, a methacryloyl group, a vinyl group, an isocyanate group, an oxacyclopropyl group, or the like is preferable.

[0164] As the functional silane coupling agent, for example, trimethoxysilylbenzoic acid, γ-methacryloyloxypropyltrimethoxysilane, vinyltriacetyloxy silane, vinyltrimethoxysilane, γ-isocyanatopropyltriethoxysilane, γ-glycidoxypropyltrimethoxysilane, β-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, β-(3,4-epoxycyclohexyl)ethyltriethoxysilane, or the like can be exemplified.

[0165] The present composition can contain one or a combination of two or more of the adhesion aids (I).

[0166] In the case where the present composition contains the adhesion aid (I), the content ratio (in the case of containing a plurality, the total content ratio) of the adhesion aid (I) 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, further preferably 1 part by mass or more and 35 parts by mass or less, further more preferably 1 part by mass or more and 15 parts by mass or less, particularly preferably 3 parts by mass or more and 10 parts by mass or less, with respect to 100 parts by mass of the particles (A) contained in the present composition.

[0167] <Sensitizer (J)>

[0168] In the present application, a sensitizer is used for the purpose of promoting polymerization. As the sensitizer, for example, an amine-based sensitizer, an alkoxyanthracene-based sensitizer can be listed. As the amine-based sensitizer, triethanolamine, methyldiethanolamine, triisopropanolamine, methyl 4-dimethylamino benzoate, ethyl 4-dimethylamino benzoate, isoamyl 4-dimethylamino benzoate, 2-dimethylaminoethyl benzoate, 2-ethylhexyl 4-dimethylamino benzoate, N,N-dimethyl-p-toluidine, 4,4'-bis(dimethylamino)benzophenone (commonly: Michler's ketone), 4,4'-bis(diethylamino)benzophenone, 4,4'-bis(ethylmethylamino)benzophenone, and the like can be listed. As the alkoxyanthracene-based sensitizer, 9,10-dimethoxyanthracene, 9,10-dibutoxyanthracene, 2-ethyl-9,10-dimethoxyanthracene, 9,10-diethoxyanthracene, 2-ethyl-9,10-diethoxyanthracene, and the like can be listed.

[0169] In the case where the present composition contains the sensitizer (J), the content ratio (in the case of containing a plurality, the total content ratio) of the sensitizer (J) 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, further preferably 0.05 parts by mass or more and 5 parts by mass or less, further more preferably 0.05 parts by mass or more and 3 parts by mass or less, with respect to 100 parts by mass of the particles (A) contained in the present composition.

[0170] As other components, in addition to the above, for example, a polymerization inhibitor, an antioxidant, a softening agent, a plasticizer, an ultraviolet absorber, and the like can be listed. The blending ratio of these components is appropriately selected within a range not impairing the effects of the present disclosure according to each component.

[0171] The present composition (1) can be obtained by mixing the particles (A), the radical polymerizable compound (B), the photoradical generator (C), the dehydrating agent (D), and other components, if any, at a prescribed ratio, and the present composition (2) can be obtained by mixing the particles (A), the radical polymerizable compound (B), the photoradical generator (C), and other components, if any, at a prescribed ratio. The composition obtained by mixing each component can be filtered, for example, using a filter having a pore size of 0.5 μm or less.

[0172] The solid content concentration of the present composition (i.e., the proportion of the total mass of components other than the solvent in the photosensitive composition with respect to the total mass of the photosensitive composition) can be appropriately selected in consideration of viscosity or volatility, etc. The solid content concentration of the present composition is preferably in the range of 3 to 60 mass%. If the solid content concentration is 3 mass% or more, the film thickness of the coating film can be sufficiently ensured when the present composition is applied to a substrate, which is preferable in this respect. In addition, if the solid content concentration is 60 mass% or less, the film thickness of the coating film does not become excessively large, and furthermore, the viscosity of the present composition can be moderately increased, and good coatability can be ensured, which is preferable in this respect. The solid content concentration in the present composition is more preferably 5 to 55 mass%, and furthermore preferably 10 to 50 mass%.

[0173] The amount of moisture contained in the present composition (2) is less than 2000 ppm, preferably 1500 ppm or less, more preferably 1200 ppm or less, and furthermore preferably 1000 ppm or less. By the amount of moisture being in the range described above, stable coatability can be obtained. The amount of moisture in the composition can be measured using the method described in the Examples. In addition, in the present composition (1) as well, the amount of moisture described above is preferable.

[0174] Method for producing a hardened product

[0175] By using the photosensitive composition prepared as described above, a hardened product can be produced. The present composition is particularly suitable as a negative-type pattern forming material that is exposed to light for a portion of the film formed from the photosensitive composition, the unexposed portion is dissolved in an alkaline developer, and the pattern (i.e., the portion formed from the photosensitive composition) thus obtained is hardened by heat treatment.

[0176] The hardened product of the present disclosure is produced, for example, by a method including the following processes (I) to (IV).

[0177] (I) Process of applying the present composition to a substrate

[0178] (II) Process of irradiating the present composition applied to the substrate with radiation

[0179] (III) Process of developing the present composition after the radiation

[0180] (IV) Process of heating the present composition after the development at a temperature of 100°C or lower to harden it

[0181] Hereinafter, each process (processes (I) to (IV)) in the production method of the present disclosure will be described.

