Photosensitive composition, high refractive index film, solid-state image sensor, liquid crystal display device, and organic EL display device.

Abstract

To provide a storage-stable photosensitive composition that has good resolution and good substrate adhesion and can form a high refractive index film by maintaining the refractive index.SOLUTION: A photosensitive composition comprises a dispersant (A), titanium dioxide (B), a polymerizable compound (C) (excluding the dispersant (A)), a binder resin (D), and a solvent (E), where the dispersant (A) includes a dispersant (A1) having six or more acryloyl groups represented by the general formula (1) in the figure.SELECTED DRAWING: Figure 1

Description

[Technical Field]

[0001] The present invention relates to a photosensitive composition used for forming high refractive index films and the like. [Background technology]

[0002] In fields such as imaging optical systems for on-chip color filters in electronic copiers and solid-state image sensors, sealing materials for microlenses and light-emitting elements used in liquid crystal display elements, optical components such as optical waveguides and lenses for optical elements, and optically functional films such as anti-reflective coatings, there is a demand for materials that have a high refractive index and can be easily formed with precision. Patent documents 1 to 3 disclose photosensitive compositions using metal particles and high refractive index films formed therefrom. Titanium oxide and zirconium oxide are used as metal particles to achieve a high refractive index. [Prior art documents] [Patent Documents]

[0003] [Patent Document 1] Japanese Patent Publication No. 2005-189399 [Patent Document 2] Japanese Patent Publication No. 2011-151164 [Patent Document 3] Japanese Patent Publication No. 2014-177614 [Overview of the Initiative] [Problems that the invention aims to solve]

[0004] In order to achieve precise molding in negative resists, it is generally necessary to use materials with high developer solubility to fully develop the unexposed areas and form a precise pattern. However, using materials with high developer solubility to improve resolution can worsen substrate adhesion, making it difficult to achieve both resolution and substrate adhesion with conventional high-refractive-index films, resulting in a decrease in device performance. Furthermore, formulating materials to maintain sufficient resolution and substrate adhesion often requires increasing the amount of binder resin and polymerizable compounds, which can lead to insufficient storage stability.

[0005] The present invention aims to provide a photosensitive composition that exhibits good resolution and adhesion to a substrate, maintains its refractive index, and can form a high refractive index film while maintaining good storage stability. [Means for solving the problem]

[0006] The present invention relates to a photosensitive composition comprising a dispersant (A), titanium dioxide (B), a polymerizable compound (C) (excluding the dispersant (A)), a binder resin (D), and a solvent (E), characterized in that the dispersant (A) comprises a dispersant (A1) having six or more acryloyl groups represented by the following general formula (1) (hereinafter referred to as dispersant (A1)). General formula (1) [ka]

[0007] (In general formula (1), R1 represents any of the following tetravalent organic residues, R2 represents any of the following monovalent organic residues, and R3 represents a hydrogen atom or any of the following monovalent organic residues.) [Effects of the Invention]

[0008] According to the present invention described above, it is possible to provide a photosensitive composition that can form a high refractive index film with good resolution and adhesion to the substrate, while maintaining the refractive index and having good storage stability. Furthermore, the present invention can provide a solid-state image sensor, a liquid crystal display device, and an organic EL display device equipped with a high refractive index film. [Brief explanation of the drawing]

[0009] [Figure 1] Figures 1(a) and 1(b) are schematic cross-sectional views of liquid crystal display devices equipped with color filters, respectively. [Figure 2] Figures 2(a) to 2(c) are schematic cross-sectional views of organic EL display devices equipped with color filters. [Modes for carrying out the invention]

[0010] The terms used in this specification are defined below. When "(meth)acryloyl," "(meth)acrylic," "(meth)acrylic acid," "(meth)acrylate," or "(meth)acrylamide" are used, unless otherwise specified, they refer to "acryloyl and / or methacryloyl," "acrylic and / or methacrylic," "acrylic acid and / or methacrylic acid," "acrylate and / or methacrylate," or "acrylamide and / or methacrylamide," respectively. "CI" as used herein means Color Index (CI). Colorants include pigments and dyes.

[0011] The photosensitive composition of the present invention is a photosensitive composition comprising a dispersant (A), titanium dioxide (B), a polymerizable compound (C) (excluding the dispersant (A)), a binder resin (D), and a solvent (E), wherein the dispersant (A) comprises a dispersant (A1) having six or more acryloyl groups represented by the above general formula (1).

[0012] In order to perform precise patterning in a negative resist, generally, a material with high developer solubility is used to sufficiently develop the unexposed areas to form a precise pattern. However, using a material with high developer solubility to improve resolution causes deterioration of substrate adhesion. In this specification, it is presumed that by using a dispersant having a curability due to an acryloyl group, sufficient curability and adhesion can be maintained, and the resolution can be controlled by using another polymerizable compound and a binder resin in combination. Further, since the dispersant also serves as a curing agent, it is presumed that it can be compatible with the coating film properties without impairing the storage stability.

[0013] <Dispersant (A)> The photosensitive composition of the present invention contains a dispersant (A). The dispersant (A) contains a dispersant (A1). In addition to the dispersant (A1), for example, a resin-type dispersant or the like can be used in combination with the dispersant (A).

[0014] (Dispersant (A1)) The dispersant (A1) is a dispersant having six or more acryloyl groups represented by the following general formula (1). Since the dispersant (A1) has six or more acryloyl groups, it is excellent not only in dispersibility but also in curability and substrate adhesion.

[0015] General formula (1): [Chemical formula]

[0016] In general formula (1), R1 represents any of the following tetravalent organic residues, and R2 represents any of the following monovalent organic residues. Further, R3 represents a hydrogen atom or any of the following monovalent organic residues.

[0017] [Chemical formula] [Chemical formula] [Chemical formula]

[0018] The dispersant (A1) has two sets of adjacent ester groups that contribute to the dispersibility of titanium dioxide (B), and also has six or more acryloyl groups, thus possessing high dispersibility and photocurability with respect to metal oxides. By enhancing the dispersibility and photocurability of titanium dioxide (B) with this dispersant (A1), the photosensitive composition of the present invention has good storage stability and can form a high refractive index film with good resolution and substrate adhesion while maintaining the refractive index. Therefore, it can be suitably used in fields such as imaging optical systems of on-chip color filters in electronic copiers and solid-state image sensors, sealing materials for microlenses and light-emitting elements used in liquid crystal display elements, optical components such as optical waveguides and lenses for optical elements, and optical functional films such as anti-reflective films. Because the dispersant of the photosensitive composition of the present invention has high dispersibility and photocurability with respect to metal oxides, it can contain a sufficient amount of titanium dioxide (B) and form a cured film with a high refractive index. When this is applied to a substrate with a similar refractive index, the resulting laminate does not produce reflection interference fringes and is suitably used for optical applications. Furthermore, because the refractive index of the cured product containing titanium oxide can be controlled to a high degree, it is also suitable as a encapsulating material for optical semiconductor devices.

[0019] In the above general formula (1), R1 is a tetravalent organic residue containing a phenyl skeleton, a biphenyl skeleton, a fluorene skeleton, or a butylene group. Of these, it is more preferable that it be an organic residue containing an aromatic ring, such as a phenyl skeleton, a biphenyl skeleton, or a fluorene skeleton.

[0020] The dispersant (A1) represented by general formula (1) can be synthesized, for example, by reacting a tetracarboxylic dianhydride (x1) represented by general formula (2) below with one or two compounds (x2) selected from pentaerythritol triacrylate and dipentaerythritol pentaacrylate to obtain a compound (X) having a carboxyl group, and then reacting this compound with biphenyl glycidyl ether or glycidyl methacrylate. Furthermore, the dispersant (A1) represented by general formula (1) is also preferred if the carboxyl group compound (X) is synthesized by reacting a tetracarboxylic dianhydride (x1) represented by general formula (2) below with one or two compounds (x2) selected from pentaerythritol triacrylate and dipentaerythritol pentaacrylate, because it possesses sufficient dispersibility and photocurability. Here, from the viewpoint of photocurability and hard coat properties, it is necessary that the above compound (x2) be pentaerythritol triacrylate and dipentaerythritol pentaacrylate.

[0021] General formula (2) [ka] (R1 is the same as in equation (1).)

[0022] Examples of tetracarboxylic dianhydrides (x1) represented by the general formula (2) above include 1,2,4,5-benzenetetracarboxylic dianhydride, 3,3',4,4'-biphenyltetracarboxylic dianhydride having a biphenyl skeleton, 9,9-bis(3,4-dicarboxyphenyl)fluorene dianhydride having a fluorene skeleton, or 9,9-bis[4-(3,4-dicarboxyphenoxy)phenyl]fluorene dianhydride and 1,2,3,4-butanetetracarboxylic dianhydride. Among these, 3,3',4,4'-biphenyltetracarboxylic dianhydride is preferred because it has a biphenyl skeleton, allowing for efficient introduction of the biphenyl skeleton into the molecule of compound (A). Furthermore, it is preferred because it can combine photocurability of the cured film with good dispersibility of titanium dioxide.

[0023] Specific commercially available products of the compound (x2), pentaerythritol triacrylate and dipentaerythritol pentaacrylate, include Viscoat #300 (manufactured by Osaka Organic Chemical Industry Co., Ltd.), KAYARADPET30 (manufactured by Nippon Kayaku Co., Ltd.), PETIA (manufactured by Daicel UC B Co., Ltd.), Arronix M305 (manufactured by Toagosei Co., Ltd.), NK Ester A-TMM-3 LMN (manufactured by Shin Nakamura Chemical Industry Co., Ltd.), Light Acrylate PE-3A (manufactured by Kyoeisha Chemical Co., Ltd.), SR-444 (manufactured by Sartomer Co., Ltd.), Light Acrylate DPE-6A (manufactured by Kyoeisha Chemical Co., Ltd.), KAYARADDPHA (manufactured by Nippon Kayaku Co., Ltd.), and Arronix M402 (manufactured by Toagosei Co., Ltd.).

[0024] Commercially available versions of the above compound (x2) each contain approximately 1-20% by weight of pentaerythritol diacrylate and dipentaerythritol tetraacrylate, which have two hydroxyl groups, as minor components. Therefore, in the reaction to obtain the dispersant (A1), in addition to compound (A1), a resin with high molecular weight components such as reactants derived from the minor components and the dispersant (A1) is also produced simultaneously.

[0025] The reaction between the tetracarboxylic dianhydride (x1) and compound (x2) is a reaction between the two carboxylic acid anhydride groups of the tetracarboxylic dianhydride and the hydroxyl group of compound (x2). For example, the tetracarboxylic dianhydride (x1) and compound (x2) can be reacted in an organic solvent such as cyclohexanone in the presence of a catalyst such as 1,8-diazabicyclo[5.4.0]-7-undecene at a temperature of 50-120°C. In this case, a polymerization inhibitor such as methylhydroquinone (2-METHYLHYDROQUINONE) can be added to the reaction system.

[0026] After the above reaction, the reaction product containing compound (X) having a carboxyl group is Without purification, this can be reacted with the following chemical formula (3), which is biphenyl glycidyl ether, or formula (4), which is glycidyl methacrylate.

[0027] [ka]

[0028] The reaction between compound (X) and biphenyl glycidyl ether represented by chemical formula (3) is a reaction between the carboxyl group of compound (X) and the epoxy group of biphenyl glycidyl ether, and is well known in the field. For example, this reaction can be carried out at a temperature of 50 to 120°C in the presence of an amine catalyst such as dimethylbenzylamine. The same applies to glycidyl methacrylate represented by chemical formula (4).

[0029] These reactions are carried out in the absence of a solvent or in a solvent that is inert to the reaction. Examples of such solvents include hydrocarbon solvents such as n-hexane, benzene, or toluene; ketone solvents such as acetone, methyl ethyl ketone, or methyl isobutyl ketone; ester solvents such as ethyl acetate or butyl acetate; ether solvents such as diethyl ether, tetrahydrofuran, or dioxane; halogen solvents such as dichloromethane, chloroform, carbon tetrachloride, 1,2-dichloroethane, or perclene; and polar solvents such as acetonitrile, N,N-dimethylformamide, N,N-dimethylacetamide, and N,N-dimethylimidazolidinone. These solvents can be used alone or in combination of two or more.

[0030] <Resin-type dispersant> Resin-type dispersants have affinity sites that adsorb to titanium dioxide, steric repulsion sites that are compatible with solvents, and sites that are soluble in developer solutions, thereby improving the resolution of the resist.

[0031] Examples of resin-type dispersants include urethane-based dispersants such as polyurethane, polycarboxylic acid esters such as polyacrylate, unsaturated polyamides, polycarboxylic acids, polycarboxylic acid (partial)amine salts, polycarboxylic acid ammonium salts, polycarboxylic acid alkylamine salts, polysiloxanes, long-chain polyaminoamide phosphates, hydroxyl group-containing polycarboxylic acid esters and their modified products, oily dispersants such as amides and their salts formed by the reaction of poly(lower alkyleneimines) with polyesters having free carboxyl groups, water-soluble resins and water-soluble polymer compounds such as (meth)acrylic acid-styrene copolymers, (meth)acrylic acid-(meth)acrylic acid ester copolymers, styrene-maleic acid copolymers, polyvinyl alcohol, and polyvinylpyrrolidone, polyester-based, modified polyacrylate-based, ethylene oxide / propylene oxide adduct compounds, and phosphate ester-based dispersants.

[0032] Preferred examples of resin-type dispersants having basic functional groups include nitrogen atom-containing graft copolymers, nitrogen atom-containing acrylic block copolymers and urethane polymer dispersants having functional groups in their side chains that include tertiary amino groups, quaternary ammonium bases, nitrogen-containing heterocycles, etc.

[0033] Preferred examples of resin-type dispersants having acidic functional groups include resin-type dispersants having aromatic carboxylic acid structures, which can be manufactured by known methods such as those described in WO2008 / 007776, JP 2008-029901, JP 2009-155406, JP 2010-185934, JP 2011-157416, JP 2009-251481, JP 2007-23195, and JP 1996-143651.

[0034] Furthermore, as disclosed in Japanese Patent Publication No. 2009-185277, it is also preferable to use in combination a resin-type dispersant having an aromatic carboxyl group and a vinyl resin having a tertiary amino group (which has the function of a resin-type dispersant).

[0035] The content of the dispersant (A) is preferably 8 to 16 parts by mass, and more preferably 4 to 20 parts by mass, per 100 parts by mass of the nonvolatile content of the photosensitive composition. By incorporating an appropriate amount, the storage stability of the photosensitive composition can be maintained while improving resolution and substrate adhesion.

[0036] Titanium Oxide (B) The photosensitive composition of the present invention contains titanium dioxide (B). The D50 particle size of titanium dioxide is preferably 0.005 to 0.250 μm. The D50 particle size of titanium dioxide can be measured using, for example, Nikkiso's "NanoTrack UPA" which utilizes dynamic light scattering. In titanium dioxide compositions with a D50 particle size of 0.005 μm or larger, the cohesive force between fine particles is suppressed to the extent that highly transparent primary particle-level dispersibility is maintained. Furthermore, if the D50 particle size is 0.250 μm or less, scattering to visible light is less likely to occur, and the cured film can be kept transparent. In addition, as a measure of other particle sizes, it is preferable to use primary particle sizes of 5 nm to 40 nm.

