Laminate, scintillator panel using same, electronic component, and inductor

Abstract

A laminate according to the present invention includes: a cured product layer comprising a cured product of a resin composition containing, on a substrate, (A) a polyimide resin, (B) an oxetane compound, and (C) a photocationic polymerization initiator; and an acrylic resin layer adjacent to the substrate and the cured product layer and between the substrate and the cured product layer. Provided on a substrate is a laminate which includes a cured product having a high aspect ratio and with which peeling of the cured product can be suppressed.

Description

Laminate, scintillator panel using same, electronic component, and inductor

[0001] The present invention relates to a laminate having an acrylic resin layer and a cured product layer on a substrate, and to a scintillator panel, an electronic component, and an inductor using the same.

[0002] Digital radiation detection devices such as flat panel radiation detectors (FPDs) are used in the medical field and industrial applications such as structural inspection and baggage inspection. Indirect conversion FPDs use a scintillator panel to convert X-rays into visible light. The scintillator panel has a phosphor layer (scintillator layer) containing a phosphor such as gadolinium oxysulfide (GOS), which emits light when irradiated with X-rays. The scintillator panel converts the light emitted from the scintillator panel into an electrical signal using a sensor (photoelectric conversion layer) including a thin film transistor (TFT) or a charge-coupled device (CCD), thereby converting X-ray information into digital image information. However, scintillator panels have a problem in that the light emitted from the radioactive phosphor is scattered within the phosphor layer, reducing the sharpness of the resulting image.

[0003] Therefore, in order to reduce the effect of light scattering, a method of filling a space partitioned by partitions with a phosphor has been proposed.Furthermore, as a technology for solving the problem of brightness reduction caused by partitions, a scintillator panel has been proposed which includes a substrate, partitions formed on the substrate, and a scintillator layer partitioned by the partitions and containing a phosphor, in which the partitions contain one or more compounds (P) selected from the group consisting of polyimide, polyamide, polyamideimide, and polybenzoxazole (see, for example, Patent Document 1).

[0004] On the other hand, when a scintillator panel is used for in-line inspection of foods, electronic components, etc., the luminance tends to decrease over time due to continuous irradiation with high-energy X-rays. In response to this, a scintillator panel has been proposed that has a substrate and a scintillator layer containing a phosphor, the scintillator layer including a binder resin having a π-conjugated structure composed of seven or more atoms, the glass transition point of the binder resin being 30 to 430°C, and the film thickness of the scintillator layer being 50 to 800 μm (see, for example, Patent Document 2).

[0005] International Publication No. 2021 / 200327 International Publication No. 2022 / 024860

[0006] Although these techniques can improve brightness to a certain extent, particularly in industrial applications, thicker phosphor layers and thinner barrier ribs are required to increase the amount of phosphor. That is, barrier ribs with a high aspect ratio are required. However, the inventors' studies have revealed that when barrier ribs with a high aspect ratio required for such a background are formed using a conventionally known resin composition, there is a problem in that the barrier ribs tend to peel off from the substrate during development or after curing.

[0007] In view of the problems with the conventional technology, the present invention aims to provide a laminate having a high aspect ratio cured product on a substrate, which can suppress peeling of the cured product.

[0008] The present invention, which aims to solve the above problems, mainly has the following configurations. <1> A laminate having a cured material layer on a substrate, the cured material layer comprising a cured material of a resin composition containing (A) a polyimide resin, (B) an oxetane compound, and (C) a photocationic polymerization initiator, and an acrylic resin layer adjacent to the substrate and the cured material layer, between the substrate and the cured material layer. <2> The laminate according to <1>, wherein the acrylic resin layer has an acid value of 50 mgKOH / g or more and 230 mgKOH / g or less. <3> The laminate according to <1> or <2>, wherein the acrylic resin layer has a hydroxyl value of 10 mgKOH / g or more and 150 mgKOH / g or less. <4> The laminate according to any one of <1> to <3>, wherein the acrylic resin layer has a weight-average molecular weight of 8,000 or more and 200,000 or less. <5> The laminate according to any one of <1> to <4>, wherein the (B) oxetane compound includes (B-1) a compound having four or more oxetanyl groups. <6> The laminate according to <5>, wherein the compound (B-1) having four or more oxetanyl groups has a structure represented by the following general formula (1):

[0009]