[0182] <Process (I): Coating Process>

[0183] Step (I) is a step of forming a coating film on a substrate by applying the present composition on the substrate. As the substrate, for example, glass substrates, silicon wafers, plastic substrates, plastic films, and substrates on the surfaces of which coloring resist, overcoat, anti-reflection film, various metal thin films, sealing film, and the like are formed can be exemplified. As the plastic substrates and plastic films, for example, resin substrates and films containing plastic such as polyethylene terephthalate (PET), polybutylene terephthalate (PBT), polyether sulfone, polycarbonate, polyimide, and the like can be exemplified. In these substrates, various elements (for example, light-receiving elements such as photodiodes, or light-emitting elements such as organic light-emitting diodes) can also be provided in advance.

[0184] As the application method of the present composition, for example, a suitable method such as spray method, roll coating method, spin coating method (spin coating method), slit die coating method, bar coating method, inkjet method, and the like can be employed. Among these, the spin coating method, bar coating method, or slit die coating method is preferable as the application method.

[0185] After the present composition is applied on the substrate, the present composition can be subjected to a preheating treatment (pre-baking) for the purpose of preventing dripping and the like. The conditions of the pre-baking can be suitably set depending on the kind or the use ratio of each component, and the like. The conditions of the pre-baking can be set to, for example, conditions at 60°C to 100°C for 30 seconds to 10 minutes or so. From the viewpoint that the present composition can be applied to an organic EL element, the pre-baking temperature is preferably 60°C to 90°C. The film thickness of the coating film formed is preferably 0.1 μm to 20 μm, more preferably 0.2 μm to 15 μm, based on the value after the pre-baking.

[0186] <Step (II): Exposure Step>

[0187] Step (II) is a step of irradiating at least a part of the coating film formed in Step (I) with a radiation. By the radiation irradiation, a hardening reaction is performed in the exposed part. In Step (II), the radiation irradiation of the coating film is usually performed with a mask interposed. The mask can also be a multi-gray scale mask such as a halftone mask or a gray tone mask.

[0188] As the radiation to be irradiated to the coating film, for example, ultraviolet rays, far ultraviolet rays, X-rays, charged particle beams, and the like can be exemplified. As the ultraviolet rays, for example, g-rays (wavelength: 436 nm), i-rays (wavelength: 365 nm), KrF excimer laser light (wavelength: 248 nm), and the like can be exemplified. As the X-rays, for example, synchrotron radiation and the like can be exemplified. As the charged particle beams, for example, electron beams and the like can be exemplified. Among these, the radiation to be irradiated to the coating film is preferably ultraviolet rays, and more preferably ultraviolet rays having a wavelength of 200 nm or more and 380 nm or less. As the light source to be used, for example, a low-pressure mercury lamp, a high-pressure mercury lamp, a deuterium lamp, a metal halide lamp, an argon resonance lamp, a xenon lamp, an excimer laser, and the like can be exemplified. As the exposure amount of the radiation, 500 J / m 2 ~ 5,000 J / m 2 (50 mJ / cm 2 ~ 500 mJ / cm 2 ).

[0189] <Process (III): Developing Process>

[0190] Process (III) is a process of developing the coating film on which the radiation has been irradiated by Process (II), thereby forming a pattern on the substrate. By the developing process, the unexposed portion in the coating film formed on the substrate can be removed, and a pattern including the exposed portion can be formed on the substrate.

[0191] As the developing solution, for example, an aqueous solution of an alkali (basic compound) 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, 1,5-diazabicyclo[4.3.0]-5-nonane, and the like can be exemplified. In addition, an aqueous solution obtained by adding an appropriate amount of a water-soluble organic solvent such as methanol or ethanol or a surfactant to the aqueous solution of the alkali, or adding a small amount of various organic solvents capable of dissolving the present composition can also be used as the developing solution.

[0192] As the developing method, for example, a suitable method such as a coat method, an immersion method, a shake immersion method, a spray method, and the like can be employed. The developing time can be appropriately adjusted depending on the composition of the present composition. The developing time is, for example, 20 seconds to 120 seconds.

[0193] <Process (IV): Heating Process>

[0194] Process (IV) is a process of heating the pattern after development at 100°C or lower. By the heating treatment of process (IV), further hardening is performed, and a hardened product showing good heat resistance and chemical resistance can be obtained. The heating treatment can be performed using a heating device such as an oven or a hot plate, for example. In the case where a lenticule is obtained in the form of a hardened product, the pattern after development can be made to flow by the heating treatment of process (IV), and thus a semispherical lenticule can be obtained.

[0195] From the viewpoint of being able to be applied to an organic EL element, the heating temperature in process (IV) is 100°C or lower, preferably 95°C or lower, and more preferably 90°C or lower. In addition, from the viewpoint of obtaining a hardened product having high heat resistance and chemical resistance, the heating temperature in process (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 the heating device or the like. For example, in the case where heating is performed using a hot plate, the heating time is, for example, 5 minutes to 60 minutes. In addition, in the case where heating is performed using an oven, the heating time is, for example, 10 minutes to 90 minutes. In process (IV), a step-and-repeat baking method in which heating treatment is performed a plurality of times can also be used.