[0037] Titanium dioxide may be treated on its surface with organic or inorganic substances. Examples of organic treatments include saturated fatty acids and polysiloxane compounds, while examples of inorganic treatments include silicon dioxide, aluminum oxide, and aluminum hydroxide. However, since increasing the amount of surface treatment lowers the titanium dioxide concentration and thus the refractive index, it is preferable to use titanium dioxide with a concentration of 75% or higher.

[0038] From the viewpoint of refractive index and storage stability, rutile-type titanium dioxide is preferred. Rutile-type crystals have a higher refractive index than anatase-type crystals, which can further improve the refractive index of the cured film of the photosensitive composition. In addition, their photocatalytic activity is lower than that of anatase-type crystals, which improves the storage stability of the photosensitive composition.

[0039] Commercially available titanium dioxide products include those manufactured by Ishihara Sangyo Co., Ltd.: ET-300W (ATO coated titanium dioxide), TTO-55(A), TTO-55(B), TTO-55(C), TTO-55(D), TTO-55(S), TTO-55(N), TTO-51(A), TTO-51(C), TTO-S-1, TTO-S-2, TTO-S-3, TTO-S-4, TTO-F-1 (iron-containing titanium dioxide), TTO-F-2 (iron-containing titanium dioxide), TTO-F-3 (iron-containing titanium dioxide), Examples include TTO-F-11 (iron-containing titanium oxide), ST-01, ST-21, ST-30L, ST-31; manufactured by Sakai Chemical Industry Co., Ltd.: STR-60C, STR-60C-LP, STR-100C, STR-100C-LP, STR-100A-LP, STR-100W; manufactured by Teika Co., Ltd.: MT-02, MT-100S, MT-100HD, MT-100SA, MT-500HD, MT-500SA, MT-600SA, MT-700HD, SMT-100SAS, etc.

[0040] The amount of titanium dioxide (B) included is preferably 30 to 70% by mass, and more preferably 40 to 60% by mass, based on 100% by mass of the nonvolatile content of the photosensitive composition. The desired refractive index can be achieved by incorporating an appropriate amount.

[0041] <Polymerizable compound (C)> The photosensitive composition of the present invention contains a polymerizable compound (C). The polymerizable compound (C) is a monomer or oligomer containing a polymerizable unsaturated group. Unlike the dispersant (A1), it does not have a structure with two sets of two adjacent ester groups, and therefore does not contribute to the dispersion of titanium dioxide (B). Polymerizable compounds (C) include polymerizable compounds (C1) with four or fewer polymerizable unsaturated groups, polymerizable compounds with five or more polymerizable unsaturated groups, polymerizable compounds containing acid groups, polymerizable compounds containing urethane bonds, and the like.

[0042] Polymerizable compounds (C1) with four or fewer polymerizable unsaturated groups can improve resolution because the coating film does not harden excessively due to the four or fewer polymerizable unsaturated groups, and therefore has sufficient developability. (Polymerizable compound (C1)) Polymerizable compounds (C1) with four or fewer polymerizable unsaturated groups include, for example, methyl (meth)acrylate, ethyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, cyclohexyl (meth)acrylate, β-carboxyethyl (meth)acrylate, polyethylene glycol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, triethylene glycol di(meth)acrylate, tripropylene glycol di(meth)acrylate, trimethylolpropane tri(meth)acrylate, trimethylolpropane PO-modified tri(meth)acrylate, trimethylolpropane EO-modified tri(meth)acrylate, pentaerythritol tri(meth)acrylate, and 1,6-hexanediol diglycidyl Examples include ether di(meth)acrylate, bisphenol A diglycidyl ether di(meth)acrylate, neopentyl glycol diglycidyl ether di(meth)acrylate, ditrimethylolpropane tetra(meth)acrylate, pentaerythritol tetra(meth)acrylate, ester acrylate, (meth)acrylic acid esters of methylolated melamine, epoxy(meth)acrylate, urethane acrylate, and various other acrylic acid esters and methacrylic acid esters, (meth)acrylic acid, styrene, vinyl acetate, hydroxyethyl vinyl ether, ethylene glycol divinyl ether, pentaerythritol trivinyl ether, (meth)acrylamide, N-hydroxymethyl(meth)acrylamide, N-vinylformamide, acrylonitrile, and the like.

[0043] The polymerizable compound (C1) content is preferably 1 to 19% by mass, and more preferably 5 to 15% by mass, based on 100% by mass of the nonvolatile content of the photosensitive composition. Adding an appropriate amount further improves curability and developability.

[0044] Examples of polymerizable compounds with five or more polymerizable unsaturated groups include pentaerythritol tetra(meth)acrylate, dipentaerythritol hexa(meth)acrylate, and dipentaerythritol penta(meth)acrylate.

[0045] (Acid group-containing polymerizable compound) Examples of acidic groups in polymerizable compounds containing acidic groups include sulfonic acid groups, carboxyl groups, and phosphate groups.

[0046] Examples of polymerizable compounds containing acid groups include esters of polyhydric alcohols and (meth)acrylic acid containing free hydroxyl groups, and dicarboxylic acids; and esters of polyhydric acids and monohydroxyalkyl (meth)acrylates. Specific examples include monoesterified compounds containing free carboxyl groups between monohydroxyoligoacrylates or monohydroxyoligomethacrylates such as trimethylolpropane diacrylate, trimethylolpropane dimethacrylate, pentaerythritol triacrylate, pentaerythritol trimethacrylate, dipentaerythritol pentaacrylate, and dipentaerythritol pentamethacrylate and dicarboxylic acids such as malonic acid, succinic acid, glutaric acid, and phthalic acid; and oligoesterified compounds containing free carboxyl groups between tricarboxylic acids such as propane-1,2,3-tricarboxylic acid (tricarbaryl acid), butane-1,2,4-tricarboxylic acid, benzene-1,2,3-tricarboxylic acid, benzene-1,3,4-tricarboxylic acid, and benzene-1,3,5-tricarboxylic acid and monohydroxymonoacrylates or monohydroxymonomethacrylates such as 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl acrylate, and 2-hydroxypropyl methacrylate.

[0047] (Polymerizable compound containing urethane bonds) Examples of polymerizable compounds containing urethane bonds include polyfunctional urethane acrylates obtained by reacting a polyfunctional isocyanate with a (meth)acrylate having a hydroxyl group, and polyfunctional urethane acrylates obtained by reacting an alcohol with a polyfunctional isocyanate and then reacting that with a (meth)acrylate having a hydroxyl group.

[0048] Examples of hydroxyl group-containing (meth)acrylates include 2-hydroxyethyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, trimethylolpropane di(meth)acrylate, pentaerythritol tri(meth)acrylate, ditrimethylolpropane tri(meth)acrylate, dipentaerythritol penta(meth)acrylate, dipentaerythritol ethylene oxide-modified penta(meth)acrylate, dipentaerythritol propylene oxide-modified penta(meth)acrylate, dipentaerythritol caprolactone-modified penta(meth)acrylate, glycerol acrylate methacrylate, glycerol dimethacrylate, 2-hydroxy-3-acryloylpropyl methacrylate, reaction products of epoxy group-containing compounds and carboxy(meth)acrylate, and hydroxyl group-containing polyol polyacrylates.

[0049] Furthermore, polyfunctional isocyanates include tolylene diisocyanate, hexamethylene diisocyanate, diphenylmethylene diisocyanate, isophorone diisocyanate, and polyisocyanates.

[0050] Polymerizable compound (C) can be used alone or in combination of two or more types.

[0051] The amount of polymerizable compound (C) is preferably 1 to 19% by mass, and more preferably 5 to 15% by mass, based on 100% by mass of the nonvolatile content of the photosensitive composition. Adding an appropriate amount further improves curability and developability. <Binder resin (D)> The binder resin (D) is preferably a resin that, when a 2 μm thick film is formed, has a transmittance of 80% or more in the entire wavelength range of 400 to 700 nm. A transmittance of 95% or more is preferable. Furthermore, since the binder resin (D) is alkali-soluble, the film formed from the photosensitive composition can be patterned by photolithography. The binder resin (D) may also have thermosetting groups. Examples of such thermosetting groups include epoxy groups and oxetanyl groups.

[0052] The binder resin (D) preferably contains one or more selected from non-photosensitive binder resins (D-1) or photosensitive binder resins (D-2).

[0053] <Non-photosensitive binder resin (D-1)> The non-photosensitive binder resin (D-1) is preferably an alkali-soluble resin having acidic groups such as carboxyl groups and sulfonate groups. Examples of binder resins (D-1) include acrylic resins having acidic groups, α-olefin / (anhydride) maleic acid copolymers, styrene / styrene sulfonic acid copolymers, ethylene / (meth)acrylic acid copolymers, or isobutylene / (anhydride) maleic acid copolymers. Among these, acrylic resins having acidic groups and styrene / styrene sulfonic acid copolymers are preferred in terms of improved developability, heat resistance, and transparency.

[0054] The non-photosensitive binder resin (D-1) may contain one or more cyclic structures selected from aliphatic or aromatic rings. This increases rigidity, improves development resistance, and enhances substrate adhesion. Aliphatic rings include, for example, alicyclic hydrocarbon skeletons having 5 to 20 carbon atoms. Examples of alicyclic hydrocarbon skeletons include cyclopentane, cyclohexane, cyclooctane, cyclodecane, norbornane, dicyclopentane, and tricyclodecane skeletons. Among these, the tricyclodecane skeleton is preferred from the viewpoint of improving pattern formation. The aromatic ring is preferably a benzene ring, and examples of compounds containing a benzene ring include styrene compounds and benzyl (meth)acrylate.

[0055] <Photosensitive binder resin (D-2)> The photosensitive binder resin (D-2) is, for example, a resin to which photocrosslinking groups have been added to a non-photosensitive binder resin (D-1). Similar to the polymerizable compound (C), the binder resin (D-2) undergoes three-dimensional crosslinking upon light irradiation, increasing the crosslinking density and thus improving the chemical resistance of the coating. The photosensitive binder resin (D-2) is preferably a resin synthesized by the following methods (i) or (ii).

[0056] [Method (i)] Method (i) is, for example, to first synthesize polymers of epoxy group-containing monomers and other monomers. Then, a monocarboxyl group-containing monomer is added to the epoxy group of the polymer, and the resulting hydroxyl group is reacted with a polybasic acid anhydride to obtain an alkali-soluble photosensitive resin. Note that the monocarboxyl group-containing monomer is a monomer having one carboxyl group.

[0057] Examples of epoxy group-containing monomers include glycidyl (meth)acrylate, methylglycidyl (meth)acrylate, 2-glycidoxyethyl (meth)acrylate, 3,4-epoxybutyl (meth)acrylate, and 3,4-epoxycyclohexyl (meth)acrylate. Among these, glycidyl (meth)acrylate is preferred from the viewpoint of reactivity.

[0058] Monocarboxyl group-containing monomers include, for example, (meth)acrylic acid, crotonic acid, o-, m-, p-vinylbenzoic acid, and monocarboxylic acids such as α-haloalkyl, alkoxyl, halogen, nitro, and cyano-substituted derivatives of (meth)acrylic acid.

[0059] Examples of polybasic acid anhydrides include tetrahydrophthalic anhydride, phthalic anhydride, hexahydrophthalic anhydride, succinic anhydride, and maleic anhydride. Polybasic acid anhydrides may also have carboxyl groups that do not form acid anhydrides.

[0060] Other monomers include (meth)acrylates such as methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, isopropyl (meth)acrylate, n-butyl (meth)acrylate, isobutyl (meth)acrylate, t-butyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, cyclohexyl (meth)acrylate, stearyl (meth)acrylate, lauryl (meth)acrylate, tetrahydrofurfuryl (meth)acrylate, isobornyl (meth)acrylate, phenyl (meth)acrylate, benzyl (meth)acrylate, phenoxyethyl (meth)acrylate, phenoxydiethylene glycol (meth)acrylate, methoxypolypropylene glycol (meth)acrylate, or ethoxypolyethylene glycol (meth)acrylate. Alternatively, examples include (meth)acrylamides such as (meth)acrylamide, N,N-dimethyl(meth)acrylamide, N,N-diethyl(meth)acrylamide, N-isopropyl(meth)acrylamide, diacetone(meth)acrylamide, or styrenes such as acryloylmorpholine, or styrenes such as α-methylstyrene, vinyl ethers such as ethyl vinyl ether, n-propyl vinyl ether, isopropyl vinyl ether, n-butyl vinyl ether, or isobutyl vinyl ether, and vinyl fatty acid compounds such as vinyl acetate or vinyl propionate.

[0061] Also, cyclohexylmaleimide, phenylmaleimide, methylmaleimide, ethylmaleimide, 1,2-bismaleimideethane, 1,6-bismaleimidehexane, 3-maleimidepropionic acid, 6,7-methylenedioxy-4-methyl-3-maleimidocoumarin, 4,4'-bismaleimidediphenylmethane, bis(3-ethyl-5-methyl-4-maleimidephenyl)methane, N,N'-1,3-phenylenedimaleimide, N,N'-1,4-phenylenedimaleimide, N-(1-pyrenyl)maleimide, N-(2,4,6-trichlorophenyl)maleimide, N-(4-aminophenyl)maleimide, N-(4-nitrophenyl)maleimide, N-benzylmaleimide, N-bromomethyl-2,3-dichloromaleimide, N-succinimidyl-3-maleimide Examples include N-substituted maleimides such as midobenzoate, N-succinimidyl-3-maleimide propionate, N-succinimidyl-4-maleimide butyrate, N-succinimidyl-6-maleimide hexanoate, N-[4-(2-benzimidazolyl)phenyl]maleimide, and 9-maleimide acridine; EO-modified cresol acrylate, n-nonylphenoxypolyethylene glycol acrylate, phenoxyethyl acrylate, ethoxylated phenyl acrylate, ethylene oxide (EO)-modified (meth)acrylate of phenol, EO or propylene oxide (PO)-modified (meth)acrylate of paracumylphenol, EO-modified (meth)acrylate of nonylphenol, and PO-modified (meth)acrylate of nonylphenol.

[0062] Method (ii) involves, for example, synthesizing a polymer by combining a hydroxyl group-containing monomer, a carboxyl group-containing monomer, and other monomers. Then, a photosensitive resin is synthesized by reacting the hydroxyl group of the polymer with the isocyanate group of an isocyanate group-containing monomer.