[0010] In the above general formula (1), R １ represents an n-valent group having a siloxane bond. ２represents a hydrogen atom or a monovalent organic group having 1 to 6 carbon atoms. n represents a range of 4 to 30. <7> The laminate according to any one of <1> to <6>, wherein the resin composition further contains (D) an epoxy compound. <8> The laminate according to any one of <1> to <7>, wherein the (B) oxetane compound and / or the (D) epoxy compound has a polyalkylene glycol chain. <9> A scintillator panel comprising the laminate according to any one of <1> to <8>, wherein the scintillator panel has, on the substrate, cells partitioned by partition walls made of the cured material layer, and wherein the cells have a phosphor layer. <10> An electronic device comprising the laminate according to any one of <1> to <8>. <11> The electronic device according to <10>, wherein the substrate of the laminate is a silicon substrate, a silicon carbide substrate, or a gallium nitride substrate. <12> An inductor having an insulating film and a coil, wherein the inductor has the laminate according to any one of <1> to <8> and a coil, and the insulating film is the cured material layer of the laminate.

[0011] The laminate of the present invention is a laminate having a high aspect ratio cured material layer on a substrate, and is capable of suppressing peeling of the cured material.

[0012] 1 is a cross-sectional view schematically showing the structure of a laminate of the present invention. FIG. 2 is a cross-sectional view schematically showing a radiation detector member including a scintillator panel having the laminate shown in FIG. 1. FIG. 3 is a cross-sectional view schematically showing the structure of an inductor of the present invention.

[0013] The laminate of the present invention is a laminate having a cured material layer on a substrate, the cured material layer comprising a cured product of a resin composition containing (A) a polyimide resin, (B) an oxetane compound, and (C) a photocationic polymerization initiator, and an acrylic resin layer adjacent to the substrate and the cured material layer between the substrate and the cured material layer. The cured material layer may be provided over the entire surface of the substrate via the acrylic resin layer, or may be provided partially on the substrate in a necessary location. To utilize the effect of suppressing peeling of a high aspect ratio cured material layer, which is a feature of the present invention, it is preferable that the cured material layer be provided partially on the substrate in a necessary location. The acrylic resin layer has the effect of adhering the cured material layer to the substrate, and can particularly suppress peeling of the cured material layer during development or after curing. When the cured material layer is provided on a portion of the substrate, the acrylic resin layer may be provided over the entire surface of the substrate, or may be provided only partially on the substrate in a necessary location, such as the portion having the cured material layer.

[0014] 1 is a cross-sectional view schematically illustrating the structure of a laminate of the present invention. An acrylic resin layer 2 is provided over the entire surface of a substrate 3, and a cured material layer 1 is partially provided via the acrylic resin layer 2. The cured material layer 1 has a trapezoidal cross-sectional shape, with a height of L1, a width (central width) of the cured material layer at a position halfway along the height L1 of L3, and a distance between adjacent cured material layers 1 of L2.

[0015] From the viewpoint of further improving the aspect ratio of the cured material layer, the height L1 of the cured material layer is preferably 100 μm or more, more preferably 200 μm or more, while the height L1 of the cured material layer is preferably 3,000 μm or less, more preferably 1,000 μm or less.

[0016] The distance L2 between adjacent cured material layers is preferably 40 μm or more and 1,000 μm or less.

[0017] The aspect ratio (L1 / L3) of the height L1 to the central width L3 of the cured material layer is preferably 5.0 or more, more preferably 12 or more, more preferably 14 or more, and even more preferably 15 or more. On the other hand, the aspect ratio of the cured material layer is preferably 100 or less, more preferably 50 or less.

[0018] The height L1, spacing L2, and central width L3 of the cured material layer can be measured by observing a cross section perpendicular to the substrate using a scanning electron microscope. The cross section perpendicular to the substrate can be obtained by breaking the partition walls or by exposing them using a polishing device such as a cross-section polisher. Each of the lengths L1 to L3 is calculated by averaging the measurements of three randomly selected locations on the cured material layer.

[0019] Methods for controlling the aspect ratio (L1 / L3) within the above range include a method in which the components and contents of the resin composition constituting the cured product layer are set within the preferred ranges described below.

[0020] <Substrate> Examples of materials constituting the substrate include metals, semiconductors, plastics, glass, and ceramics. Metals include aluminum (including aluminum alloys), zinc, copper, and iron. Semiconductors include silicon, silicon carbide, gallium nitride, aluminum nitride, and gallium arsenide. Plastics include cellulose acetate, polyethylene terephthalate (PET), polyethylene, polyester, polyamide, polyimide, polyphenylene sulfide, polystyrene, polypropylene, polycarbonate, polyvinyl acetal, aramid, silicone, polyolefin, tetrafluoroethylene-ethylene copolymer (ETFE), α-polyolefin resin, polycaprolactone resin, acrylic resin, silicone resin, and copolymer resins of these with ethylene. Substrates include metal plates and foils, semiconductor wafers, plastic films, plastic films laminated or vapor-deposited with the above metals, glass plates, and ceramic plates. In the case of metal plates and foils, the surfaces may be plated with chromium, copper, nickel, or other metals, or may be ceramic-coated.