[0196] The production method of the present disclosure can further include, as an arbitrary process, a process of irradiating a hardened product before or after the heating process based on process (IV) with a radiation (hereinafter, also referred to as "post-exposure process"). By the irradiation of the radiation (hereinafter, also referred to as "post-exposure") in the post-exposure process, the heat resistance or chemical resistance or the like can be further improved, and a hardened product having higher reliability can be produced. As for the kind of the radiation or the exposure conditions in the post-exposure, the same conditions as those of process (II) can be adopted. In addition, the wavelength or the amount of irradiation of the light source or the like conditions at the time of the post-exposure can be the same as or different from those of process (II).

[0197]

[0198] A hardened film of the present disclosure can be formed by hardening the photosensitive composition. According to the present composition, a hardened product having a high refractive index, specifically, a hardened product having a refractive index of 1.60 or higher at a wavelength of 550 nm can be obtained. In addition, according to the present composition, a hardened film having a high refractive index, preferably, a refractive index of 1.68 or higher, and more preferably, a refractive index of 1.70 or higher at a wavelength of 550 nm can be obtained.

[0199] The present composition has high solubility to an alkali developer, and has excellent storage stability or coating properties over time. Therefore, according to the present composition, by the exposure treatment and the development treatment of the present composition, a hardened product having a desired pattern shape can be obtained, and the same hardened product can be obtained even after a certain period of time.

[0200] ​The hardened film is suitable as an optical member for a display element or an imaging element. The optical member is preferably an optical path adjusting member that adjusts the path of light for a light condensing member that improves the light extraction efficiency of a display element, a light receiving element (photodiode) included in a camera or the like, or the like.

[0201] Display element

[0202] The display element of the present application includes a hardened film formed from the photosensitive composition. As the display element, for example, a liquid crystal display element, an organic EL display element, a micro light emitting diode (LED) display element, or the like can be exemplified.

[0203] Imaging element

[0204] The imaging element of the present application includes a hardened film formed from the photosensitive composition. The hardened film of the present application is preferably used as an optical path adjusting member that adjusts the path of light for a light condensing member that improves the light extraction efficiency of a display element, a light receiving element (photodiode) included in a camera or the like, or the like.

[0205] Examples

[0206] Hereinafter, the present application will be specifically described by way of examples, but the present application is not limited to these examples. Furthermore, "parts" and "%" in the examples and comparative examples are mass-based unless otherwise specified. In the present examples, the weight average molecular weight (Mw) of the polymer (binder resin) is measured by the following method.

[0207] [Weight average molecular weight (Mw)]

[0208] The Mw of the polymer (binder resin) is a polystyrene conversion value measured by the following method and conditions.

[0209] • Measurement method: Gel Permeation Chromatography (GPC) method

[0210] • Apparatus: GPC-101 manufactured by Showa Denko K.K.

[0211] • GPC column: GPC-KF-801, GPC-KF-802, GPC-KF-803, and GPC-KF-804 manufactured by Shimadzu GLC, Inc. combined

[0212] • Mobile phase: Tetrahydrofuran

[0213] • Column temperature: 40°C

[0214] • Flow rate: 1.0 mL / minute

[0215] • Sample concentration: 1.0 mass%

[0216] • Sample injection amount: 100 μL

[0217] • Detector: differential refractometer

[0218] • Standard substance: monodisperse polystyrene

[0219] [average particle diameter]

[0220] The average particle diameter of the particles is the D50 particle diameter (particle diameter indicating the 50% cumulative value of the cumulative distribution curve, i.e., the median diameter) in the measurement using the dynamic light scattering method, and was measured using a Microtrac Wave II-EX150 manufactured by Microtrac Bell.

[0221] < Synthesis of the adhesive resin (G-1) >

[0222] [Synthesis Example 1]

[0223] A flask including a cooling tube and a stirrer was charged with propylene glycol monomethyl ether acetate 100 parts by mass and subjected to nitrogen substitution. It was heated to 80°C, and at this temperature, a mixed solution of propylene glycol monomethyl ether acetate 100 parts by mass, methyl methacrylate 15 parts by mass, styrene 15 parts by mass, benzyl methacrylate 5 parts by mass, 2-hydroxyethyl methacrylate 15 parts by mass, 2-ethylhexyl methacrylate 23 parts by mass, N-phenylmaleimide 12 parts by mass, succinic acid mono(2-acryloyloxyethyl) ester 15 parts by mass, and 2,2'-azobis(2,4-dimethylvaleronitrile) 6 parts by mass was added dropwise over 1 hour, the temperature was maintained, and polymerization was performed for 2 hours. Then, the temperature of the reaction solution was raised to 100°C, and further polymerization was performed for 1 hour, thereby obtaining an adhesive resin solution (solid content concentration: 33 mass%). The Mw of the obtained adhesive resin solution was 12,200. The adhesive resin solution was used as the "adhesive resin (G-1)".