[0063] Examples of hydroxyl group-containing monomers include hydroxyalkyl methacrylates such as 2-hydroxyethyl (meth)acrylate, 2- or 3-hydroxypropyl (meth)acrylate, 2- or 3- or 4-hydroxybutyl (meth)acrylate, glycerol mono(meth)acrylate, or cyclohexanedimethanol mono(meth)acrylate. Also included are polyether mono(meth)acrylates obtained by addition polymerization of ethylene oxide, propylene oxide, and / or butylene oxide to hydroxyalkyl (meth)acrylate, and polyester mono(meth)acrylates obtained by adding polyγ-valerolactone, polyε-caprolactone, and / or poly12-hydroxystearic acid. Among these, 2-hydroxyethyl methacrylate and glycerol mono(meth)acrylate are preferred, and glycerol mono(meth)acrylate is more preferred.

[0064] Examples of isocyanate group-containing monomers include 2-(meth)acryloylethyl isocyanate, 2-(meth)acryloyloxyethyl isocyanate, or 1,1-bis[methacryloyloxy]ethyl isocyanate.

[0065] Other monomers that can be used besides the monomers mentioned above include the monomers exemplified in method (i) above, as well as monomers containing phosphate ester groups, and so on.

[0066] A phosphate ester group-containing monomer is, for example, a compound obtained by reacting the hydroxyl group of a hydroxyl group-containing monomer with a phosphate esterifying agent such as phosphorus pentoxide or polyphosphate.

[0067] The binder resin (D) can be used alone or in combination of two or more types.

[0068] The binder resin (D) content is preferably 15 to 35% by mass, and more preferably 19 to 29% by mass, based on 100% by mass of the nonvolatile content of the photosensitive composition. An appropriate amount allows for easy film formation.

[0069] The weight-average molecular weight (Mw) of the binder resin (D) is preferably 2,000 to 40,000, more preferably 3,000 to 30,000, and even more preferably 4,000 to 20,000. The Mw / Mn value is preferably 10 or less. Note that Mn is the number-average molecular weight.

[0070] The acid value of the binder resin (D) is preferably 50-200 mgKOH / g, more preferably 60-180 mgKOH / g, and even more preferably 60-170 mgKOH / g. An appropriate acid value allows for a high degree of balance between alkali solubility, adhesion, and residue suppression.

[0071] <Solvent (E)> Photosensitive compositions can contain solvents. This facilitates viscosity adjustment of the photosensitive composition, making it easier to form a smooth film. The solvent should be selected appropriately according to the intended use, and included in an appropriate amount.

[0072] Examples of solvents include ester solvents (solvents containing -COO- but not -O- in the molecule), ether solvents (solvents containing -O- but not -COO- in the molecule), ether ester solvents (solvents containing both -COO- and -O- in the molecule), ketone solvents (solvents containing -CO- but not -COO- in the molecule), alcohol solvents (solvents containing OH in the molecule but not -O-, -CO-, and -COO- in the molecule), aromatic hydrocarbon solvents, amide solvents, dimethyl sulfoxides, and the like.

[0073] Among these, solvents with a boiling point of 120°C to 180°C at 1 atm are preferred in terms of applicability and drying properties. For example, propylene glycol monomethyl ether acetate, ethyl lactate, butyl lactate, propylene glycol monomethyl ether, ethyl 3-ethoxypropionate, ethylene glycol monomethyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, 4-hydroxy-4-methyl-2-pentanone, N,N-dimethylformamide, and N-methylpyrrolidone are more preferred, and propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, ethyl lactate, and ethyl 3-ethoxypropionate are even more preferred.

[0074] Solvents can be used individually or in mixtures of two or more types.

[0075] <UV absorber (F)> UV absorbers are organic compounds that have UV absorption properties, and examples include benzophenone-based, benzotriazole-based, triazine-based, quinolinone-based, benzoate-based, cyanoacrylate-based, benzoxazole-based, salicylate-based, and conjugated diene-based compounds.

[0076] (Benzophenone-based UV absorber) Examples of benzophenone compounds include 2,4-di-hydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-n-octoxybenzophenone, 2,2'-di-hydroxy-4-methoxybenzophenone, 2,2'-dihydroxy-4,4'-dimethoxybenzophenone, 4-dodecyloxy-2-hydroxybenzophenone, 2-hydroxy-4-octadecyloxybenzophenone, 2,2'-dihydroxy-4,4'-dimethoxybenzophenone, 2,2',4,4'-tetrahydroxybenzophenone, and 2-hydroxy-4-methoxy-2'-carboxybenzophenone. Examples of commercially available products include 2,2',4,4'-tetrahydroxybenzophenone (Cypro Chemical Co., Ltd.'s "Seesorb 106", BASF Japan Ltd.'s "Uvinul 3050"), 2,2'-dihydroxy-4,4'-dimethoxybenzophenone (Cypro Chemical Co., Ltd.'s "Seesorb 107", BASF Japan Ltd.'s "Uvinul 3049"), and 2,2'-methylenebis[4-(1,1,3,3-tetramethylbutyl)-6-(2H-benzotriazole-2-yl)phenol] (ADEKA Corporation's "ADEKA Stab LA-31", Chemipro Chemical Co., Ltd.'s "Kemisorb 279").

[0077] (Benzotriazole-based UV absorbers) Benzotriazole compounds include, for example, 2-(5-methyl-2-hydroxyphenyl)benzotriazole, 2-(2-hydroxy-5-t-butylphenyl)-2H-benzotriazole, 2-[2-hydroxy-3,5-bis(α,α-dimethylbenzyl)phenyl]-2H-benzotriazole, 2-(3-t-butyl-5-methyl-2-hydroxyphenyl)-5-chlorobenzotriazole, and 2-(2'-hydroxy-5'-t-octylphenyl)benzotriazole, 5% of 2 -Methoxy-1-methylethyl acetate and 95% benzenepropanoic acid, a mixture of 3-(2H-benzotriazole2-yl)-(1,1-dimethylethyl)-4-hydroxy, C7-9 side chain and linear alkyl ester, 2-(2H-benzotriazole2-yl)-4,6-bis(1-methyl-1-phenylethyl)phenol, 2-(2H-benzotriazole2-yl)-6-(1-methyl-1-phenylethyl)-4-(1,1,3,3-tetramethylbutyl)phenol, methyl Reaction product of 3-(3-(2H-benzotriazole2-yl)-5-t-butyl-4-hydroxyphenyl)propionate / polyethylene glycol 300, 2-(2H-benzotriazole2-yl)-4-(1,1,3,3-tetramethylbutyl)phenol, 2,2'-methylenebis[6-(2H-benzotriazole2-yl)-4-(1,1,3,3-tetramethylbutyl)phenol], 2-(2H-benzotriazole2-yl)-p-cresol, 2-(5-chloro-2H-benzotriazole2-yl)-6-t-butyl Examples include 4-methylphenol, 2-(3,5-di-t-amyl-2-hydroxyphenyl)benzotriazole, 2-[2-hydroxy-5-[2-(methacryloyloxy)ethyl]phenyl]-2H-benzotriazole, octyl-3-[3-tert-butyl-4-hydroxy-5-(5-chloro-2H-benzotriazole2-yl)phenyl]propionate, and 2-ethylhexyl-3-[3-tert-butyl-4-hydroxy-5-(5-chloro-2H-benzotriazole2-yl)phenyl]propionate.Examples of commercially available products include 2-(2'-hydroxy-5'-tert-octylphenyl)benzotriazole (Cypro Chemical Co., Ltd.'s "Seesorb 709"), BASF Japan's "Tinuvin 326", BASF Japan's "Tinuvin 384-2", and 2-(2H-benzotriazol-2-yl)-4,6-bis(1-methyl-1-phenylethyl)phenol (BASF Japan's "Tinuvin 900").

[0078] (Triazine-based UV absorber) Triazine-based UV absorbers, for example, 2,4-diphenyl-6-(2-hydroxy-4-methoxyphenyl)-1,3,5-triazine, 2,4-diphenyl-6-(2-hydroxy-4-ethoxyphenyl)-1,3,5-triazine, 2,4-diphenyl-(2-hydroxy-4-propoxyphenyl)-1,3,5-triazine, 2,4-diphenyl-(2-hydroxy-4-butoxyphenyl)-1,3,5-triazine, 2,4-diphenyl-6-(2-hydroxy-4-butoxyphenyl)-1,3,5-triazine, 2,6-diphenyl Nyl-4-(2-hydroxy-4-hexyloxyphenyl)-1,3,5-triazine, 2,4-diphenyl-6-(2-hydroxy-4-octyloxyphenyl)-1,3,5-triazine, 2,4-diphenyl-6-(2-hydroxy-4-dodecyloxyphenyl)-1,3,5-triazine, 2,4-diphenyl-6-(2-hydroxy-4-benzyloxyphenyl)-1,3,5-triazine, 2,4,6-tris(2-hydroxy-4-propoxyphenyl)-1,3,5-triazine, 2,4,6-tris(2-hydroxy-4 -Butoxyphenyl)-1,3,5-triazine, 2,4,6-Tris(2-hydroxy-4-butoxyphenyl)-1,3,5-triazine, 2,4,6-Tris(2-hydroxy-4-hexyloxyphenyl)-1,3,5-triazine, 2,4,6-Tris(2-hydroxy-4-octyloxyphenyl)-1,3,5-triazine, 2,4,6-Tris(2-hydroxy-4-dodecyloxyphenyl)-1,3,5-triazine, 2,4,6-Tris(2-hydroxy-4-benzyloxyphenyl)-1,3,5-triazine, 2, 4,6-Tris(2-hydroxy-4-ethoxyethoxyphenyl)-1,3,5-triazine, 2,4,6-Tris(2-hydroxy-4-butoxyethoxyphenyl)-1,3,5-triazine, 2,4,6-Tris(2-hydroxy-4-propoxyethoxyphenyl)-1,3,5-triazine, 2,4,6-Tris(2-hydroxy-4-methoxycarbonylpropyloxyphenyl)-1,3,5-triazine, 2,4,6-Tris(2-hydroxy-4-ethoxycarbonylethyloxyphenyl)-1,3,5-triazine, 2,4,6-Tris(2-hydroxy-4-(1-(2-ethoxyhexyloxy)-1-oxopropane-2-yloxy)phenyl)-1,3,5-triazine, 2,4,6-Tris(2-hydroxy-3-methyl-4-ethoxyphenyl)-1,3,5-triazine, 2,4,6-Tris(2-hydroxy-3-methyl-4-propoxyphenyl)-1,3,5-triazine, 2,4,6-Tris(2-hydroxy-3-methyl-4-butoxyphenyl)-1,3,5-triazine, 2,4,6-Tris(2-hydroxy-3-methyl-4-butoxyphenyl)-1,3,5-triazine Tris(2-hydroxy-3-methyl-4-hexyloxyphenyl)-1,3,5-triazine, Tris(2-hydroxy-3-methyl-4-octyloxyphenyl)-1,3,5-triazine, Tris(2-hydroxy-3-methyl-4-dodecyloxyphenyl)-1,3,5-triazine, Tris(2-hydroxy-3-methyl-4-dodecyloxyphenyl)-1,3,5-triazine, Tris(2-hydroxy-3-methyl-4-benzyloxyphenyl)-1,3,5-triazine, Tris(2-hydroxy-3, Tris(2-hydroxy-3-methyl-4-butoxyethoxyphenyl)-1,3,5-triazine, 2,4,6-tris(2-hydroxy-3-methyl-4-butoxyethoxyphenyl)-1,3,5-triazine, 2,4,6-tris(2-hydroxy-3-methyl-4-propoxyethoxyphenyl)-1,3,5-triazine, 2,4,6-tris(2-hydroxy-3-methyl-4-methoxycarbonylpropyloxyphenyl)-1,3,5-triazine, 2,4,6-tris(2-hydroxy-3-methyl-4-ethoxycarbonyl Examples include triazines (2-hydroxy-3-methyl-4-(1-(2-ethoxyhexyloxy)-1-oxopropane-2-yloxy)phenyl)-1,3,5-triazine, 2,4-bis(2,4-dimethylphenyl)-6-(2-hydroxy-4-N-octyloxyphenyl)-1,3,5-triazine, and 2-(4,6-diphenyl-1,3,5-triazine-2-yl)-5-(2-(2-ethylhexanoyloxy)ethoxy)phenol.

[0079] Commercially available products include 2,4-bis(2,4-dimethylphenyl)-6-(2-hydroxy-4-N-octyloxyphenyl)-1,3,5-triazine (Kemisorb 102, manufactured by Chemipro Chemical Co., Ltd.), 2,4,6-tris(2-hydroxy-3-methyl-4-hexyloxyphenyl)-1,3,5-triazine (ADEKA Corporation's Adeka Stab LA-F70), 2-(4,6-diphenyl-1,3,5-triazine-2-yl)-5-(2-(2-ethylhexanoyloxy)ethoxy)phenol (ADEKA Corporation's Adeka Stab LA-46), and 2,4-diphenyl-6-(2-hydroxy-4-hexyloxyphenyl)-1,3,5-triazine (Chinubin 1577, manufactured by BASF Japan, and Chinuvin 477, manufactured by BASF Japan).

[0080] (Indole-based UV absorber) Examples of indole-based UV absorbers include 2-[(1-methyl-2-phenyl-1H-indole-3-yl)methylene]propanedinitrile (BONASORB UA-3901, manufactured by Orient Chemical Industries, Ltd.).

[0081] (Quinolinone-based UV absorber) Examples of quinolinone-based UV absorbers include 4-hydroxy-3-[(phenylimino)methyl]-2(1H)-quinolinone (BONASORB UA-3701, manufactured by Orient Chemical Industries, Ltd.).

[0082] (Benzoate-based UV absorbers) Examples of benzoate-based UV absorbers include 2,4-di-t-butylphenyl-3',5'-di-t-butyl-4'-hydroxybenzoate, 2,6-di-t-butylphenyl-3',5'-di-t-butyl-4'-hydroxybenzoate, n-hexadecyl-3,5-di-t-butyl-4-hydroxybenzoate, and n-octadecyl-3,5-di-t-butyl-4-hydroxybenzoate.

[0083] (Cyanoacrylate-based UV absorber) Examples of cyanoacrylate-based UV absorbers include 2'-ethylhexyl-2-cyano-3,3-diphenyl acrylate and ethyl-2-cyano-3-(3',4'-methylenedioxyphenyl)-acrylate.

[0084] (Salicylate-based UV absorber) Examples of salicylate ester compounds include phenyl salicylate, p-octylphenyl salicylate, and p-tert-butylphenyl salicylate.

[0085] (Conjugated diene UV absorber) Conjugated diene-based external radiation absorbers are compounds represented by the following general formula (I). [ka]

[0086] [In general formula (I), R 1 and R 2 Each of these independently represents a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, or an aryl group having 6 to 20 carbon atoms. 1 and R 2 These may be identical or different from each other, but they do not simultaneously represent a hydrogen atom, R 1 and R 2 R may form a cyclic amino group with the nitrogen atom. 3 and R 4 Each of these independently represents an electron-withdrawing group.