[0021] When the laminate of the present invention is used in a scintillator panel, the material constituting the substrate preferably has radiation transparency, and for example, those exemplified as materials constituting the substrate in WO 2021 / 200327 are preferred. Among these, from the viewpoint of adhesion to the acrylic resin layer, glass plates and plastic films are preferred, and as plastics, polyesters such as polyethylene terephthalate and polyethylene naphthalate, polyamides, polyimides, etc. are particularly preferred.

[0022] When the laminate of the present invention is used in an electronic component, the substrate is preferably a substrate selected from a silicon substrate, a silicon carbide substrate, and a gallium nitride substrate.

[0023] The thickness of the substrate is preferably 3.0 mm or less.

[0024] <Cured Material Layer> The cured material layer is composed of a cured product of a resin composition (hereinafter sometimes referred to as a resin composition for the cured material layer) containing (A) a polyimide resin, (B) an oxetane compound, and (C) a photocationic polymerization initiator. The (A) polyimide resin maintains the shape of the resin composition, improves processability, and enables the formation of patterns with high aspect ratios. By containing the (B) oxetane compound and the (C) photocationic polymerization initiator, the (C) photocationic polymerization initiator generates acid upon irradiation with light, which polymerizes the (B) oxetane compound, resulting in negative photosensitivity that makes the layer insoluble in a developer. It is also preferable that the cured material layer further contains a (D) epoxy compound. The inclusion of the (D) epoxy compound can further improve adhesion to the acrylic resin layer.

[0025] <(A) Polyimide Resin> The weight-average molecular weight of the (A) polyimide resin is preferably 1,000 or more and 20,000 or less. By making the weight-average molecular weight of the (A) polyimide resin 1,000 or more, the film-forming properties of the resin composition can be improved. The weight-average molecular weight of the (A) polyimide resin is more preferably 2,000 or more. On the other hand, by making the weight-average molecular weight of the (A) polyimide resin 20,000 or less, the solubility of the resin composition during development can be improved. The weight-average molecular weight of the (A) polyimide resin is more preferably 10,000 or less. The weight-average molecular weight of the (A) polyimide resin in the present invention is measured by gel permeation chromatography (GPC) and calculated in terms of polystyrene.

[0026] From the viewpoint of cationic polymerization, it is preferable that the (A) polyimide resin is substantially free of basic functional groups such as amino groups that can inhibit cationic polymerization. By being substantially free of groups that inhibit cationic polymerization, cationic polymerization can be improved, and patterns with higher aspect ratios can be formed. Here, "substantially free" specifically refers to a polyimide resin having an equivalent weight of basic functional groups of 1,000 g / eq or more.

[0027] The polyimide resin (A) preferably has an alkali-soluble group, which provides adequate solubility when the resin composition is developed with an alkali developer, thereby enhancing the contrast between exposed and unexposed areas. Examples of the alkali-soluble group include a phenolic hydroxyl group, a carboxyl group, a silanol group, and a sulfo group. Two or more of these groups may be present. Among these, a phenolic hydroxyl group is preferred.

[0028] The polyimide resin having a phenolic hydroxyl group preferably has a diamine residue having a phenolic hydroxyl group. Examples of the diamine residue having a phenolic hydroxyl group include residues derived from aromatic diamines such as bis(3-amino-4-hydroxyphenyl)hexafluoropropane, bis(3-amino-4-hydroxyphenyl)sulfone, bis(3-amino-4-hydroxyphenyl)propane, bis(3-amino-4-hydroxyphenyl)methylene, bis(3-amino-4-hydroxyphenyl)ether, bis(3-amino-4-hydroxy)biphenyl, 2,2'-ditrifluoromethyl-5,5'-dihydroxyl-4,4'-diaminobiphenyl, bis(3-amino-4-hydroxyphenyl)fluorene, and 2,2'-bis(trifluoromethyl)-5,5'-dihydroxybenzidine, as well as compounds in which a portion of the hydrogen atoms in these aromatic rings or hydrocarbons are substituted with alkyl groups or fluoroalkyl groups having 1 to 10 carbon atoms, halogen atoms, or the like. Two or more of these may be contained, and a diamine residue having no phenolic hydroxyl group may also be contained.