[0224] < Preparation of the particle dispersion liquid >

[0225] [Preparation Example 1] Zirconium oxide particle dispersion liquid (A-1)

[0226] Pure water 268 g was mixed into a zirconium 2-ethylhexanoate mineral spirit solution (manufactured by the First Dilution Element Chemical Industry (Co.)) 782 g. The obtained mixture was charged into an autoclave with a stirrer, and the atmosphere in the reaction vessel was replaced with nitrogen. Then, the reaction solution was heated to 180°C, and the reaction was carried out for 16 hours, whereby zirconia was synthesized. The pressure in the vessel at the time of reaction at 180°C was 1.03 MPa. The reaction solution after the reaction was taken out, and the precipitate deposited at the bottom was separated by filtration, washed with acetone, and dried. The dried precipitate 100 g was dispersed in toluene 800 mL, and a white turbid solution was obtained.

[0227] Next, as a purification step, the precipitate was filtered again using a quantitative filter paper (manufactured by Advantec Toyo (Co.), No. 5C) to remove coarse particles and the like. Next, white zirconia particles were recovered by removing toluene from the filtrate after concentration under reduced pressure.

[0228] The obtained zirconia particles 10 g were dispersed in toluene 90 g, and a transparent dispersion liquid was obtained. In the obtained transparent dispersion liquid, 3-methacryloyloxypropyltrimethoxysilane 1.5 g (manufactured by Shin-Etsu Chemical Industry (Co.), KBM-503) was added as a surface coating agent, and the mixture was heated to reflux at 90°C for 1 hour. Then, the dispersed particles were coagulated by adding n-hexane to the dispersion liquid after the reflux treatment, and the dispersion liquid became white turbid. The coagulated particles were separated from the white turbid liquid using a filter paper, and dried at room temperature, whereby zirconia particles surface-treated with 2-ethylhexanoic acid and 3-methacryloyloxypropyltrimethoxysilane were prepared. The average particle diameter of the obtained coated zirconia particles was 12 nm. In addition, propylene glycol monomethyl ether (PGME) was added to the white powder and stirred, and a zirconia particle dispersion liquid containing 80% by mass of the coated zirconia particles was obtained (this was used as "zirconia particle dispersion liquid (A-1)"). The average particle diameter of the coagulated particles in the zirconia particle dispersion liquid (A-1) was 12 nm.

[0229] [Preparation Example 2] Zirconia Particle Dispersion Liquid (A-2)

[0230] A zirconia particle dispersion liquid (A-2) was prepared in the same manner as in Preparation Example 1, except that the solvent (PGME) of the particle dispersion liquid (A-1) was changed to propylene glycol monomethyl ether acetate (PGMEA). The average particle diameter of the particles in the zirconia particle dispersion liquid (A-2) was 12 nm.

[0231] [Preparation Example 3] Zirconium oxide particle dispersion liquid (A-3)

[0232] Zirconium dioxide particles, a dispersant, a binder resin (G-1), and a solvent were mixed so that the amounts of the zirconium dioxide particles, the dispersant, and the binder resin (G-1) and the solvent in the dispersion liquid would be the following amounts, to prepare the particle dispersion liquid (A-3). Further, the following amounts of the solvent are the total amounts including the amounts of the solvent contained in the dispersant and the binder resin (G-1) used when the particle dispersion liquid (A-3) was prepared.

[0233] • Zirconium dioxide particles (manufactured by the First Rare Element Chemical Industry (K.K.), UEP) 100.00 parts by mass

[0234] • Dispersant (manufactured by BYK-Chemie, DISPERBYK-111) 6.67 parts by mass / conversion to solid content

[0235] • Binder resin (G-1) 6.67 parts by mass / conversion to solid content

[0236] • Solvent (PGMEA) 138.51 parts by mass

[0237] The components were sufficiently stirred to obtain a mixed liquid (which will be referred to as mixed liquid Lqb). Next, 20 g of zirconium oxide beads having a diameter of 0.3 mm and 10 g of the mixed liquid Lqb were subjected to dispersion treatment for 6 hours at 25°C to 45°C using a paint shaker. After the dispersion treatment was completed, the beads were separated from the dispersion liquid using a filter, to prepare a zirconium oxide dispersion liquid (A-3) having a content ratio of 45% by mass of the total solid content. The average particle diameter of the particles in the zirconium oxide particle dispersion liquid (A-3) was 38 nm.

[0238] [Preparation Example 4] Titanium dioxide particle dispersion liquid (A-4)

[0239] (1) Manufacture of rutile-type titanium oxide hydrosol

[0240] In a 1 L glass beaker, a titanium oxychloride aqueous solution having a TiO2 concentration of 25% was placed at 240 g (60 g as TiO2), and zirconium oxychloride powder having a ZrO2 concentration of 35% was placed at 5 g (1.8 g as ZrO2), water was added so that the total amount was 1 L, and the zirconium oxychloride powder was confirmed to be dissolved. This solution was referred to as A liquid. In a 2 L flask including a stirring mechanism and a reflux cooler, water was placed at 1 kg, and a tin chloride aqueous solution having a SnO2 concentration of 30% was placed at 20 g (6 g as SnO2), heating was performed with stirring, the temperature was maintained at 60°C at the point in time at which the temperature reached 60°C, and the A liquid was added dropwise over 15 minutes, after which heating was performed until boiling, and the boiling state was maintained under reflux for 3 hours. Then, the temperature was cooled to 40°C, 28% aqueous ammonia solution was used to adjust the pH to 7.0, and filtration and washing were performed, and a filter cake was obtained. Water and 36% hydrochloric acid were added to the filter cake and stirred, and a titanium oxide hydrosol having a pH of 1.3, a TiO2 concentration of 20%, 10% SnO2, and 3% ZrO2 with respect to TiO2 was produced at 300 g.