[0087] Examples of electron-withdrawing groups include acyl groups, acyloxy groups, carbamoyl groups, alkyloxycarbonyl groups, aryloxycarbonyl groups, cyano groups, nitro groups, dialkylphosphono groups, diarylphosphono groups, diarylphosphinyl groups, alkylsulfinyl groups, arylsulfinyl groups, alkylsulfonyl groups, arylsulfonyl groups, sulfonyloxy groups, acylthio groups, sulfamoyl groups, thiocyanate groups, thiocarbonyl groups, alkyl groups substituted with at least two halogen atoms, alkoxy groups substituted with at least two halogen atoms, aryloxy groups substituted with at least two halogen atoms, alkylamino groups substituted with at least two halogen atoms, heterocyclic groups, chlorine atoms, bromine atoms, azo groups, or selenocyanate groups.

[0088] (Other UV absorbers) In addition to the UV absorbers mentioned above, other UV absorbers include, for example, 7-(dimethylamino)-4-methylcoumarin and benzoxazole-based 2,5-bis(5-tert-butyl-2-benzoxazolyl)thiophene (BASF Japan Ltd. "TINOPAL OB") and 4,4'-bis(2-benzoxazolyl)stilbene. Among these, benzoxazole-based absorbers are preferred.

[0089] The content of the ultraviolet absorber (F) is preferably 0.1 to 12% by mass, and more preferably 1 to 7% by mass, based on 100% by mass of the nonvolatile content of the photosensitive composition. When an appropriate amount is included, the amount of exposure can be reduced by the ultraviolet absorber in unwanted areas near the edges of the pattern, thereby suppressing photocuring and improving resolution.

[0090] <Polymerization inhibitor (G)> The photosensitive composition may contain a polymerization inhibitor. This suppresses photosensitivity due to diffracted light on the mask during exposure in photolithography, making it easier to obtain patterns of the desired shape.

[0091] Polymerization inhibitors include alkylcatechol compounds such as catechol, resorcinol, 1,4-hydroquinone, 2-methylcatechol, 3-methylcatechol, 4-methylcatechol, 2-ethylcatechol, 3-ethylcatechol, 4-ethylcatechol, 2-propylcatechol, 3-propylcatechol, 4-propylcatechol, 2-n-butylcatechol, 3-n-butylcatechol, 4-n-butylcatechol, 2-tert-butylcatechol, 3-tert-butylcatechol, 4-tert-butylcatechol, 3,5-di-tert-butylcatechol, 2-methylresorcinol, 4-methylresorcinol, 2-ethylresorcinol, 4-ethylresorcinol, 2-propylresorcinol, 4-propylresorcinol, 2-n-butylcatechol, 2-propylresorcinol, 2-propylresorcinol Examples include alkylresorcinol compounds such as cyrrresorcinol, 4-n-butylresorcinol, 2-tert-butylresorcinol, and 4-tert-butylresorcinol; alkylhydroquinone compounds such as methylhydroquinone, ethylhydroquinone, propylhydroquinone, tert-butylhydroquinone, and 2,5-di-tert-butylhydroquinone; phosphine compounds such as tributylphosphine, trioctylphosphine, tricyclohexylphosphine, triphenylphosphine, and tripenzylphosphine; phosphine oxide compounds such as trioctylphosphine oxide and triphenylphosphine oxide; phosphite compounds such as triphenylphosphine and trisnonylphenylphosphine; pyrogallol and phloroglucin.

[0092] The polymerization inhibitor content is preferably 0.01 to 0.4% by mass of 100% by mass of the non-volatile content of the photosensitive composition. Including an appropriate amount makes it easier to obtain a good pattern shape.

[0093] <Photopolymerization initiator> Examples of photopolymerization initiators include 4-phenoxydichloroacetophenone, 4-t-butyl-dichloroacetophenone, diethoxyacetophenone, 1-(4-isopropylphenyl)-2-hydroxy-2-methylpropan-1-one, 1-hydroxycyclohexylphenyl ketone, 2-methyl-1-[4-(methylthio)phenyl]-2-morpholinopropan-1-one, 2-(dimethylamino)-1-[4-(4-morpholino)phenyl]-2-(phenylmethyl)-1-butanone, or 2-(dimethylamino)-2-[(4-methylthio)phenyl] Acetophenone compounds such as [4-(4-morpholinyl)phenyl]-1-butanone; benzoin compounds such as benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, or benzyldimethyl ketal; benzophenone, benzoylbenzoic acid, methyl benzoylbenzoate, 4-phenylbenzophenone, hydroxybenzophenone, acrylic benzophenone, 4-benzoyl-4'-methyldiphenyl sulfide, or 3,3',4,4'-tetra(t-) Benzophenone compounds such as thioxanthone ((p-p-p-p((p-p-p((p-p((p-p((p-p((p-p((p-p((p-p((p-p((p-p((p-p((p-p((p-p(((p-p(((p-p(((p-p((((p-p(((((((((((((((((((((((((((((((((((((((((((((((((((((((((((((((((( Triazine compounds such as lichloromethyl)-s-triazine, 2-piperonyl-4,6-bis(trichloromethyl)-s-triazine, 2,4-bis(trichloromethyl)-6-styryl-s-triazine, 2-(naphtho-1-yl)-4,6-bis(trichloromethyl)-s-triazine, 2-(4-methoxynaphtho-1-yl)-4,6-bis(trichloromethyl)-s-triazine, 2,4-trichloromethyl-(piperonyl)-6-triazine, or 2,4-trichloromethyl-(4'-methoxystyryl)-6-triazine;Examples include oxime ester compounds such as 1,2-octanedione, 1-[4-(phenylthio)phenyl-,2-(O-benzoyl oxime)], or ethanone, 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazole-3-yl]-,1-(O-acetyl oxime); phosphine compounds such as bis(2,4,6-trimethylbenzoyl)phenylphosphine oxide or diphenyl-2,4,6-trimethylbenzoylphosphine oxide; quinone compounds such as 9,10-phenanthrenequinone, camphorquinone, and ethylanthraquinone; borate compounds; carbazole compounds; imidazole compounds; or titanocene compounds. Among these, oxime ester compounds are preferred.

[0094] Photopolymerization initiators can be used alone or in combination of two or more types.

[0095] (Oxime ester compounds) Oxime ester compounds undergo cleavage of the oxime's NO bond upon absorption of ultraviolet light, generating iminyl radicals and alkyloxy radicals. These radicals can be further decomposed to generate highly reactive radicals, allowing for pattern formation with minimal exposure. While high colorant concentrations in photosensitive compositions can lead to low UV transmittance and reduced hardening of the coating film, oxime ester compounds are suitable for use due to their high quantum efficiency.

[0096] Examples of oxime ester compounds include oxime ester photopolymerization initiators described in Japanese Patent Publication No. 2007-210991, Japanese Patent Publication No. 2009-179619, Japanese Patent Publication No. 2010-037223, Japanese Patent Publication No. 2010-215575, Japanese Patent Publication No. 2011-020998, and the like.

[0097] The content of the photopolymerization initiator is preferably 0.1 to 10% by mass, and more preferably 0.5 to 5% by mass, based on 100% by mass of the nonvolatile content of the photosensitive composition. Adding an appropriate amount further improves photocurability and developability.

[0098] <Thermosetting compounds> The photosensitive composition may contain a thermosetting compound for the purpose of increasing the crosslinking density of the coating.

[0099] Examples of thermosetting compounds include epoxy compounds, oxetane compounds, benzoguanamine compounds, rosin-modified maleic acid compounds, rosin-modified fumaric acid compounds, melamine compounds, urea compounds, and phenolic compounds. Among these, epoxy compounds and oxetane compounds are preferred.

[0100] Epoxy compounds include polycondensates of bisphenols (bisphenol A, bisphenol F, bisphenol S, biphenol, bisphenol AD, etc.), phenols (phenol, alkyl-substituted phenol, aromatic-substituted phenol, naphthol, alkyl-substituted naphthol, dihydroxybenzene, alkyl-substituted dihydroxybenzene, dihydroxynaphthalene, etc.) and various aldehydes (formaldehyde, acetaldehyde, alkylaldehyde, benzaldehyde, alkyl-substituted benzaldehyde, hydroxybenzaldehyde, naphthaldehyde, glutaraldehyde, phthalaldehyde, crotonaldehyde, cinnamaldehyde, etc.), and various diene compounds (dicyclopentadiene, terpenes, vinylcyclohexene, norbornadiene, vinylnorbornene, tetrahydroindene, divinylbenzene, di Examples include polymers of vinyl biphenyls (such as vinyl biphenyls, diisopropenyl biphenyls, butadienes, isoprene, etc.), polycondensates of phenols and ketones (such as acetone, methyl ethyl ketone, methyl isobutyl ketone, acetophenone, benzophenone, etc.), polycondensates of phenols and aromatic dimethanols (such as benzenedimethanol, α,α,α',α'-benzenedimethanol, biphenyldimethanol, α,α,α',α'-biphenyldimethanol, etc.), polycondensates of phenols and aromatic dichloromethyls (such as α,α'-dichloroxylene, bischloromethylbiphenyl, etc.), polycondensates of bisphenols and various aldehydes, glycidyl ether epoxy resins, alicyclic epoxy resins, heterocyclic epoxy resins, aliphatic epoxy resins, glycidylamine epoxy resins, and glycidyl ester epoxy resins obtained by glycidylating alcohols, etc.

[0101] (Oxetane compounds) Oxetane compounds are compounds that contain an oxetane group. Examples of oxetane compounds include monofunctional oxetane compounds, difunctional oxetane compounds, and trifunctional or multifunctional oxetane compounds.

[0102] Examples of monofunctional oxetane compounds include (3-ethyloxetane-3-yl)methyl acrylate, (3-ethyloxetane-3-yl)methyl methacrylate, 3-ethyl-3-hydroxymethyl oxetane, 3-ethyl-3-(2-ethylhexyloxymethyl)oxetane, 3-ethyl-3-(phenoxymethyl)oxetane, 3-ethyl-3-(2-methacryloxymethyl)oxetane, and 3-ethyl-3-{[3-(triethoxysilyl)propoxy]methyl}oxetane.

[0103] Examples of bifunctional oxetane compounds include 4,4'-bis[(3-ethyl-3-oxetanyl)methoxymethyl]biphenyl), 1,4-bis[(3-ethyl-3-oxetanyl)methoxymethyl]benzene, 1,4-bis{[(3-ethyl-3-oxetanyl)methoxy]methyl}benzene, di[1-ethyl(3-oxetanyl)]methyl ether, di[1-ethyl(3-oxetanyl)]methyl ether-3-ethyl-3-hydroxymethyloxetane, 3 -Ethyl-3-(2-ethylhexyloxymethyl)oxetane, 3-ethyl-3-(2-phenoxymethyl)oxetane, 3,7-bis(3-oxetanyl)-5-oxa-nonane, 1,2-bis[(3-ethyl-3-oxetanylmethoxy)methyl]ethane, 1,3-bis[(3-ethyl-3-oxetanylmethoxy)methyl]propane, ethyleneglycosyl bis(3-ethyl-3-oxetanylmethyl)ether, dicyclopentenyl bis(3-ethyl Examples include bis(3-ethyl-3-oxetanylmethyl) ether, triethylene glycol bis(3-ethyl-3-oxetanylmethyl) ether, tetraethylene glycol bis(3-ethyl-3-oxetanylmethyl) ether, 1,4-bis(3-ethyl-3-oxetanylmethoxy)butane, 1,6-bis(3-ethyl-3-oxetanylmethoxy)hexane, polyethylene glycol bis(3-ethyl-3-oxetanylmethyl) ether, ethylene oxide (EO) modified bisphenol A bis(3-ethyl-3-oxetanylmethyl) ether, propylene oxide (PO) modified bisphenol A bis(3-ethyl-3-oxetanylmethyl) ether, EO modified hydrogenated bisphenol A bis(3-ethyl-3-oxetanylmethyl) ether, PO modified hydrogenated bisphenol A bis(3-ethyl-3-oxetanylmethyl) ether, and EO modified bisphenol F (3-ethyl-3-oxetanylmethyl) ether.

[0104] Oxetane compounds with three or more functionalities include pentaerythritol tris(3-ethyl-3-oxetanylmethyl) ether, pentaerythritol tetrakis(3-ethyl-3-oxetanylmethyl) ether, dipentaerythritol hexa(3-ethyl-3-oxetanylmethyl) ether, dipentaerythritol pentakis(3-ethyl-3-oxetanylmethyl) ether, dipentaerythritol tetrakis(3-ethyl-3-oxetanylmethyl) ether, and caprolactone-modified dipentae. Examples include lithritol hexa(3-ethyl-3-oxetanylmethyl) ether, caprolactone-modified dipentaerythritol pentakis(3-ethyl-3-oxetanylmethyl) ether, ditrimethylolpropanetetrakis(3-ethyl-3-oxetanylmethyl) ether, resins containing oxetane groups (for example, the oxetane-modified phenol novolac resin described in Japanese Patent No. 3783462), and polymers obtained by radical polymerization of (meth)acrylic monomers such as the aforementioned OXE-30.

[0105] The thermosetting compound content is preferably 0.5 to 50% by mass, and more preferably 1 to 40% by mass, based on 100% by mass of the nonvolatile content of the photosensitive composition. Including an appropriate amount further improves the solvent resistance of the coating.

[0106] <Sensitizer> The photosensitive composition may further contain a sensitizer. Examples of sensitizers include chalcone derivatives, unsaturated ketones such as dibenzalacetone, 1,2-diketone derivatives such as benzyl and camphorquinone, benzoin derivatives, fluorene derivatives, naphthoquinone derivatives, anthraquinone derivatives, xanthene derivatives, thioxanthene derivatives, xanthone derivatives, thioxanthone derivatives, coumarin derivatives, ketocoumarin derivatives, cyanine derivatives, merocyanine derivatives, polymethine dyes such as oxonol derivatives, acridine derivatives, azine derivatives, thiaidine derivatives, oxazine derivatives, indoline derivatives, azulene derivatives, azulenium derivatives, squarylium derivatives, porphyrin derivatives, tetraphenylporphyrin derivatives, triarylmethane derivatives, tetrabenzoporphyrin derivatives, and tetrapyradinoporphyrazine derivatives. Examples include phthalocyanine derivatives, tetraazaporphyrazine derivatives, tetraquinoxaliloporphyrazine derivatives, naphthalocyanine derivatives, subphthalocyanine derivatives, pyrylium derivatives, thiopyrillium derivatives, tetraphylline derivatives, annulene derivatives, spiropyran derivatives, spirooxazine derivatives, thiospilopyran derivatives, metal arene complexes, organoruthenium complexes, or Michler ketone derivatives, α-acyloxyesters, acylphosphine oxides, methylphenylglyoxylates, benzyl, 9,10-phenanthrenequinone, camphorquinone, ethylanthraquinone, 4,4'-diethylisophthalophenone, 3,3' or 4,4'-tetra(t-butylperoxycarbonyl)benzophenone, 4,4'-bis(diethylamino)benzophenone, and the like. Among these, thioxanthone derivatives, Michler ketone derivatives, and carbazole derivatives are preferred. Specifically, 2,4-diethylthioxanthone, 2-chlorothioxanthone, 2,4-dichlorothioxanthone, 2-isopropylthioxanthone, 4-isopropylthioxanthone, 1-chloro-4-propoxythioxanthone, 4,4'-bis(dimethylamino)benzophenone, 4,4'-bis(diethylamino)benzophenone, 4,4'-bis(ethylmethylamino)benzophenone, N-ethylcarbazole, 3-benzoyl-N-ethylcarbazole, and 3,6-dibenzoyl-N-ethylcarbazole are more preferred.