[0029] The content of the (A) polyimide resin in the solid content of the resin composition for the cured material layer is preferably 15 to 70% by mass. The solid content refers to the components constituting the resin composition, excluding volatile substances such as organic solvents and water. By including 15% by mass or more of the (A) polyimide resin, the processability and thermal properties of the cured material layer can be improved. The content of the (A) polyimide resin is more preferably 25% by mass or more. On the other hand, by including 70% by mass or less of the (A) polyimide resin, development residues can be suppressed when the resin composition is developed.

[0030] <(B) Oxetane Compound> Examples of the (B) oxetane compound include 3-methyl-3-hydroxymethyloxetane, 3-ethyl-3-hydroxymethyloxetane, 2-ethylhexyl (3-ethyl-3-oxetanylmethyl) ether, 2-hydroxyethyl (3-ethyl-3-oxetanylmethyl) ether, 2-hydroxypropyl (3-ethyl-3-oxetanylmethyl) ether, 1,4-bis[(3-ethyl-3-oxetanylmethoxy)methyl]benzene, oxetanyl silsesquioxane, phenol novolac oxetane, and OXT-191 (trade name, manufactured by Toagosei Co., Ltd.). Two or more of these compounds may be contained. In the present invention, compounds having an oxetanyl group, even if they are resins or compounds having an epoxy group, are classified as (B) oxetane compounds. Among these, (B-1) compounds having four or more oxetanyl groups are preferred. A pattern with a high aspect ratio can be formed by selecting, as the (B) oxetane compound, (B-1) a compound having four or more oxetanyl groups, which has excellent curing properties among various oxetane compounds.The (B) oxetane compound may contain, together with the (B-1) oxetane compound, an oxetane compound having one to three oxetanyl groups.

[0031] (B-1) Examples of compounds having four or more oxetanyl groups include oxetanyl silsesquioxane, phenol novolac oxetane, and OXT-191 (trade name, manufactured by Toa Gosei Co., Ltd.). Two or more of these may be contained. The number of oxetanyl groups per molecule is preferably 7 or more, which further improves the curability of the resin composition and enables the formation of patterns with higher aspect ratios. On the other hand, the number of oxetanyl groups per molecule is preferably 20 or less, which enables the occurrence of cracks during pattern processing to be suppressed. Examples of oxetane compounds having 7 or more and 20 or less oxetanyl groups per molecule include OXT-191 (trade name, manufactured by Toa Gosei Co., Ltd.).

[0032] The (B-1) compound having four or more oxetanyl groups preferably has a structure represented by the following general formula (1): When the (B-1) compound having four or more oxetanyl groups has a structure represented by the following general formula (1), the crosslinking density of the cured product can be increased, and a pattern with a higher aspect ratio can be formed.

[0033]

[0034] In the above general formula (1), R １ represents an n-valent group having a siloxane bond. ２ represents a hydrogen atom or a monovalent organic group having 1 to 6 carbon atoms. n represents a number ranging from 4 to 30, preferably from 7 to 20.

[0035] R １ has a siloxane bond. The siloxane bond is hydrolyzed by an alkaline developer, and therefore, when developed with an alkaline developer, it has a suitable solubility, which can enhance the contrast between the exposed and unexposed areas. １ As the silicate, silicate and polysilicate are preferred.

[0036] R ２ The organic group constituting R is preferably an alkyl group such as a methyl group or an ethyl group. The alkyl group may be substituted with a halogen such as fluorine, and when it has a substituent, it is preferably a perfluoroalkyl group such as a trifluoromethyl group or a pentafluoroethyl group. ２ By containing a hydrogen atom or a monovalent organic group having 1 to 6 carbon atoms, the resin composition has excellent solubility in an alkaline developer, and developability can be improved.

[0037] Examples of oxetane compounds having the structure represented by the general formula (1) include oxetanylsilsesquioxane, OXT-191 (trade name, manufactured by Toagosei Co., Ltd.).

[0038] (B-1) The compound having four or more oxetanyl groups more preferably has a structure represented by the following general formula (2):

[0039]

[0040] In the above general formula (2), R ３ represents R in general formula (1). ２ m is the number of repetitions and is an integer of 1 or more. m is preferably in the range of 1 to 10.

[0041] In the above general formula (2), R ３ By containing a hydrogen atom or a monovalent organic group having 1 to 6 carbon atoms, the resin composition has excellent solubility in an alkaline developer, and developability can be improved.