[0241] (2) Coating treatment of the hydrosol

[0242] In a 2 L glass beaker, 200 g (40 g as Ti02) of the titanium oxide sol of 20% Ti02concentration obtained in the above (1) was placed, ion exchange water was added to dilute it to 4% Ti02concentration, and 5.2 g of 3-glycidyloxypropyltrimethoxysilane (manufactured by Shin-Etsu Chemical Co., organosilane KBM-403) was added thereto while stirring. The solution was referred to as B liquid. In another 5 L glass beaker, 40 g (4 g as Si02) of a sodium silicate aqueous solution of 10% Si02concentration and 2 g of a 48% sodium hydroxide aqueous solution were placed, and ion exchange water was added to dilute it to a total amount of 1200 g. The B liquid was added dropwise to the solution while stirring over 15 minutes. The pH after the dropwise addition was 10. Next, a 20 g (6 g as Sn02) tin chloride aqueous solution of 30% Sn02concentration was added dropwise to the mixed solution while maintaining the pH at 10 over 15 minutes, and then a 20 g (2 g as Si02) sodium silicate aqueous solution of 10% Si02concentration was added, and the temperature was raised to 80°C. After that, the pH was adjusted to 8 with 1% hydrochloric acid, and the temperature was maintained for 120 minutes. The temperature was lowered to 20°C, the pH was adjusted to 3 with a 10% citric acid aqueous solution, and the liquid was passed through an ultrafiltration module (manufactured by Asahi Kasei Corp., MICROZA SLP-1 053) while supplying ion exchange water equivalent to the amount of filtration, to reduce the electrolyte components until the conductivity was 3 x 10 -3 S / cm or less at a Ti02concentration of 3%. At this stage, the citric acid used as the pH adjuster was removed without remaining. Further, the pH was adjusted to 8 with t-butylamine, and then the same ultrafiltration module was used to concentrate it until the solid content concentration was 20%, to obtain a rutile titanium oxide sol having a solid content concentration of 20%, 15% Si02, and 15% Sn02coated on Ti02.

[0243] (3) Propylene glycol monomethyl ether solvent replacement of the sol

[0244] The coated titanium oxide sol obtained in the above (2) was diluted to 5% Ti02concentration with propylene glycol monomethyl ether, and passed through the same ultrafiltration module while supplying propylene glycol monomethyl ether equivalent to the amount of filtration, and finally the supply of propylene glycol monomethyl ether was stopped, to obtain a titanium dioxide particle dispersion liquid (A-4) having a solid content concentration of 20%, 15% Si02, and 15% Sn02coated on Ti02, and a moisture content of 1% or less. The average particle diameter of the particles in the titanium dioxide particle dispersion liquid (A-4) was 36 nm.

[0245] [Preparation Example 5] Barium titanate particle dispersion liquid (A-5)

[0246] In a Perfluoroalkoxy alkane (PFA) container, 100 parts by mass of barium titanate (manufactured by Sigma-Aldrich, primary particle diameter less than 100 nm) was added with 11 parts by mass of Marpon AC-F3 (polyoxyethylene secondary alkyl ether) manufactured by Matsumoto Yushi Pharmaceutical Co., Ltd., 192 parts by mass of propylene glycol monomethyl ether, and 900 parts by mass of zirconia beads (manufactured by NIKKATO Co., Ltd.) having a particle diameter of 0.1 mm. The mixture was subjected to one-hour oscillation using a paint conditioner (manufactured by RED DEVIL) 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 liquid (A-5). The average particle diameter of the particles in the barium titanate particle dispersion liquid (A-5) was 50 nm.

[0247] [Preparation Example 6] Perylene black particle dispersion liquid (A-6)

[0248] A perylene black particle dispersion liquid (A-6) was prepared by treating 12 parts by mass of C.I. Pigment Black 788 as a perylene black-based black pigment, 6 parts by mass of BYK-LPN21116 (manufactured by BYK-Chemie) as a dispersant (solid content concentration: 40 mass%), 4 parts by mass of the binder resin (G-1) (solid content concentration: 33 mass%) as an adhesive resin, and 78 parts by mass of PGMEA as a solvent, using a bead mill. The average particle diameter of the particles in the perylene black particle dispersion liquid (A-6) was 42 nm.

[0249] <Synthesis of the polymerizable compound (B-3)>

[0250] [Synthesis Example 2]

[0251] In 440 parts by weight of a 50% (w / w) sodium hydroxide aqueous solution / dichloromethane (w / w 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 an interlayer migration catalyst were added, and the mixture was stirred at room temperature under a nitrogen atmosphere for 6 hours. Subsequently, the salts generated from the reaction solution were removed using a glass filter, and the residue was washed thoroughly with dichloromethane. The obtained filtrate was purified three times by separation with dichloromethane and distilled water, and then extracted with dichloromethane. A small amount of activated carbon was then added to the dichloromethane layer to remove discoloration, followed by drying with magnesium sulfate, and finally, the solvent was distilled off by vacuum concentration. The 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 (polymeric compound (B-3)).