[0107] Sensitizers can be used alone or in combination of two or more types.

[0108] The sensitizer content is preferably 3 to 60 parts by mass, and more preferably 5 to 50 parts by mass, per 100 parts by mass of the photopolymerization initiator. Including an appropriate amount further improves photocurability and developability.

[0109] <Chain movement agent> The photosensitive composition of the present invention preferably contains a thiol-based chain transfer agent. By using thiols together with a photopolymerization initiator, thiyl radicals are generated in the radical polymerization process after light irradiation that act as chain transfer agents and are less susceptible to polymerization inhibition by oxygen, resulting in a highly sensitive colored composition.

[0110] Furthermore, polyfunctional aliphatic thiols with two or more thiol groups bonded to aliphatic groups such as methylene or ethylene groups are preferred. More preferably, polyfunctional aliphatic thiols with four or more thiol groups are preferred. Increasing the number of functional groups improves the polymerization initiation function, allowing curing from the surface of the pattern to near the substrate.

[0111] The thiol group is preferably a primary or secondary thiol group. Primary thiol groups are highly reactive and can further improve the sensitivity of the photosensitive composition. Secondary thiol groups are slightly less reactive than primary thiol groups, resulting in improved storage stability.

[0112] Examples of ether compounds having two primary thiol groups include trimethylolpropanedipropanthol and pentaerythritoldipropanthol; ether compounds having three primary thiol groups include pentaerythritoltripropanthol; ether compounds having four primary thiol groups include pentaerythritoltetrapropanthol; ester compounds having two primary thiol groups include butanediol bisthiopropionate and ethylene glycol bisthiopropionate; ester compounds having three primary thiol groups include tris-[(3-mercaptopropionyloxy)-ethyl]-isocyanurate and trimethylolpropanetris(3-mercaptopropionate); and ester compounds having four primary thiol groups include pentaerythritoltetrakis(3-mercaptopropionate) and pentaerythritoltetrakisthioglycolate.

[0113] Secondary thiol compounds having at least one skeleton selected from the group consisting of a pentaerythritol skeleton and an isocyanuric ring skeleton include 1,4-bis(3-mercaptobutyryloxy)butane, 1,3,5-tris(3-mercaptobutyryloxyethyl)-1,3,5-triazine-2,4,6(1H,3H,5H)-trione, trimethylolpropanetris(3-mercaptobutyrate), and pentaerythritoltetrakis(3-mercaptobutyrate).

[0114] Examples of commercially available chain transfer agents having two or more secondary thiol groups include 1,4-bis(3-mercaptobutyryloxy)butane (Showa Denko Corporation's "Kalenz MT® BD1"), pentaerythritol tetrakis(3-mercaptobutyrate) (Showa Denko Corporation's "Kalenz MT® PE"), 1,3,5-tris[2-(3-mercaptobutyryloxyethyl)]-1,3,5-triazine-2,4,6(1H,3H,5H)-trione (Showa Denko Corporation's "Kalenz MT® NR1"), trimethylolethanetris(3-mercaptobutyrate) (Showa Denko Corporation's "TEMB"), and trimethylolpropanetris(3-mercaptobutyrate) (Showa Denko Corporation's "TPMB").

[0115] Other secondary thiol compounds not listed above include secondary butanethiol, 2,3-butanedithiol, hexa-5-ene-3-thiol, secondary dodecanethiol, secondary heptanethiol, secondary hexanethiol, secondary octadecanethiol, secondary octanthiol, and 2-methyl-2-propanethiol.

[0116] Examples of ether compounds having two primary thiol groups include trimethylolpropanedipropanthol and pentaerythritoldipropanthol; ether compounds having three primary thiol groups include pentaerythritoltripropanthol; ether compounds having four primary thiol groups include pentaerythritoltetrapropanthol; ester compounds having two primary thiol groups include butanediol bisthiopropionate and ethylene glycol bisthiopropionate; ester compounds having three primary thiol groups include tris-[(3-mercaptopropionyloxy)-ethyl]-isocyanurate and trimethylolpropanetris(3-mercaptopropionate); and ester compounds having four primary thiol groups include pentaerythritoltetrakis(3-mercaptopropionate) and pentaerythritoltetrakisthioglycolate.

[0117] <Other chain movement agents> Other chain transfer agents include, for example, 3-mercaptopropionic acid and 4-mercaptobutyric acid, which have monofunctional thiol groups.

[0118] <Antioxidant> Photosensitive compositions may contain antioxidants. Antioxidants prevent the film formed from the photosensitive composition from yellowing due to oxidation during thermal processes such as heat curing and ITO annealing, and suppress the decrease in the film's transmittance. In particular, when the pigment concentration of the photosensitive composition is high, the content of photopolymerizable compounds decreases relatively, so increasing the amount of photopolymerization initiator or adding thermosetting compounds can easily cause the film to yellow. Therefore, including antioxidants can prevent yellowing due to oxidation during the heating process and suppress the decrease in the film's transmittance.

[0119] Antioxidants are compounds that have radical scavenging or peroxide decomposition functions. Examples of antioxidants include hindered phenol compounds, hindered amine compounds, phosphorus compounds, sulfur compounds, and hydroxylamine compounds. It is preferable that antioxidants do not contain halogen atoms.

[0120] Among these, hindered phenol-based antioxidants, hindered amine-based antioxidants, phosphorus-based antioxidants, and sulfur-based antioxidants are preferred from the viewpoint of achieving both the transmittance and sensitivity of the coating film.

[0121] Antioxidants can be used alone or in combination of two or more types.

[0122] The antioxidant content is preferably 0.5 to 5.0% by mass of 100% by mass of the non-volatile content of the photosensitive composition. This improves transmittance, spectral characteristics, and sensitivity.

[0123] <Leveling agent> The photosensitive composition may contain a leveling agent. This further improves the wettability to the transparent substrate during film formation and the drying properties of the film. Examples of leveling agents include silicone-based surfactants, fluorine-based surfactants, nonionic surfactants, cationic surfactants, and anionic surfactants.

[0124] The leveling agent content is preferably 0.001 to 2.0% by mass, and more preferably 0.005 to 1.0% by mass, based on 100% by mass of the non-volatile content of the photosensitive composition. Within this range, the balance between the applicability, pattern adhesion, and transmittance of the photosensitive composition is further improved.

[0125] <Storage stabilizer> Photosensitive compositions may contain storage stabilizers to stabilize the viscosity of the composition over time. Examples of storage stabilizers include quaternary ammonium chlorides such as benzyltrimethyl chloride and diethylhydroxyamine, organic acids such as lactic acid and oxalic acid and their methyl ethers, organic phosphines such as t-butylpyrocatechol, tetraethylphosphine, and tetraphenylphosphine, and phosphates.

[0126] The storage stabilizer content is preferably 0.1 to 10% by mass of 100% by mass of the nonvolatile content of the photosensitive composition.

[0127] <Adhesion enhancer> Silane coupling agents include, for example, vinylsilanes such as vinyltrimethoxysilane and vinyltriethoxysilane, (meth)acryloxysilanes such as 3-methacryloxypropylmethyldimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropylmethyldiethoxysilane, 3-methacryloxypropyltriethoxysilane, and 3-acryloxypropyltrimethoxysilane, epoxysilanes such as 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, and 3-glycidoxypropyltriethoxysilane, N-2-( Examples include aminosilanes such as aminoethyl)-3-aminopropyltrimethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-triethoxysilyl-N-(1,3-dimethylbutylidene)propylamine, N-phenyl-3-aminopropyltrimethoxysilane, and hydrochloride salts of N-(vinylbenzyl)-2-aminoethyl-3-aminopropyltrimethoxysilane; mercaptos such as 3-mercaptopropylmethyldimethoxysilane and 3-mercaptopropyltrimethoxysilane; styryls such as p-styryltrimethoxysilane; ureidos such as 3-ureidopropyltriethoxysilane; sulfides such as bis(triethoxysilylpropyl)tetrasulfide; and isocyanates such as 3-isocyanatetopropyltriethoxysilane.

[0128] The adhesion enhancer content is preferably 0.01 to 10% by mass, and more preferably 0.05 to 5% by mass, based on 100% by mass of the photosensitive composition. When an appropriate amount is included, the photosensitivity of the photosensitive composition is improved, the adhesion of the coating is further improved, and the resolution of the pattern is also improved.

[0129] <Method for producing a photosensitive composition> A photosensitive composition can be prepared, for example, by stirring and mixing a dispersant (A), titanium dioxide (B), a polymerizable compound (C), a binder resin (D), and a solvent (E). The timing of adding each material is arbitrary. A dispersion step can also be performed as appropriate.

[0130] Examples of the devices used for stirring and mixing include the TK homomixer and TK pipeline homomixer from Primix, the ULTRA-TURRAX series and Dispax-Reactor series from IKA WERKE GmbH & Co.KG, the High Shear Mixer from Silverson Machines, Inc., the Milder and Cavitron from Taiheiyo Kiko, the Creamix from M-Technique, and the homomixer and pipeline mixer from Mizuho Industries.

[0131] <Moisture content in the photosensitive composition> The photosensitive composition of the present invention preferably contains 2% by mass or less of water. This water content allows the photosensitive composition to exhibit excellent dispersion stability and sensitivity even after storage over time. More preferably, the water content in the photosensitive composition is 1.8% by mass or less, and even more preferably 1.6% by mass or less. Within this range, problems with dispersion stability and sensitivity are unlikely to occur even after storage over time.

[0132] There are no particular limitations on the method for controlling the water content, and known methods can be used. For example, methods include manufacturing the photosensitive composition while blowing in a dry inert gas, or adding molecular sieves after manufacturing to dehydrate it. Among these, the method of manufacturing while blowing in a dry inert gas is preferred.

[0133] The water content can be measured by known methods such as the Karl Fischer method.

[0134] <Amount of toluene in the photosensitive composition> The photosensitive composition of the present invention may contain toluene. The toluene content is preferably 0.1 to 10 ppm by mass in the photosensitive composition. The upper limit of the toluene content is preferably 9 ppm by mass or less, more preferably 8 ppm by mass or less, and even more preferably 7 ppm by mass or less. The lower limit is preferably 0.2 ppm by mass or more, more preferably 0.3 ppm by mass or more, and even more preferably 0.4 ppm by mass or more.

[0135] <Substrate, coating method, and pattern formation> The photosensitive composition is coated onto a substrate and dried to form a film. The film is a high refractive index film. Examples of substrates include substrates and microlenses made of materials such as glass, resin, and silicon. An organic light-emitting layer may be formed on these substrates. An image sensor such as a CCD or CMOS may also be formed on the substrate. Furthermore, a primer layer may be provided on the substrate as needed to improve adhesion with the upper layer, prevent diffusion of materials, and flatten the substrate surface.

[0136] A known coating method can be used. Examples include the drop method, slit coating method, spray method, roll coating method, rotary coating method, casting coating method, inkjet method, flexographic printing, screen printing, gravure printing, and offset printing.

[0137] The thickness of the coating can be adjusted as appropriate depending on the purpose. The film thickness is preferably 0.05 to 20.0 μm, and more preferably 0.3 to 10.0 μm.

[0138] Next, the coating is patterned. Methods for forming the pattern include photolithography and dry etching. Note that when used as a flat film, the patterning step is not necessary; the coating is dried as needed after application.

[0139] The following describes in detail how to form the pattern.

[0140] [Exposure process] The exposure process involves exposing the coating to a specific pattern through a mask using an exposure device such as a stepper. This allows the exposed area to harden. Examples of active energy rays used for exposure include ultraviolet rays such as g-rays (wavelength 436 nm), h-rays (wavelength 405 nm), and i-rays (wavelength 365 nm). Light with a wavelength of 300 nm or less can also be used. Examples of light with a wavelength of 300 nm or less include KrF rays (wavelength 248 nm) and ArF rays (wavelength 193 nm). Furthermore, exposure may be performed by continuously irradiating with light, or by repeatedly irradiating and pausing with light in short cycles (for example, at the millisecond level or less) (pulsed exposure).

[0141] [Development process] Next, by performing an alkaline development treatment, the unexposed areas of the coating dissolve in the alkaline aqueous solution, leaving only the hardened areas and resulting in a patterned coating. Examples of alkaline developers include alkaline compounds such as sodium hydroxide, potassium hydroxide, sodium carbonate, sodium silicate, sodium metasilicate, aqueous ammonia, ethylamine, diethylamine, dimethylethanolamine, tetramethylammonium hydroxide, tetraethylammonium hydroxide, choline, pyrrole, piperidine, and 1,8-diazabicyclo-[5.4.0]-7-undecene. The concentration of the alkaline developer is preferably 0.001 to 10% by mass, and more preferably 0.01 to 1% by mass. The pH of the alkaline developer is preferably 11 to 13, and more preferably 11.5 to 12.5. Using an appropriate pH suppresses pattern roughness and peeling, and improves the residual film rate after development. Development methods include, for example, the dip method, spray method, and paddle method. The development temperature is preferably 15 to 40°C. After alkaline development, it is preferable to wash with pure water.

[0142] [Heat treatment process] After development, heat treatment can be performed if necessary. Post-baking improves the durability of the film. The temperature is preferably between 80 and 300°C. The duration is preferably between 2 minutes and 1 hour. When a material with low heat resistance is used as the substrate, or when an organic electroluminescent element is used as the light source, the temperature is preferably 150°C or lower, and more preferably 130°C or lower.

[0143] <High refractive index film> The high refractive index film of the present invention can be produced by going through the aforementioned coating process, exposure and development process as needed, and heat treatment process.

[0144] <Liquid crystal display device> Figures 1(a) and 1(b) are schematic cross-sectional views of a liquid crystal display device. In Figure 1(a), the high refractive index film 18 is formed between the color filter 17 and the glass substrate 13. In Figure 1(b), the high refractive index film 18 is formed between the color filter 17 and the counter electrode plate 16.

[0145] <Organic EL display device> Figures 2(a), 2(b), and 2(c) are schematic cross-sectional views of an organic EL display device. In Figure 2(a), the high refractive index film 25 is formed between the substrate 21 and the color filter 24. In Figure 2(b), the high refractive index film 25 is formed between the color filter 24 and the organic EL layer 23. In Figure 2(c), the high refractive index film 25 is formed as a microlens between the resin layer 26 and the color filter 24.