[0042] In general formula (2), the resin composition has a silicate structure in which four oxygen atoms are bonded to silicon, which improves the heat resistance of the resin composition. In addition, the resin composition has many siloxane bonds, which enhances the contrast between exposed and unexposed areas by hydrolysis with an alkaline developer.

[0043] Examples of oxetane compounds having the structure represented by the general formula (2) include OXT-191 (trade name, manufactured by Toagosei Co., Ltd.).

[0044] The content of the (B) oxetane compound in the resin composition for the cured product layer is preferably 30 to 160 parts by mass per 100 parts by mass of the (A) polyimide resin. By making the content of the (B) oxetane compound 30 parts by mass or more, the curability of the resin composition can be further improved, and a pattern with a higher aspect ratio can be formed. The content of the (B) oxetane compound is more preferably 50 parts by mass or more. On the other hand, by making the content of the (B) oxetane compound 160 parts by mass or less, the resolution during pattern processing can be improved. The content of the (B) oxetane compound is more preferably 130 parts by mass or less.

[0045] <(C) Photocationic Polymerization Initiator> The (C) photocationic polymerization initiator generates an acid when exposed to light, causing cationic polymerization. The (C) photocationic polymerization initiator preferably has an acid dissociation constant pKa of 1.0 or less. Examples of the (C) photocationic polymerization initiator include aromatic iodonium salts, aromatic sulfonium salts, and aromatic borate salts. Examples of the anion components of these salts include hexafluorophosphate anion, hexafluoroantimonate anion, antimony hexafluoride anion, phosphorus hexafluoride anion, and tetrakis(pentafluorophenyl)borate anion. Two or more of these may be contained. Among these, aromatic sulfonium salts are preferred, and examples thereof include diphenyl[(phenylsulfanyl)phenyl]sulfonium hexafluorophosphate, diphenyl[4-(phenylthio)phenyl]sulfonium hexafluoroantimonate(V), diphenyl[4-(phenylsulfanyl)phenyl]sulfonium trifluoride tris(pentafluoroethane-1-ide)phosphate, diphenyl[(phenylsulfanyl)phenyl]sulfonium tetrakis(pentafluorophenyl)borate, CPI-310B, CPI-310FG, CPI-410S, and CPI-410B (trade names, all manufactured by San-Apro Co., Ltd.). The acid dissociation constant pKa of the photocationic polymerization initiator can be determined in accordance with the pH measurement method in Section 8.1 of the test method of JIS K 8802:2011.

[0046] The content of the (C) photocationic polymerization initiator in the resin composition for the cured product layer is preferably 0.3 parts by mass or more per 100 parts by mass of the (A) polyimide resin, which further improves the curability of the resin composition and enables the formation of a pattern with a higher aspect ratio. On the other hand, the content of the (C) photocationic polymerization initiator is preferably 10 parts by mass or less per 100 parts by mass of the (A) polyimide resin, which enables the stability of the resin composition to be improved.

[0047] <(D) Epoxy Compound> Examples of the epoxy compound (D) include aromatic epoxy compounds, alicyclic epoxy compounds, aliphatic epoxy compounds, etc. Two or more of these may be contained.

[0048] Examples of aromatic epoxy compounds include glycidyl ethers of mono- or polyhydric phenols having at least one aromatic ring (phenol, bisphenol A, phenol novolak, and alkylene oxide adducts thereof).

[0049] Examples of alicyclic epoxy compounds include compounds obtained by epoxidizing a compound having at least one cyclohexene or cyclopentene ring with an oxidizing agent (e.g., 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate).

[0050] Examples of aliphatic epoxy compounds include polyglycidyl ethers of aliphatic polyhydric alcohols or their alkylene oxide adducts (1,4-butanediol diglycidyl ether, 1,6-hexanediol diglycidyl ether, etc.), polyglycidyl esters of aliphatic polybasic acids (diglycidyl tetrahydrophthalate, etc.), and epoxidized long-chain unsaturated compounds (epoxidized soybean oil, epoxidized polybutadiene, etc.).

[0051] The (B) oxetane compound and / or the (D) epoxy compound preferably have a polyalkylene glycol chain, which has high flexibility, making it possible to suppress cracking of the film or cured product after drying.