[0252] <Preparation of Photosensitive Compositions>

[0253] The following shows the types and abbreviations of the particles (A), free radical polymerizable compounds (B), free radical polymerization initiators (C), dehydrating agents (D), photoacid generators (E), solvents (F), adhesive resins (G), surfactants (H), and bonding aids (I) used in the preparation of the photosensitive composition.

[0254] <(A) particle>

[0255] A-1 to A-6: Particle dispersions (A-1) to (A-6) obtained by preparation examples 1 to 6.

[0256] <(B) Free radical polymerizable compounds>

[0257] B-1: A mixture of dipentaerythritol pentaacrylate and dipentaerythritol hexaacrylate (trade name: KAYARAD DPHA, manufactured by Nippon Kayaku Co., Ltd.)

[0258] B-2: 3-Phenoxybenzyl acrylate (trade name: Light Acrylate POB-A, manufactured by Kyoei Chemical Co., Ltd.)

[0259] B-3: 3-[(4-vinylbenzyl)oxymethyl]-3-ethyloxetane obtained in Synthesis Example 2

[0260] <(C) Photoradical generator>

[0261] C-1: NCI-930 (product name, manufactured by ADEKA (stock))

[0262] <(D) Dehydrating agent>

[0263] D-1: Methyl orthoformate

[0264] D-2: Methyl orthoacetate

[0265] D-3: Triethyl orthoacetate

[0266] D-4: Trimethyl orthobenzoate

[0267] D-5: Triethyl orthobenzoate

[0268] D-6: Acetic anhydride

[0269] <(E) Photoacid Generator>

[0270] E-1: Triphenylsulfonium hexafluoroantimonate

[0271] <(F) Solvent>

[0272] F-1: Propylene glycol monomethyl ether acetate

[0273] F-2: Propylene glycol monomethyl ether

[0274] F-3: 3-Methoxybutylacetic acid ester

[0275] F-4: Diethylene glycol ethyl methyl ether

[0276] F-5: Diacetone alcohol

[0277] F-6: Dipropylene glycol methyl ether acetate

[0278] <(G) Adhesive Resin>

[0279] G-1: The adhesive resin (G-1) obtained by synthesis example 1.

[0280] <(H) surfactant>

[0281] H-1: Polyether-modified silicone additive (trade name: DOWSIL™ SH28 Paint Additive, manufactured by Toray Dow Corning)

[0282] <(I) Adhesive agent>

[0283] I-1: 3-Glycidoxypropyltrimethoxysilane

[0284] I-2: 3-Methacryloxypropyltrimethoxysilane (Trade name: SilaAce S710, manufactured by Chisso Inc.)

[0285] [Example 1] Preparation of photosensitizing composition

[0286] 100.0 parts by weight (converted to solid content) of zirconium oxide particle dispersion (A-1) as particles (A), 10.0 parts by weight (converted to solid content) of binder resin (G-1), 10.0 parts by weight of polymeric compound (B-1) as polymeric compound (B), 15.0 parts by weight of polymeric compound (B-2), 4.0 parts by weight of (C-1) as photoradical generator (C), 10.0 parts by weight of (D-1) as dehydrating agent (D), and 0.05 parts by weight of (H-1) as surfactant (H) were added. Then, (F-1) and (F-2) as solvent (F) were added in a 50:50 ratio (mass ratio) to achieve a solid content concentration of 40.0% by weight. The mixture was stirred and then filtered through a 0.5 μm filter to prepare the photosensitive composition (S-1).

[0287] Preparation of photosensitizing compositions (S-2) to (S-24) [Examples 2 to 21, Comparative Example 1, Comparative Example 2]

[0288] Regarding the particle dispersion, binder resin, free radical polymerizable compound, photoradical generator, dehydrating agent, surfactant, adhesion promoter, and solvent, the materials were mixed according to the ratios listed in Table 1, and photosensitive compositions (S-2) to (S-24) were prepared in the same manner as photosensitive composition (S-1). Furthermore, in Table 1, "-" indicates that the corresponding component was not used. Additionally, in Table 1, the % in the solvent column indicates the mass ratio of each component. For example, in Example 2, a mixed solvent consisting of (F-1) and (F-2) mixed at a mass ratio of 50:50 was used; in Example 10, (F-1) was used alone.

[0289] [Table 1]

[0290]

[0291] <Evaluation Method for Time-Related Coating (Injector Blockage)>

[0292] A 10 mL transparent syringe (manufactured by Musashi Engineering, PSY-10E) is fitted with a stainless steel (SUS) needle (manufactured by Musashi Engineering, SNA-20G-B, inner diameter × needle outer diameter). (mm): 0.61 × 0.91). Place 5 g of the photosensitive composition (S-1 to S-24) into each transparent syringe and quickly cap it with the syringe tip cap (manufactured by Musashi Engineering Co., Ltd., HC-10C). The photosensitive composition flows out from the SUS needle but stops after approximately 20 seconds. Let the transparent syringe stand for a certain period. After this time, remove the syringe tip cap. If the photosensitive composition flows through, it is considered "no clogging in the syringe"; if not, it is considered "clogging in the syringe." Evaluate according to the following criteria.

[0293] A: No syringe blockage occurred even after more than 100 minutes.