[0146] <Solid-state image sensor> The high refractive index film of the present invention can be used in solid-state image sensors. The form in which it is used in a solid-state image sensor is not particularly limited, but for example, it may have a substrate on which a plurality of photodiodes constituting the light-receiving area of ​​a solid-state image sensor (CCD image sensor, CMOS image sensor, etc.) and transfer electrodes made of polysilicon or the like are provided, a light-shielding film with an opening only for the light-receiving portion of the photodiode is provided on the photodiodes and transfer electrodes, a device protection film made of silicon nitride or the like is provided on the light-shielding film so as to cover the entire surface of the light-shielding film and the light-receiving portion of the photodiode, and a filter is provided on the device protection film. Furthermore, it may have a configuration in which a light-gathering means (e.g., a microlens, etc.; the same applies hereinafter) is provided on the device protection film below the filter (closer to the substrate), or a configuration in which the light-gathering means is provided on the filter. The filter may also have a structure in which a hardened film forming each colored pixel is embedded in a space partitioned, for example, in a grid pattern by partitions. In this case, it is preferable that the partitions have a low refractive index with respect to each colored pixel. The imaging device equipped with the solid-state image sensor of the present invention can be used in a variety of applications, such as digital cameras, electronic devices with imaging functions (smartphones, tablet terminals, etc.), in-vehicle cameras, surveillance cameras, and optical sensors.

[0147] <Other uses> The high refractive index film of the present invention can be used as an optical component as an optical functional film included in anti-reflective films, reflective films, semi-transparent and semi-reflective films, visible light reflective infrared transmitting films, infrared reflective visible light transmitting films, blue reflective films, green reflective or red reflective films, bright line cut filters, color correction films, and undercoats, and can be used in infrared sensors, micro-LED display devices, head-up displays, etc. [Examples]

[0148] The present invention will be described below with reference to examples. However, the present invention is not limited to these examples. In the examples, "parts" refers to "parts by mass" and "%" refers to "mass%".

[0149] Prior to the examples, the methods for calculating the average molecular weight of the resin and the acid value of the resin will be explained.

[0150] (Average molecular weight of resin) The number-average molecular weight (Mn) and mass-average molecular weight (Mw) of the resin were measured by gel permeation chromatography (GPC) equipped with a radioisotope detector. An HLC-8220GPC (Tosoh Corporation) was used, with two separation columns connected in series. Both columns were packed with two TSK-GEL SUPER HZM-N columns. Measurements were performed at an oven temperature of 40°C, using THF solution as the eluent, and a flow rate of 0.35 ml / min. The sample was dissolved in a 1 wt% solution of the above eluent and injected in 20 microliters. All molecular weights are polystyrene equivalents.

[0151] (Acid value of resin) 0.5 to 1 g of resin solution was mixed with 80 ml of acetone and 10 ml of water and stirred to dissolve uniformly. A 0.1 mol / L aqueous KOH solution was used as the titrant, and the solution was titrated using an automatic titrator ("COM-555," manufactured by Hiranuma Sangyo Co., Ltd.) to measure the acid value (mgKOH / g) of the resin solution. The acid value per unit of non-volatile content of the resin was then calculated from the acid value of the resin solution and the concentration of non-volatile content of the resin solution. (Average particle size of titanium dioxide particle dispersion) The average particle size of the titanium dioxide particle dispersion was measured using the "NanoTrack UPA" manufactured by Nikkiso Co., Ltd. (Refractive index of coating film) The refractive index of the coating film was measured using the "M-2000UI" manufactured by J.A. Woolam Japan Co., Ltd. (viscosity) The viscosity of the photosensitive composition was measured using an E-type viscometer (ELD-type viscometer manufactured by Toki Sangyo Co., Ltd.) at 25°C and a rotation speed of 50 rpm.

[0152] <Dispersant (A1)> (Synthesis Example 1: Dispersant (A1-1)) Into a four-necked flask equipped with a stirrer, a reflux condenser, a dry air inlet tube, and a thermometer, 80.0 parts of 3,3',4,4'-biphenyltetracarboxylic dianhydride (manufactured by Mitsubishi Chemical Corporation, trade name BPDA), 250.0 parts of pentaerythritol triacrylate with a hydroxyl value of 122 mgKOH / g (manufactured by Nippon Kayaku Co., Ltd., trade name: KAYARAD PET-30, containing pentaerythritol tetraacrylate as a by-product), 0.24 parts of methylhydroquinone (manufactured by Wako Pure Chemical Industries, Ltd.), and 217.8 parts of cyclohexanone were charged, and the temperature was raised to 60 °C. Next, 1.65 parts of 1,8-diazabicyclo[5.4.0]-7-undecene (manufactured by Tokyo Chemical Industry Co., Ltd.) was added as a catalyst, and the mixture was stirred at 90 °C for 8 hours. After confirming by IR measurement of the reaction product that the peaks of the acid anhydride groups, that is, the peaks around 1780 cm -1 and 1850 cm -1 had disappeared, the mixture was cooled and the reaction was stopped. Subsequently, 140.0 parts of biphenyl glycidyl ether (manufactured by Sanko Co., Ltd., trade name: OPP-G) and 91.0 parts of cyclohexanone were added to this solution, and then 2.65 parts of dimethylbenzylamine (manufactured by Wako Pure Chemical Industries, Ltd.) was added as a catalyst, and the mixture was stirred at 100 °C for 6 hours to cause a reaction. While continuing the reaction, the acid value of the reaction product was periodically measured. When the acid value reached 5.0 mgKOH / g or less, the mixture was cooled to room temperature to stop the reaction, and a compound solution containing compound (A1-1) was obtained. (Non-volatile content: 60%)

[0153] (Synthesis Example 2: Dispersant (A1-2)) In a four-necked flask equipped with a stirrer, reflux condenser, dry air inlet, and thermometer, 80.0 parts of 3,3',4,4'-biphenyltetracarboxylic dianhydride (Mitsubishi Chemical Corporation, trade name: BPDA), 250.0 parts of pentaerythritol triacrylate with a hydroxyl value of 122 mg KOH / g (Nippon Kayaku Co., Ltd., trade name: KAYARAD PET-30, also containing pentaerythritol tetraacrylate as a by-product), 0.24 parts of methylhydroquinone (Wako Pure Chemical Industries, Ltd.), and 217.8 parts of cyclohexanone were charged and the mixture was heated to 60°C. Then, 1.65 parts of 1,8-diazabicyclo[5.4.0]-7-undecene (Tokyo Chemical Industries, Ltd.) was added as a catalyst, and the mixture was stirred at 90°C for 8 hours. IR measurement of the reaction product showed a peak for the acid anhydride group, i.e., 1780 cm⁻¹. -1 and 1850cm -1 After confirming that the nearby peaks had disappeared, the reaction was stopped by cooling. Next, 78.3 parts of methacrylate glycidyl ether (manufactured by Dow Chemical Japan, GMA) and 54.0 parts of cyclohexanone were added to this solution. Then, 2.65 parts of dimethylbenzylamine (manufactured by Wako Pure Chemical Industries, Ltd.) were added as a catalyst, and the mixture was stirred at 100°C for 6 hours. The acid value of the reactants was measured periodically while the reaction continued. When the acid value fell below 5.0 mg KOH / g, the reaction was stopped by cooling to room temperature, yielding a compound solution containing compounds (A1-2). (Non-volatile content: 60%)

[0154] (Synthesis Example 3: Dispersant (A1-3)) In a four-necked flask equipped with a stirrer, reflux condenser, dry air inlet, and thermometer, 80.0 parts of 3,3',4,4'-biphenyltetracarboxylic dianhydride (Mitsubishi Chemical Corporation, trade name: BPDA), 250.0 parts of pentaerythritol triacrylate with a hydroxyl value of 122 mg KOH / g (Nippon Kayaku Co., Ltd., trade name: KAYARADPET-30, also containing pentaerythritol tetraacrylate as a by-product), 0.24 parts of methylhydroquinone (Wako Pure Chemical Industries, Ltd.), and 217.8 parts of cyclohexanone were charged and the mixture was heated to 60°C. Then, 1.65 parts of 1,8-diazabicyclo[5.4.0]-7-undecene (Tokyo Chemical Industries, Ltd.) was added as a catalyst, and the mixture was stirred at 90°C for 8 hours. IR measurement of the reaction product showed a peak for the acid anhydride group, i.e., 1780 cm⁻¹. -1 and 1850cm -1 After confirming that the nearby peaks had disappeared, the solution was cooled to obtain a compound solution containing compound (A1-3). (Non-volatile content: 60%)

[0155] <Other dispersants> (Synthesis Example 4: Dispersant (A2)) In a four-necked flask equipped with a stirrer, reflux condenser, dry air inlet, and thermometer, 80.0 parts of 3,3',4,4'-biphenyltetracarboxylic dianhydride (Mitsubishi Chemical Corporation, trade name: BPDA), 63.1 parts of 2-hydroxyethyl acrylate (Nippon Shokubai Co., Ltd., trade name: HEA) with a hydroxyl value of 483 mg KOH / g, 0.11 parts of methylhydroquinone (Wako Pure Chemical Industries, Ltd.), and 94.6 parts of cyclohexanone were charged and the mixture was heated to 60°C. Next, 0.72 parts of 1,8-diazabicyclo[5.4.0]-7-undecene (Tokyo Chemical Industries, Ltd.) was added as a catalyst, and the mixture was stirred at 90°C for 8 hours. IR measurement of the reaction product showed a peak for the acid anhydride group, i.e., 1780 cm⁻¹. -1 and 1850cm -1 After confirming that the nearby peaks had disappeared, the reaction was stopped by cooling. Next, 78.3 parts of methacrylate glycidyl ether (manufactured by Dow Chemical Japan, GMA) and 51.1 parts of cyclohexanone were added. Then, 1.15 parts of dimethylbenzylamine were added as a catalyst, and the mixture was stirred at 100°C for 6 hours. The acid value of the reactants was measured periodically while the reaction continued. When the acid value fell below 5.0 mg KOH / g, the mixture was cooled to room temperature to stop the reaction, and a compound solution containing compound (A2) was obtained. (Non-volatile content: 60%)

[0156] <Titanium dioxide particles (B)> Titanium dioxide particles (B-1): Product name: SMT-100SAS (manufactured by Teika Co., Ltd., primary particle size: 15 nm, titanium dioxide concentration: 82%, surface treatment: aluminum hydroxide, hydrated silica, trimethylsiloxysilicate) Titanium dioxide particles (B-2): Product name: MT-02 (manufactured by Teika Co., Ltd., primary particle size: 10 nm, titanium dioxide concentration: 76%, surface treatment: aluminum hydroxide, hydrated silica, methylhydrogenpolysiloxane) Titanium dioxide particles (B-3): Product name: MT-500SAS (manufactured by Teika Co., Ltd., primary particle size: 35 nm, titanium dioxide concentration: 90%, surface treatment: aluminum hydroxide, hydrated silica, methylhydrogenpolysiloxane)

[0157] <Method for producing titanium dioxide particle dispersion> (Manufacturing example 1: Titanium dioxide particle dispersion (1)) A dispersion of titanium dioxide particles (1) with a non-volatile content of 23% was prepared by dispersing 5.0 parts of the dispersant (A1-1) prepared according to the above synthesis example 1, 20.0 parts of titanium dioxide particles (B-1), 37.5 parts of methyl ethyl ketone, and 37.5 parts of methoxybutanol. The dispersion method was carried out in two stages: pre-dispersion (using zirconia beads (0.5 mm) as a medium and dispersing in a paint shaker for 1 hour) and main dispersion (using zirconia beads (0.1 mm) as a medium and dispersing in a Kotobuki Kogyo Co., Ltd. disperser UAM-015).

[0158] (Manufacturing examples 2-10: Titanium dioxide particle dispersion (2)-(10)) Dispersant (A) and titanium dioxide (B) were combined as shown in Table 1, and titanium dioxide dispersions (2) to (10) were obtained in the same manner as in Production Example 1.

[0159] [Table 1]

[0160] <Example of binder resin (D) manufacturing> (Preparation of binder resin (D-1-1) solution) 150 parts of cyclohexanone were placed in a reaction vessel, and the vessel was heated to 80°C while nitrogen gas was injected into the vessel. The polymerization reaction was carried out by dropwise adding the mixture of monomers and thermal polymerization initiators listed below over 1 hour at the same temperature. After dropwise adding 20.0 parts of methacrylic acid, 10.0 parts of methyl methacrylate, 55.0 parts of n-butyl methacrylate, 15.0 parts of hydroxyethyl methacrylate, and 4.0 parts of azobisisobutyronitrile, the reaction was continued at 80°C for 3 hours. Then, a mixture of 1.0 part of azobisisobutyronitrile dissolved in 50 parts of cyclohexanone was added, and the reaction was continued at 80°C for another hour to obtain an acrylic resin solution with a non-volatile acid value of 124 mg KOH / g and a weight-average molecular weight of approximately 40,000. After cooling to room temperature, approximately 2 g of the resin solution was sampled and heated and dried at 180°C for 20 minutes to measure the non-volatile content. Cyclohexanone was then added to the previously synthesized resin solution to prepare a binder resin (D-1-1) solution so that the non-volatile content was 30% by weight.

[0161] (Preparation of binder resin (D-1-2) solution) A reaction vessel was prepared by fitting a thermometer, condenser, nitrogen gas inlet, dropping tube, and stirrer into a separable four-neck flask. 190 parts of propylene glycol monomethyl ether acetate were charged into the vessel, and the temperature was raised to 80°C. After purging the reaction vessel with nitrogen, a mixture of 37.2 parts n-butyl methacrylate, 12.9 parts 2-hydroxyethyl methacrylate, 12.0 parts methacrylic acid, 20.7 parts paracumylphenol ethylene oxide modified acrylate (Toagosei Co., Ltd. "Aronics M110"), and 1.1 parts 2,2'-azobisisobutyronitrile was added dropwise over 2 hours via the dropping tube. After the dropwise addition was complete, the reaction was continued for another 3 hours to obtain an acrylic resin solution. After cooling to room temperature, approximately 2 parts of the resin solution were sampled and heated and dried at 180°C for 20 minutes to measure the non-volatile content. Propylene glycol monomethyl ether acetate was then added to the previously synthesized resin solution to prepare a binder resin (D-1-2) solution so that the non-volatile content was 30% by weight. The non-volatile acid value was 93 mgKOH / g, and the weight-average molecular weight (Mw) was 26000.

[0162] (Preparation of binder resin (D-2-1) solution) A reaction vessel was prepared by fitting a thermometer, condenser, nitrogen gas inlet, dropping tube, and stirrer into a separable four-neck flask. 207 parts of cyclohexanone were charged into this vessel, and the temperature was raised to 80°C. After purging the reaction vessel with nitrogen, a mixture of 20 parts methacrylic acid, 20 parts paracumylphenol ethylene oxide-modified acrylate (Aronics M110, manufactured by Toagosei Co., Ltd.), 45 parts methyl methacrylate, 8.5 parts 2-hydroxyethyl methacrylate, and 1.33 parts 2,2'-azobisisobutyronitrile was added dropwise over 2 hours via the dropping tube. After the dropwise addition was complete, the reaction was continued for another 3 hours to obtain a copolymer solution. Next, the entire copolymer solution was stirred while injecting dry air for 1 hour after stopping the nitrogen gas supply, and then cooled to room temperature. A mixture of 6.5 parts 2-methacryloyloxyethyl isocyanate (Kalenz MOI, Showa Denko Co., Ltd.), 0.08 parts dibutyltin laurate, and 26 parts cyclohexanone was added dropwise at 70°C for 3 hours. After the dropwise addition was complete, the reaction was continued for another hour to obtain an acrylic resin solution. After cooling to room temperature, approximately 2 parts of the resin solution were sampled and heated and dried at 180°C for 20 minutes to measure the non-volatile content. Cyclohexanone was then added to the previously synthesized resin solution to prepare a binder resin (E-2-1) with a non-volatile content of 30%. The non-volatile acid value was 129 mgKOH / g, and the weight-average molecular weight (Mw) was 18000.