[0052] The number-average molecular weight of the compound having a polyalkylene glycol chain is preferably 300 to 4,000 from the viewpoint of compatibility with (A) polyimide resin. By setting the number-average molecular weight to 300 or more, compatibility with (A) polyimide resin and flexibility can be further improved, and cracking can be further suppressed. On the other hand, by setting the number-average molecular weight to 4,000 or less, the epoxy / oxetane equivalent can be appropriately suppressed, curability can be further improved, and patterns with higher aspect ratios can be formed. The chemical structure of the compound having a polyalkylene glycol chain can be analyzed by a combination of nuclear magnetic resonance (NMR), Fourier transform infrared spectroscopy (FT-IR), and high-performance liquid chromatography / mass spectrometry (HPLC / MS). The number-average molecular weight of the compound having a polyalkylene glycol chain can be measured by gel permeation chromatography (GPC).

[0053] From the viewpoint of hydrophilicity, the number of carbon atoms in the alkylene group in the repeating unit of the polyalkylene glycol chain is preferably 2 to 6, and more preferably 2. By setting the number of carbon atoms in the alkylene group within this range, the resin composition can have excellent solubility in an alkaline developer and improved developability.

[0054] Furthermore, the number of epoxy groups and oxetanyl groups in the (B) oxetane compound and / or (D) epoxy compound having a polyalkylene glycol chain is preferably 2 or more, which further improves the curability of the resin composition and enables the formation of patterns with higher aspect ratios. Examples of such (B) oxetane compounds include bis-[(3-ethyloxetan-3-yl)methoxy]polyethylene glycol. Examples of such (D) epoxy compounds include polyethylene glycol diglycidyl ether and polypropylene glycol diglycidyl ether.

[0055] The (B) oxetane compound and the (D) epoxy compound are preferably water-soluble compounds from the viewpoint of solubility in an aqueous developer during development. Specifically, at least one of the (B) oxetane compound and / or the (D) epoxy compound is preferably a water-soluble compound that dissolves in 900 parts by mass of water at 20°C within 1 minute per 100 parts by mass of the compound. Specific examples include 3-methyl-3-hydroxymethyloxetane, 3-ethyl-3-hydroxymethyloxetane, glycerol polyglycidyl ether, polyglycerol polyglycidyl ether, ethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether, phenol (EO), ５ Glycidyl ether, lauryl alcohol (EO) １５ Glycidyl ethers and the like.

[0056] The total content of the (B) oxetane compound and (D) epoxy compound in the resin composition for the cured product layer is preferably 50 to 170 parts by mass per 100 parts by mass of the (A) polyimide resin. By making their total content 50 parts by mass or more, it is possible to suppress the occurrence of cracks in the resin composition coating film. The total content of these is more preferably 70 parts by mass or more. On the other hand, by making their total content 170 parts by mass or less, it is possible to suppress the occurrence of tackiness in the resin composition coating film. The total content of these is more preferably 140 parts by mass or less.

[0057] <Other Components> The resin composition for the cured product layer may contain, in addition to the (B) oxetane compound and the (D) epoxy compound, a cationically polymerizable compound other than these. Examples of the cationically polymerizable compound other than the (B) oxetane compound and the (D) epoxy compound include an ethylenically unsaturated compound, a bicycloorthoester, a spiroorthocarbonate, and a spiroorthoester. Two or more of these may be contained.

[0058] Examples of ethylenically unsaturated compounds include aliphatic monovinyl ethers, aromatic monovinyl ethers, polyfunctional vinyl ethers, styrene, and cationically polymerizable nitrogen-containing monomers. Examples of aliphatic monovinyl ethers include methyl vinyl ether, ethyl vinyl ether, butyl vinyl ether, and cyclohexyl vinyl ether. Examples of aromatic monovinyl ethers include 2-phenoxyethyl vinyl ether, phenyl vinyl ether, and p-methoxyphenyl vinyl ether. Examples of polyfunctional vinyl ethers include butanediol-1,4-divinyl ether and triethylene glycol divinyl ether. Examples of styrenes include styrene, α-methylstyrene, p-methoxystyrene, and tert-butoxystyrene. Examples of cationically polymerizable nitrogen-containing monomers include N-vinylcarbazole and N-vinylpyrrolidone.

[0059] Examples of bicyclo orthoesters include 1-phenyl-4-ethyl-2,6,7-trioxabicyclo[2.2.2]octane, 1-ethyl-4-hydroxymethyl-2,6,7-trioxabicyclo-[2.2.2]octane, and the like.

[0060] Examples of spiro orthocarbonates include 1,5,7,11-tetraoxaspiro[5.5]undecane and 3,9-dibenzyl-1,5,7,11-tetraoxaspiro[5.5]undecane.

[0061] Examples of spiro orthoesters include 1,4,6-trioxaspiro[4.4]nonane, 2-methyl-1,4,6-trioxaspiro[4.4]nonane, and 1,4,6-trioxaspiro[4.5]decane.