[0294] B: The syringe was not blocked after less than 80 minutes, but the syringe became blocked after more than 80 minutes but less than 100 minutes.

[0295] C: The syringe was not blocked when the time was less than 60 minutes, but the syringe became blocked when the time was more than 60 minutes but less than 80 minutes.

[0296] D: The syringe was not blocked after less than 20 minutes, but became blocked after more than 20 minutes but less than 60 minutes.

[0297] E: Syringe blockage occurred in less than 20 minutes.

[0298] <Storage Stability Evaluation (Viscosity Change Rate)>

[0299] For the photosensitive compositions (S-1 to S-24), the viscosity immediately after preparation (initial viscosity) was measured using an E-type viscometer. The photosensitive compositions were then stored at 25°C for one month, and the viscosity was measured again (viscosity after storage). The viscosity change rate was calculated using the following formula, and the compositions were evaluated according to the following evaluation criteria.

[0300] [Number 1]

[0301]

[0302] A: Viscosity change rate is less than 2%.

[0303] B: Viscosity change rate is greater than 2% and less than 5%.

[0304] C: Viscosity change rate is greater than 5% and less than 10%.

[0305] D: Viscosity change rate is above 10%

[0306] <Evaluation of Preservation Stability (Resolution Change)>

[0307] For the photosensitive compositions (S-1 to S-24), the resolution immediately after preparation (initial resolution) was measured according to the following method. Then, the photosensitive compositions were 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 evaluation criteria.

[0308] Resolution change (μm) = (Initial resolution) - (Resolution after storage)

[0309] (Resolution evaluation method)

[0310] Photosensitive compositions (S-1 to S-24) were coated onto 6-inch glass wafers using a spinner, followed by pre-baking at 85°C on a hot plate for 60 seconds to form a 3.0 μm thick coating. A high-pressure mercury lamp (SUSS) was used, with a photomask having a 20 μm aperture, to achieve a cumulative irradiation dose of 100 mJ / cm². 2 Exposure was performed using a 2.38% TMAH aqueous solution (developer temperature: 25°C) for 60 seconds, followed by rinsing with water. The substrate was then heated in a clean oven at 85°C for 60 minutes to form a hardened film on a 6-inch glass wafer. The lower width of the obtained aperture was confirmed using an optical microscope to evaluate the resolution.

[0311] A: Resolution change is less than 1 μm

[0312] B: Resolution variation is greater than 1 μm and less than 3 μm

[0313] C: Resolution change is greater than 3 μm and less than 5 μm

[0314] D: Resolution change is greater than 5 μm

[0315] The evaluation results for the photosensitive compositions (S-1 to S-24) prepared in the Examples and Comparative Examples are shown in Table 2.

[0316] [Table 2]

[0317]

[0318] As shown in Table 2, the photosensitive compositions of Examples 1 to 21 all exhibited good coatability and storage stability over time. In contrast, Comparative Examples 1 to 3 showed poor coating stability, with syringes becoming clogged after less than 60 minutes.

[0319] Next, Examples 22 to 26 and Comparative Example 4 will be described. The compounds used in these examples and comparative examples are as follows.

[0320] <(A) particle>

[0321] A-2, A-4: Particle dispersions (A-2) and (A-4) obtained by preparation examples 2 and 4, respectively.

[0322] <(B) Free radical polymerizable compounds>

[0323] B-4: α-Acryloyloxy-ω-carboxymethyl-polyethylene glycol

[0324] B-5: 4'-(6-Acryloyloxyhexyloxy)biphenyl-4-carboxylic acid (CAS No.: 134903-88-1)

[0325] B-6: 2-Methyl-2-acrylate-2-hydroxyethyl phosphate (CAS No.: 52628-03-2)

[0326] B-7: 2-(2-ethoxyethoxy)ethyl acrylate (CAS No.: 7328-17-8)

[0327] B-8: α-Acryloyl-ω-(Acryloyloxy)poly(ethylene oxide) (CAS No.: 26570-48-9)

[0328] B-9: Tripropylene glycol diacrylate (CAS No.: 42978-66-5)

[0329] B-10: α,α'-[propane-2,2-dimethylbis(4,1-phenylene)]bis[ω-(methacryloyloxy)poly(ethylene oxide)] (CAS No.: 41637-38-1)

[0330] B-11: 3-Ethyl-3-(2,3-epoxypropoxymethyl)oxetane (CAS No.: 15957-34-3)

[0331] B-12: 3,3'-[oxybis(methylene)]bis(3-ethyloxetane) (CAS No.: 18934-00-4)

[0332] <(C) Photoradical generator>

[0333] C-2: Irgacure OXE-01 (manufactured by BASF)

[0334] C-3: Irgacure OXE-02 (manufactured by BASF)

[0335] <(D) Dehydrating agent>

[0336] D-4: Trimethyl orthobenzoate

[0337] <(E) Photoacid Generator>

[0338] E-2: Diphenyl[4-(phenylthio)phenyl]sulfonium hexafluorophosphate

[0339] E-3: 4-Isobutylphenyl-4'-Toluyliodohexafluorophosphate

[0340] <(F) Solvent>

[0341] F-1: Propylene glycol monomethyl ether acetate

[0342] F-2: Propylene glycol monomethyl ether

[0343] F-3: 3-Methoxybutylacetic acid ester

[0344] F-5: Diacetone alcohol

[0345] <(H) surfactant>

[0346] H-2: BYK-310 (manufactured by BYK-Chemie (BYK) Co., Ltd.)