[0163] (Preparation of binder resin (D-2-2) solution) 170 parts of cyclohexanone were placed in a separable four-necked flask equipped with a thermometer, condenser, nitrogen gas inlet tube, dropping tube, and stirrer. The temperature was raised to 80°C, and the flask was purged with nitrogen. A mixture of 18 parts of paracumylphenol ethylene oxide-modified acrylate (Aronics M110, manufactured by Toagosei Co., Ltd.), 10 parts of benzyl methacrylate, 18.2 parts of glycidyl methacrylate, 25 parts of methyl methacrylate, and 2.0 parts of 2,2'-azobisisobutyronitrile was added dropwise over 2 hours via the dropping tube. After the dropwise addition, the mixture was reacted at 100°C for 3 hours, and then 1.0 part of azobisisobutyronitrile dissolved in 50 parts of cyclohexanone was added. The reaction was then continued at 100°C for 1 hour. Next, the container was replaced with an air purging system, and 9.3 parts acrylic acid (equivalent to 100 mol% of glycidyl groups), 0.5 parts trisdimethylaminophenol, and 0.1 parts hydroquinone were added to the container. The reaction was continued at 120°C for 6 hours until the non-volatile acid value reached 0.5 mg KOH / g, at which point the reaction was terminated to obtain an acrylic resin solution. Subsequently, 19.5 parts tetrahydrophthalic anhydride (equivalent to 100 mol% of the generated hydroxyl groups) and 0.5 parts triethylamine were added and the reaction was continued at 120°C for 3.5 hours to obtain an acrylic resin solution. After cooling to room temperature, approximately 2 g of the resin solution was sampled and heated and dried at 180°C for 20 minutes to measure the non-volatile content. PGMAc was then added to the previously synthesized resin solution to achieve a non-volatile content of 30% by mass to prepare a binder resin (D-2-2) solution. The non-volatile acid value was 70 mg KOH / g, and the weight-average molecular weight (Mw) was 19000.

[0164] (Preparation of binder resin (D-2-3) solution) In a flask equipped with a stirrer, thermometer, reflux condenser, dropping funnel, and nitrogen inlet tube, 182 g of PGMAc was introduced. After changing the atmosphere inside the flask from air to nitrogen, the temperature was raised to 100°C. A solution consisting of 70.5 g (0.40 mol) of benzyl methacrylate, 43.0 g (0.5 mol) of methacrylic acid, 22.0 g (0.10 mol) of tricyclodecane skeleton monomethacrylate (FA-513M, Hitachi Chemical Co., Ltd.), and 136 g of PGMAc, to which 3.6 g of azobisisobutyronitrile was added, was added dropwise to the flask from the dropping funnel over 2 hours, and the mixture was then stirred at 100°C for 5 hours. Next, the atmosphere inside the flask was changed from nitrogen to air, and 35.5 g of glycidyl methacrylate [0.25 mol, (50 mol% relative to the carboxyl groups of the methacrylic acid used in this reaction)], 0.9 g of trisdimethylaminomethylphenol, and 0.145 g of hydroquinone were added to the flask. The reaction was continued at 110°C for 6 hours and then terminated. Cyclohexanone was added to obtain an alkali-soluble resin (D-2-3) solution so that the non-volatile content was 30% by mass. The weight-average molecular weight was 13,000, the molecular weight distribution (Mw / Mn) was 2.1, and the non-volatile acid value was 79 mg KOH / g.

[0165] [Example 1] (Preparation of photosensitive composition (X-1)) A titanium dioxide particle dispersion (23% by mass of non-volatile content), a polymerizable compound, a binder resin solution (30% by mass of non-volatile content), a solvent, an ultraviolet absorber, a polymerization inhibitor, a photopolymerization initiator, and a leveling agent solution (3% of non-volatile content) were mixed by stirring until homogeneous. The mixture was then filtered through a 5.0 μm pore size filter to prepare a photosensitive composition (X-1). The proportions of materials other than the solvent were calculated based on their non-volatile content, totaling 100 parts. Dispersant (A1-1): 7.50 parts Titanium dioxide particles (B-1): 50.00 parts Polymerizable compound (C-2): 10.00 parts Binder resin (D-2-2): 29.34 parts Solvent (E): 36.49 parts UV absorber (F-3): 2.00 parts Polymerization inhibitor (G): 0.10 parts Photopolymerization initiator (H-1): 1.00 part Leveling agent (I): 0.06 parts

[0166] [Examples 2-29, Comparative Examples 1, 3-4] (Preparation of photosensitive compositions (X-2~29, X-31, 33~34)) Photosensitive compositions (X-2~29, X-31, 33~34) were prepared in the same manner as in Example 1, except that the material types and masses were changed as described in Tables 1-1 and 1-2.

[0167] [Example 30] (Preparation of photosensitive composition (X-30)) A titanium dioxide particle dispersion (23% by mass of non-volatile content), a polymerizable compound, a binder resin solution (30% by mass of non-volatile content), a solvent, an ultraviolet absorber, a polymerization inhibitor, a photopolymerization initiator, a leveling agent solution (3% of non-volatile content), a thermosetting compound, a sensitizer, a chain transfer agent, an antioxidant, a storage stabilizer, and an adhesion enhancer were mixed and stirred until uniform. The mixture was then filtered through a 5.0 μm pore size filter to prepare a photosensitive composition (X-30). The proportions of materials other than the solvent were calculated based on their non-volatile content, totaling 100 parts. Dispersant (A1-1): 7.50 parts Titanium dioxide particles (B-1): 50.00 parts Polymerizable compound (C-2): 10.00 parts Binder resin (D-2-2): 25.54 parts Solvent (E): 38.04 parts UV absorber (F-3): 2.00 parts Polymerization inhibitor (G-1): 0.10 parts Photopolymerization initiator (H-1): 1.00 part Leveling agent (I): 0.06 parts Thermosetting compound (J-1): 1.50 parts Thermosetting compound (J-2): 1.50 parts Sensitizer (K): 0.20 parts Chain transfer agent (L): 0.20 parts Antioxidant (M): 0.10 parts Storage stabilizer (N): 0.10 parts Adhesion enhancer (O): 0.20 parts

[0168] [Comparative Example 2] (Preparation of photosensitive composition (X-32)) Titanium dioxide, polymerizable compound, binder resin solution (30% by mass of non-volatile content), solvent, UV absorber, polymerization inhibitor, photopolymerization initiator, and leveling agent solution (3% of non-volatile content) were mixed by stirring until homogeneous, and then filtered through a 5.0 μm pore size filter to prepare a photosensitive composition (X-32). Note that the proportions of materials other than the solvent are calculated based on their non-volatile content, totaling 100 parts. Titanium dioxide particles (B-1): 50.00 parts Polymerizable compound (C-2): 17.50 parts Binder resin (D-2-2): 29.34 parts Solvent (E): 78.93 parts UV absorber (F-3): 2.00 parts Polymerization inhibitor (G-1): 0.10 parts Photopolymerization initiator (H-1): 1.00 part Leveling agent (I): 0.06 parts

[0169] [Table 2-1]

[0170] [Table 2-2]

[0171] <Polymerizable compound (C)> (C-1) Bifunctional bisphenol A type (meth)acrylate [ABE-300 (manufactured by Shin-Nakamura Chemical Co., Ltd.)] (C-2) Trifunctional acrylic monomer Trimethylolpropane triacrylate [Aronix M309 (manufactured by Toagosei Co., Ltd.)] (C-3) Trimethylolpropane EO modified triacrylate [Aronix M350 (manufactured by Toagosei Co., Ltd.)] (C-4) A mixture of pentaerythritol triacrylate and pentaerythritol tetraacrylate. [Aronix M450 (manufactured by Toagosei Co., Ltd.)] (C-5) A mixture of dipentaerythritol pentaacrylate and dipentaerythritol hexaacrylate. [Aronix M402 (manufactured by Toagosei Co., Ltd.)]

[0172] <Solvent (E)> (E-1) PGMAc 30 copies (E-2) Cyclohexanone 30 parts (E-3) 3-Ethoxypropionate 10 parts (E-4) Propylene glycol monomethyl ether 10 parts (E-5) Cyclohexanol acetate 10 parts (E-6) Dipropylene glycol methyl ether acetate 10 parts The above (E-1) to (E-6) were mixed in the above-mentioned parts by mass to obtain solvent (E).

[0173] <UV absorber (F)> (F-1) Benzonon-based UV absorber 2,2',4,4'-Tetrahydroxybenzophenone [Uvinul3050 (manufactured by BASF Japan)] (F-2) Benzotriazole-based UV absorber 2,2'-Methylenebis[4-(1,1,3,3-tetramethylbutyl)-6-(2H-benzotriazol-2-yl)phenol] [KEMISORB 279 (manufactured by Chemipro Chemical Co., Ltd.)] (F-3) Benzotriazole-based UV absorber 2-(2'-hydroxy-5'-tert-octylphenyl)benzotriazole [TINUVIN326 (manufactured by BASF Japan)] (F-4) Benzotriazole-based UV absorber 2-(2H-benzotriazol-2-yl)-4,6-bis(1-methyl-1-phenylethyl)phenol [TINUVIN900 (manufactured by BASF Japan)] (F-5) The following method was used for synthesis. 3-Anilinoacroleinyl (13.3 parts) and ethylphenylsulfonyl acetate (14.3 parts) were heated in acetic anhydride (40 parts) at 85-90°C for 2 hours. The acetic anhydride was removed under reduced pressure drying, and ethanol (40 parts) and di-n-hexylamine (24.1 parts) were added and refluxed for 2 hours. The ethanol was removed, the residue was purified by column chromatography, and recrystallized from the ethanol.

[0174] UV absorber (F-5) [ka]

[0175] <Polymerization inhibitor (G)> (G-1)3-methylcatechol (G-2) Methylhydroquinone (G-3) tert-butylhydroquinone The above (G-1) to (G-3) were mixed in equal amounts to form polymerization inhibitor (G).

[0176] <Photopolymerization initiator (H)> (H-1) Carbazole-based oxime ester photopolymerization initiator Ethane-1-one, 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazole-3-yl], 1-(O-acetyloxime) [Irgacure OXE02 (manufactured by BASF Japan)] (H-2) Diphenyl oxime ester photopolymerization initiator 1,2-Octadione-1-[4-(phenylthio)phenyl-,2-(O-benzoyloxime)] [Irgacure OXE01 (manufactured by BASF Japan)] (H-M1) The following (H-3) to (H-6) were mixed in equivalent amounts to form the photopolymerization initiator (H-M1). (H-3) Carbazole-based oxime ester photopolymerization initiator: Photopolymerization initiator synthesized by the method described below. 100.0 parts of N-benzophenoylcarbazole were dissolved in 1000 parts of chloroform, and 85.0 parts of aluminum chloride were added. Under stirring at 0°C, a solution of 32.0 parts of propionyl chloride dissolved in 500 parts of chloroform was added dropwise over 2 hours. After the addition was complete, the mixture was stirred at 25°C for 4 hours. The reaction mixture was poured into 2000 parts of ice water and extracted with 2000 parts of chloroform. The organic layer was dried over magnesium sulfate, and after filtering off the drying agent (magnesium sulfate), the residue was recrystallized with chloroform / methanol to obtain 113.0 parts of intermediate compound (a1). Next, 100.0 parts of compound (a1) were dissolved in a mixed solution of 1000 parts of tetrahydrofuran and 500 parts of concentrated hydrochloric acid. Under stirring at room temperature, 38.4 parts of tert-butyl nitrite were added dropwise over 1 hour. After the addition was complete, the mixture was stirred at room temperature for 5 hours. The reaction mixture was poured into 1600 parts of ice water and extracted with 1600 parts of chloroform. The organic layer was washed with water (500 parts x 3 times), dried over magnesium sulfate, filtered to remove the drying agent (magnesium sulfate), and the solvent was removed. The residue was washed with n-hexane to obtain 99.8 parts of precursor compound (b1). Next, 30.0 parts of compound (b1) was stirred in 300 parts of ethyl acetate, to which 6.3 parts of acetic anhydride and 10.6 parts of sodium acetate were added, and the mixture was heated under reflux for 3 hours. After that, the reaction mixture was poured into 500 parts of ice water, the compounds were extracted with ethyl acetate, the organic layer was washed with water (300 parts x 3 times), dried over magnesium sulfate, filtered to remove the drying agent (magnesium sulfate), and the solvent was removed. The residue was recrystallized with ethyl acetate-hexane to obtain 31.4 g of photopolymerization initiator (H-3).

[0177] Photopolymerization initiator (H-3) [ka]

[0178] (H-4) Carbazole-based oxime ester photopolymerization initiator: Photopolymerization initiator synthesized by the method described below. 100.0 parts of N-benzophenoylcarbazole were dissolved in 1000 parts of chloroform, and 84.0 parts of aluminum chloride were added. Under stirring at 0°C, a solution of 36.8 parts of butanoyl chloride dissolved in 500 parts of chloroform was added dropwise over 2 hours. After the addition was complete, the mixture was stirred at 25°C for 4 hours. The reaction mixture was poured into 2000 parts of ice water and extracted with 2000 parts of chloroform. The organic layer was dried over magnesium sulfate, and after filtering off the drying agent (magnesium sulfate), the residue was recrystallized with chloroform / methanol to obtain 109.3 parts of intermediate compound (a2). Next, 100.0 parts of compound (a2) were dissolved in a mixed solution of 1000 parts of tetrahydrofuran and 500 parts of concentrated hydrochloric acid. Under stirring at room temperature, 43.1 parts of tert-butyl nitrite were added dropwise over 1 hour. After the addition was complete, the mixture was stirred at room temperature for 5 hours. The reaction mixture was poured into 1600 parts of ice water and extracted with 1600 parts of chloroform. The organic layer was washed with water (500 parts x 3 times), dried over magnesium sulfate, filtered to remove the drying agent (magnesium sulfate), and the solvent was removed. The residue was washed with n-hexane to obtain 89.3 parts of precursor compound (b2). Next, 30.0 parts of compound (b2) was stirred in 300 parts of ethyl acetate, to which 6.1 parts of acetic anhydride and 10.3 parts of sodium acetate were added, and the mixture was heated under reflux for 3 hours. After that, the reaction mixture was poured into 500 parts of ice water, the compounds were extracted with ethyl acetate, the organic layer was washed with water (300 parts x 3 times), dried over magnesium sulfate, filtered to remove the drying agent (magnesium sulfate), and the solvent was removed. The residue was recrystallized with ethyl acetate-hexane to obtain 30.0 parts of photopolymerization initiator (H-4).