[0062] The resin composition for the cured product layer may further contain additives such as a sensitizer and a surfactant, inorganic particles, a solvent, etc., as necessary. The solvent is preferably one that dissolves the components constituting the resin composition, and examples thereof include ethers such as ethylene glycol monoethyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, ethylene glycol dimethyl ether, ethylene glycol diethyl ether, and ethylene glycol dibutyl ether; esters such as ethylene glycol monoethyl ether acetate, propylene glycol monomethyl ether acetate, propyl acetate, butyl acetate, isobutyl acetate, 3-methoxybutyl acetate, and 3-methyl-3-methoxybutyl acetate; alcohols such as 3-methyl-2-butanol, 3-methyl-3-methoxybutanol, and diacetone alcohol; N,N-dimethylformamide, N,N-dimethylacetamide, dimethyl sulfoxide, and γ-butyrolactone. Two or more of these may be contained.

[0063] The resin composition can be produced, for example, by adding the components (A) to (C) and, if necessary, the epoxy compound (D), a solvent, and other additives, followed by stirring.

[0064] The resin composition can be used after being processed into various forms such as a varnish or a film.

[0065]

[0033] <Acrylic Resin Layer> The laminate of the present invention has an acrylic resin layer adjacent to the substrate and the cured product layer. The acrylic resin layer preferably has high film strength from the viewpoint of suppressing cohesive failure within the layer, and is preferably formed by curing, for example, a resin composition containing an acrylic resin, a polymerizable monomer, and a radical polymerization initiator (hereinafter, may be referred to as a resin composition for the acrylic resin layer).

[0066] The acrylic resin preferably has an ethylenically unsaturated group, and the polymerization reaction with the polymerizable monomer can suppress the occurrence of cracks in the acrylic resin layer.

[0067] The acrylic resin preferably has a hydrophilic group, which can further improve adhesion and further suppress peeling of the cured material layer by interacting with polar groups in the substrate and the cured material layer. Examples of hydrophilic groups include a hydroxyl group, an amino group, a mercapto group, a carboxyl group, a sulfo group, and a phosphate group. Among these, from the viewpoint of suppressing the leaching and contamination of salt components, which are a polymerization inhibitor, from the substrate during cationic polymerization of the resin composition that forms the cured material layer, and further suppressing interlayer peeling, a group selected from a hydroxyl group and a carboxyl group is more preferred, and it is more preferred that the acrylic resin has both a hydroxyl group and a carboxyl group.

[0068] Examples of acrylic resin skeletons having a hydrophilic group include (meth)acrylic acid copolymers, (meth)acrylic acid-(meth)acrylic acid ester copolymers, styrene-(meth)acrylic acid copolymers, styrene-(meth)acrylic acid-(meth)acrylic acid ester copolymers, styrene-maleic acid-(meth)acrylic acid copolymers, styrene-maleic acid-(meth)acrylic acid ester copolymers, etc. Here, (meth)acrylic acid is a general term for acrylic acid and methacrylic acid.

[0069] Examples of methods for introducing ethylenically unsaturated groups into these acrylic resins having hydrophilic groups include a method of subjecting an ethylenically unsaturated compound having a glycidyl group or an isocyanate group, or acrylic acid chloride, methacrylic acid chloride, or allyl chloride to an active hydrogen-containing group in the resin, such as a mercapto group, an amino group, a hydroxyl group, or a carboxyl group. Examples of ethylenically unsaturated compounds having a glycidyl group include glycidyl (meth)acrylate, allyl glycidyl ether, glycidyl crotonate, and glycidyl isocrotonate. Examples of ethylenically unsaturated compounds having an isocyanate group include (meth)acryloyl isocyanate and (meth)acryloylethyl isocyanate. Here, (meth)acryloyl is a general term for acryloyl and methacryloyl.

[0070] The weight-average molecular weight of the acrylic resin is preferably 5,000 or more, more preferably 10,000 or more, and even more preferably 20,000 or more. By making the weight-average molecular weight of the acrylic resin 5,000 or more, cohesive failure within the acrylic resin layer can be suppressed and adhesion can be further improved. On the other hand, from the viewpoint of film-forming properties of the acrylic resin layer, the weight-average molecular weight of the acrylic resin is preferably 100,000 or less, more preferably 70,000 or less, and even more preferably 50,000 or less. The weight-average molecular weight of the acrylic resin is a polystyrene-equivalent value measured using gel permeation chromatography (GPC).