[0347] H-3: BYK-313 (manufactured by BYK-Chemie (BYK) Co., Ltd.)

[0348] H-4: BYK-320 (manufactured by BYK-Chemie (BYK) Inc.)

[0349] H-5: BYK-331 (manufactured by BYK-Chemie (BYK) Co., Ltd.)

[0350] <(I) Adhesive agent>

[0351] I-3: β-(3,4-epoxycyclohexyl)ethyltrimethoxysilane (CAS No.: 3388-04-3)

[0352] I-4: β-(3,4-epoxycyclohexyl)ethyltriethoxysilane

[0353] <(J) Sensers>

[0354] J-1: Ethyl 4-(dimethylamino)benzoate (CAS No.: 10287-53-3)

[0355] J-2: 9,10-Dibutoxyanthracene (CAS No.: 76275-14-4)

[0356] [Example 22] Preparation of photosensitizing composition

[0357] 10.0 parts by mass (converted to solid content) of zirconium oxide particle dispersion (A-2) as particles (A), 16.0 parts by mass of polymeric compound (B-4) and polymeric compound (B-7) as polymeric compound (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 parts by mass of (D-4) as dehydrating agent (D), 6.0 parts by mass of (I-3) as adhesion promoter (I), and 1.0 parts by mass of (H-2) as surfactant (H) were added. Then, (F-3) as solvent (F) was added to achieve a solid content concentration of 40.0% by mass. The mixture was stirred and then filtered through a 0.5 μm filter to prepare the photosensitive composition (S-25).

[0358] [Examples 23-26, Comparative Example 4] Preparation of photosensitive compositions (S-26) to photosensitive compositions (S-30)

[0359] Regarding the particle dispersion, polymerizable compound, photoradical generator, photoacid generator, sensitizer, dehydrating agent, surfactant, adhesion promoter, and solvent, the materials are mixed according to the ratios listed in Table 3 to prepare photosensitive compositions (S-26) to (S-30) in the same manner as photosensitive composition (S-25). Furthermore, in Table 3, "-" indicates that the corresponding component was not used. Additionally, in Table 3, the % in the solvent column indicates the mass ratio of each component.

[0360] [Table 3]

[0361]

[0362] The evaluation results for the photosensitive compositions (S-25 to S-30) prepared in the Examples and Comparative Examples are shown in Table 4.

[0363] [Table 4]

[0364]

[0365] As shown in Table 4, the photosensitive compositions of Examples 22 to 26 all exhibited good coatability and storage stability over time. In contrast, Comparative Example 4 showed poorer coatability and storage stability over time compared to the Examples.

[0366] The results of evaluating the correlation between the moisture content and the coating properties (syringe clogging) of the compositions of Examples 1 to 26 and Comparative Examples 1 to 4 over time are shown in Table 5. Furthermore, the moisture content was determined as follows.

[0367] <Moisture Content Assessment>

[0368] For the photosensitive compositions (S-1 to S-30), the moisture content was determined using a CA-100 electrotitration moisture meter manufactured by Mitsubishi Chemical Analytech Co., Ltd. The titration reagent used was an Aquamicron TMAX / CXU. Measurements were repeated three times, and the average value was calculated as the moisture content of each photosensitive composition.

[0369] [Table 5]

[0370]

[0371] According to the results in Table 5, in Comparative Examples 1 to 4, where the water content was 2000 ppm or higher, the particulate components in the composition tended to aggregate, resulting in poor coatability over time. On the other hand, when the water content was less than 2000 ppm, aggregation was less likely, and the coatability over time was better than in the comparative examples. In particular, when the water content was less than 1000 ppm, the particulate components in the composition did not easily aggregate, and the coatability over time was good without any problems.

Claims

1. A photosensitive composition for forming an optical component, The photosensitive composition comprises particles (A), a free radical polymerizable compound (B), a photoradical generator (C), and a dehydrating agent (D). 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 with 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), R 21 -C-(OR 11 )3 …(1) (In equation (1), R) 11 R is an alkyl or phenyl group having 1 to 4 carbon atoms. 21 It consists of 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; three Rs 11 (Same or different from each other).

4. The photosensitive composition according to claim 1, wherein the orthoester compound has an aromatic ring group.

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

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

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

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

9. A hardened material, formed by hardening the photosensitive composition as described in any one of claims 1 to 8.

10. A method for manufacturing a hardened material, comprising: The process of coating the photosensitive composition as described in any one of claims 1 to 8 onto a substrate; A process of irradiating a photosensitive composition coated on the substrate with radiation; The process of developing the photosensitive composition after irradiation with radiation; and The process of heating the developed photosensitive composition at a temperature below 100°C to harden it.

11. A display element comprising the hardened material as claimed in claim 9.

12. A camera element comprising the hardened material as described in claim 9.

13. A photosensitive composition for forming an optical component, The photosensitive composition comprises particles (A), a radical polymerizable compound (B), and a photoradical generator (C). The water content in the photosensitive composition is less than 2000 ppm.

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