[0179] Photopolymerization initiator (H-4) [ka]

[0180] (H-5) Carbazole-based oxime ester photopolymerization initiator: Photopolymerization initiator synthesized by the method described below. 100.0 parts of N-(p-nitrophenyl)carbazole were dissolved in 1000 parts of chloroform, and 101.8 parts of aluminum chloride were added. Under stirring at 0°C, a solution of 44.3 parts of butanoyl chloride dissolved in 500 parts of chloroform was added dropwise over 2 hours. After the addition was complete, the mixture was stirred at 25°C for 4 hours. The reaction mixture was poured into 2000 parts of ice water and extracted with 2000 parts of chloroform. The organic layer was dried over magnesium sulfate, and after filtering off the drying agent (magnesium sulfate), the residue was recrystallized with chloroform / methanol to obtain 113.6 parts of intermediate compound (a3). Next, 100.0 parts of compound (a3) ​​were dissolved in a mixed solution of 1000 parts of tetrahydrofuran and 500 parts of concentrated hydrochloric acid. Under stirring at room temperature, 43.1 parts of tert-butyl nitrite were added dropwise over 1 hour. After the addition was complete, the mixture was stirred at room temperature for 5 hours. The reaction mixture was poured into 1600 parts of ice water and extracted with 1500 parts of chloroform. The organic layer was washed with water (500 parts x 3 times), dried over magnesium sulfate, filtered to remove the drying agent (magnesium sulfate), and the solvent was removed. The residue was washed with n-hexane to obtain 107.2 parts of precursor compound (b3). Next, 50.0 parts of compound (b3) was stirred in 500 parts of ethyl acetate, to which 19.9 parts of acetic anhydride and 11.7 parts of sodium acetate were added, and the mixture was heated under reflux for 3 hours. After that, the reaction mixture was poured into 500 parts of ice water, the compounds were extracted with ethyl acetate, the organic layer was washed with water (500 parts x 3 times), dried over magnesium sulfate, filtered to remove the drying agent (magnesium sulfate), and the solvent was removed. The residue was recrystallized with ethyl acetate-hexane to obtain 57.6 parts of photopolymerization initiator (H-5).

[0181] Photopolymerization initiator (H-5) [ka]

[0182] (H-6) Carbazole-based oxime ester photopolymerization initiator: Photopolymerization initiator synthesized by the method described below. 100.0 parts of N-benzophenoyl-1,3-dimethylcarbazole were dissolved in 1000 parts of chloroform, and 78.6 parts of aluminum chloride were added. Under stirring at 0°C, a solution of 29.6 parts of propionyl chloride dissolved in 500 parts of chloroform was added dropwise over 2 hours. After the addition was complete, the mixture was stirred at 25°C for 4 hours. The reaction mixture was poured into 2000 parts of ice water and extracted with 2000 parts of chloroform. The organic layer was dried over magnesium sulfate, and after filtering off the drying agent (magnesium sulfate), the residue was recrystallized with chloroform / methanol to obtain 111.8 parts of intermediate compound (a4). Next, 100.0 parts of compound (a4) were dissolved in a mixed solution of 1000 parts of tetrahydrofuran and 500 parts of concentrated hydrochloric acid. Under stirring at room temperature, 35.7 parts of tert-butyl nitrite were added dropwise over 1 hour. After the addition was complete, the mixture was stirred at room temperature for 5 hours. The reaction mixture was poured into 1600 parts of ice water and extracted with 1600 parts of chloroform. The organic layer was washed with water (500 parts x 3 times), dried over magnesium sulfate, filtered to remove the drying agent (magnesium sulfate), and the solvent was removed. The residue was washed with n-hexane to obtain 98.3 parts of precursor compound (b4). Next, 30.0 parts of compound (b4) was stirred in 300 parts of ethyl acetate, to which 5.9 parts of acetic anhydride and 10.0 parts of sodium acetate were added, and the mixture was heated under reflux for 3 hours. After that, the reaction mixture was poured into 500 parts of ice water, the compounds were extracted with ethyl acetate, the organic layer was washed with water (300 parts x 3 times), dried over magnesium sulfate, filtered to remove the drying agent (magnesium sulfate), and the solvent was removed. The residue was recrystallized with ethyl acetate-hexane to obtain 31.2 parts of photopolymerization initiator (H-6).

[0183] Photopolymerization initiator (H-6) [ka]

[0184] (H-M2) The above (H-1) and the following (H-8) were mixed in equivalent amounts to form the photopolymerization initiator (H-M2).

[0185] (H-M3) The following (H-7) to (H-13) were mixed in equivalent amounts to form the photopolymerization initiator (H-M3). (H-7) Alkylphenone-based photoinitiator 2-Methyl-1-[4-(methylthio)phenyl]-2-morpholinopropan-1-one [Omnirad907 (manufactured by IGM Resins)] (H-8) Alkylphenone-based photoinitiator 2-(Dimethylamino)-2-[(4-methylphenyl)methyl]-1-[4-(4-morpholinyl)phenyl]-1-butanone [Omnirad379 (manufactured by IGM Resins)]] (H-9) Acylphosphine oxide-based photoinitiator 2,4,6-Trimethylbenzoyl-diphenyl-phosphine oxide [Omnirad TPO H (manufactured by IGM Resins)] (H-10) Imidazole-based photoinitiator 2,2’-Bis(o-chlorophenyl)-4,5,4’,5’-tetraphenyl-1,2’-biimidazole [Biimidazole (manufactured by Kurogane Kasei Co., Ltd.)] (H-11) Alkylphenone-based photoinitiator p-Dimethylaminoacetophenone [DMA (manufactured by Daiki Fine Co., Ltd.)] (H-12) Alkylphenone-based photoinitiator 1-[4-(2-Hydroxyethoxy)-phenyl]-2-hydroxy-2-methyl-1-propan-1-one [Omnirad 2959 (manufactured by IGM Resins)] (H-13) Acylphosphine oxide-based photoinitiator Bis(2,4,6-trimethylbenzoyl)-phenylphosphine oxide [Omnirad819 (manufactured by IGM Resins)]

[0186] <Leveling agent (I)> 1 part of "FZ-2122" manufactured by Toray Dow Corning, 1 part of "BYK-330" manufactured by BYK Chemie, One unit of "Megafac F-551" manufactured by DIC Corporation, A mixed solution dissolved in 97 parts of propylene glycol monomethyl ether acetate.

[0187] <Thermosetting compound (J)> · Epoxy compound (J-1) (J-1-1) 1,2-epoxy-4-(2-oxiranyl) cyclohexane adduct of 2,2'-bis(hydroxymethyl)-1-butanol [EHPE-3150 (manufactured by Daicel Corporation)], (J-1-2) Glycidyl etherified epoxy compound of sorbitol [Denacol EX611 (manufactured by Nagase ChemteX Corporation)], (J-1-3) Triglycidyl isocyanurate (J-1-1) to (J-1-3) were each mixed in the same amount to obtain epoxy compound (J-1). · Oxetane compound (J-2): 3-ethyl-3-[(3-ethyloxetan-3-yl)methoxymethyl]oxetane [Aron Oxetane OXT-221 (manufactured by Toagosei Co., Ltd.)]

[0188] <Sensitizer (K)> (K-1) 2,4-diethylthioxanthone [Kayacure DETX-S (manufactured by Nippon Kayaku Co., Ltd.)] (K-2) 4,4'-bis(diethylamino)benzophenone [Chemark DEABP (manufactured by Chemark Chemical Co., Ltd.)] Above, (K-1) and (K-2) were each mixed in the same amount to obtain sensitizer (K).

[0189] <Chain transfer agent (L)> (L-1) Secondary tetrafunctional thiol: pentaerythritol tetrakis(3-mercaptobutyrate) (L-2) Secondary trifunctional thiol: trimethylolpropane tris(3-mercaptobutyrate) (L-3) Primary tetrafunctional thiol: pentaerythritol tetrakis(3-mercaptopropionate) The above (L-1) to (L-3) were mixed in equal amounts to form the chain transfer agent (L).

[0190] <Antioxidant (M)> (M-1) Pentaerythritol tetrakis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate (M-2)3,3'-Dioctadecyl Thiodipropanoate (M-3) Tris[2,4-di-(tert)-butylphenyl]phosphine (M-4) Bis(2,2,6,6-tetramethyl-4-piperidyl) sebacate (M-5) p-octylphenyl salicylate The above (M-1) to (M-5) were mixed in equal amounts to form antioxidant (M).

[0191] <Storage stabilizer (N)> (N-1)2,6-bis(1,1-dimethylethyl)-4-methylphenol (BHT manufactured by Honshu Chemical Industry Co., Ltd.) (N-2)triphenylphosphine (“TPP” manufactured by Hokuko Chemical Industry Co., Ltd.) As described above, (N-1) and (N-2) were mixed in equal amounts to form the storage stabilizer (N).

[0192] <Adhesion enhancer (O)> (O-1)3-Glycidoxypropyltriethoxysilane [Shin-Etsu Silicone Silane Coupling Agent KBM-403 (manufactured by Shin-Etsu Chemical Co., Ltd.)] (O-2)3-methacryloxypropyltriethoxysilane [Shin-Etsu Silicone Silane Coupling Agent KBE-503 (manufactured by Shin-Etsu Chemical Co., Ltd.)] (O-3)N-2-(aminoethyl)-3-aminopropyltrimethoxysilane [Shin-Etsu Silicone Silane Coupling Agent KBM-603 (manufactured by Shin-Etsu Chemical Co., Ltd.)] (O-4)3-mercaptopropyltrimethoxysilane [Shin-Etsu Silicone Silane Coupling Agent KBM-803 (manufactured by Shin-Etsu Chemical Co., Ltd.)] Above, (O-1) to (O-4) were each mixed in the same amount to obtain the silane coupling agent (O).

[0193] <Evaluation of Photosensitive Composition> Regarding the photosensitive compositions (X-1 to 34), each test was evaluated for each of the following evaluation substrates. The test results are shown in Table 3. (Preparation of Evaluation Substrate) The evaluation substrate was spin-coated with the photosensitive composition on a silicon wafer using a spin coater so that the dry film thickness was 2.0 μm, and dried at 100 °C for 5 minutes. Next, for the obtained film, exposure of 2000 mJ / cm2 was performed with an ultra-high pressure mercury lamp with an i-line illuminance of 300 mW / cm2 through a photomask in which square pattern masks of 20 μm square and 400 μm square were arranged. For the pattern-exposed film, the unexposed part was developed using a 0.30% aqueous solution of tetramethylammonium hydroxide (TMAH), and then washed with pure water. Thereafter, water droplets were blown off with high-pressure air, the substrate was naturally dried, and post-baked on a hot plate at 100 °C for 20 minutes to form a pattern of a cured film on the silicon wafer.

[0194] <Pattern Resolution Evaluation> The above evaluation substrate was observed using an electron microscope to confirm the resolution of a 20-μm square pixel pattern. The evaluation criteria are as follows. 4: Pattern resolution is observed, there is no residue adhesion, and it is an excellent level. 3: Pattern resolution is observed, and there is slight residue adhesion, which is a good level. 2: Pattern resolution is observed, and there is residue adhesion, which is a practical level. 1: Dissolution of the unexposed part is insufficient and the pattern is not resolved, or pattern formation cannot be confirmed, which is a non-practical level.

[0195] <Pattern Adhesion Evaluation> The evaluation substrate was observed using an electron microscope to confirm the degree of retention of 20 μm square and 400 μm square square pixel patterns. The evaluation criteria are as follows: 4: All patterns adhere well to the substrate, indicating an excellent level of adhesion. 3: The pattern is mostly in close contact with the substrate, indicating a good level of adhesion. 2: Half of the patterns are in close contact with the substrate, making them usable. 1: Most of the patterns do not adhere to the substrate, making them unusable.

[0196] <Refractive index of coating film>: Using the aforementioned evaluation substrate, the refractive index of the film portion was measured using a spectroscopic ellipsometer and evaluated according to the following criteria. 3: The refractive index at 600nm is between 1.75 and 1.85, which is an excellent level. 2: A refractive index of 1.65 or higher and less than 1.75 at 600nm is within the usable range. The refractive index at 1:600nm is less than 1.65, which is unsuitable for practical use.

[0197] <Storage stability> The viscosity of the aforementioned photosensitive composition was measured immediately after preparation and after storage at 40°C for one week, and the viscosity increase rate was calculated and evaluated according to the following criteria. 3: The thickness is less than 25%, which is an excellent level. 2: A viscosity increase of 25% or more but less than 50% is considered usable. 1: A viscosity increase of 50% or more makes it unusable.

[0198] [Table 3]

[0199] The results in Table 3 show that when using the photosensitive composition of the present invention, it is possible to form a high-refractive-index film with fine patterns that exhibits excellent storage stability, high refractive index, and good pattern resolution and adhesion. On the other hand, Comparative Example 1, which did not contain the dispersant of the present invention, had insufficient adhesion to the substrate. Furthermore, Comparative Example 2, which did not use a dispersant at all, resulted in poor storage stability. Comparative Examples 3 and 4, which did not contain the polymerizable compound or binder resin respectively, had insufficient pattern resolution and could not solve the problem of the present invention. [Explanation of symbols]

[0200] 11…Backlight 12…Polarizing film 13…Glass substrate 14…Pixel electrode + TFT 15…Alignment layer + liquid crystal layer 16…Counter electrode plate 17... Color Filters 18…High refractive index film 21...Base material 22…TFT 23...Organic EL layer 24... Color Filters 25…High refractive index film 26… Resin layer

Claims

1. Dispersant (A), titanium dioxide (B), and polymerizable compound (C) (however, dispersant (A) A photosensitive composition comprising (excluding), a binder resin (D), and a solvent (E), A photosensitive composition characterized in that the dispersant (A) comprises a dispersant (A1) having two sets of adjacent ester groups represented by the following general formula (1) and six or more acryloyl groups, and the polymerizable compound (C) does not have two sets of adjacent ester groups. General formula (1) 【Chemistry 1】 (In general formula (1), R １ R represents one of the following tetravalent organic residues, ２ Which of the following It represents a monovalent organic residue. Also, R ３ This is a hydrogen atom or one of the following monovalent organic residues (Represents the base.) 【Chemistry 2】 【Transformation 3】 【Chemistry 4】

2. R in the general formula (1) １ However, the claim is characterized by being an organic residue containing an aromatic ring. The photosensitive composition described in item 1.

3. The photosensitive composition according to claim 2, characterized in that the aromatic ring is a biphenyl ring.

4. The polymerizable compound (C) includes a polymerizable compound (C1) having four or fewer polymerizable unsaturated groups. The photosensitive composition according to feature 1.

5. A high refractive index film formed by the photosensitive composition according to any one of claims 1 to 4.

6. A solid-state image sensor comprising the high refractive index film described in claim 5.

7. A liquid crystal display device comprising the high refractive index film described in claim 5.

8. An organic EL display device comprising the high refractive index film described in claim 5.

Images