[0071] The acid value of the acrylic resin is preferably 10 mgKOH / g or more, more preferably 50 mgKOH / g or more, and even more preferably 80 mgKOH / g or more, from the viewpoints of promoting the curing reaction of the cured material layer, further improving adhesion through interaction with the polar groups of the cured material layer, and further suppressing peeling of the cured material layer. On the other hand, the acid value of the acrylic resin is preferably 200 mgKOH / g or less, more preferably 160 mgKOH / g or less, and even more preferably 120 mgKOH / g or less, from the viewpoints of suppressing swelling of the acrylic resin layer due to moisture absorption and further suppressing peeling of the resin composition forming the cured material layer during development. The acid value of the acrylic resin can be determined in accordance with the neutralization titration method in Section 3.1 of the test method of JIS K 0070:1992. When the acrylic resin layer contains two or more acrylic resins, the acid value of the acrylic resin refers to the acid value of the two or more acrylic resins as a whole.

[0072] The hydroxyl value of the acrylic resin is preferably 50 mgKOH / g or more, more preferably 60 mgKOH / g or more, and even more preferably 80 mgKOH / g or more, from the viewpoints of promoting the curing reaction of the cured material layer, further improving adhesion through interaction with the polar groups of the cured material layer, and further suppressing peeling of the cured material layer. On the other hand, from the viewpoints of suppressing swelling of the acrylic resin layer due to moisture absorption during development and further suppressing peeling of the resin composition forming the cured material layer during development, it is preferably 200 mgKOH / g or less, more preferably 160 mgKOH / g or less, and even more preferably 120 mgKOH / g or less. The hydroxyl value of the acrylic resin can be determined in accordance with the neutralization titration method in Test Method 7.1 of JIS K 0070:1992. When the acrylic resin layer contains two or more acrylic resins, the hydroxyl value of the acrylic resin refers to the hydroxyl value of the two or more acrylic resins as a whole.

[0073] The polymerizable monomer is preferably one that undergoes a polymerization reaction using a free radical as a starting point, and more preferably a (meth)acrylate having a hydrophilic group. Examples of the hydrophilic group include an ethylene oxide skeleton, a carboxy group, a hydroxyl group, an amino group, and a sulfonic acid group. By having these hydrophilic groups, adhesion can be further improved through interaction with the polar group of the cured material layer, and peeling of the cured material layer can be further suppressed. Among these, groups selected from a carboxyl group and a hydroxyl group are preferred, as they can prevent salt components that inhibit polymerization from leaching from the substrate and being mixed into the resin composition during cationic polymerization of the resin composition that forms the cured material layer, thereby further suppressing interlayer peeling.

[0074] Examples of (meth)acrylates having a hydroxyl group as a hydrophilic group include (meth)acrylates of monohydric alcohols such as 2-(meth)acryloyloxyethyl succinate, 2-hydroxy-3-(meth)acryloyloxypropyl (meth)acrylate, glycerin di(meth)acrylate, 2-(meth)acryloyloxyethyl acid phosphate, and 2-hydroxybutyl (meth)acrylate; poly(meth)acrylates of polyhydric alcohols such as trimethylolpropane, glycerin, pentaerythritol, diglycerin, ditrimethylolpropane, isocyanuric acid, and dipentaerythritol; and alkylene oxide adducts thereof. More specifically, examples of the acrylate include di- or tri(meth)acrylate of trimethylolpropane, di(meth)acrylate of glycerin, di- or tri(meth)acrylate of pentaerythritol, di- or tri(meth)acrylate of diglycerin, tetrapropylene glycol di(meth)acrylate, di- or tri(meth)acrylate of ditrimethylolpropane, di-, tri-, tetra-, or penta(meth)acrylate of dipentaerythritol, and their ethylene oxide adducts, propylene oxide adducts, butylene oxide adducts, and tetramethylene oxide adducts. Two or more of these may be contained. Among these, 2-(meth)acryloyloxyethyl succinate, 2-hydroxy-3-(meth)acryloyloxypropyl (meth)acrylate, and glycerin di(meth)acrylate are more preferred from the viewpoints of interaction with the polar groups in the cured product layer and ability to capture salt components that inhibit polymerization.

[0075] The content of the polymerizable monomer in the resin composition for the acrylic resin layer is preferably 5 parts by mass or more relative to 100 parts by weight of the acrylic resin, which can improve the film strength of the acrylic resin layer and further improve adhesion. The content of the polymerizable monomer is more preferably 10 parts by mass or more, and even more preferably 20 parts by mass or more. On the other hand, the content of the polymerizable monomer is preferably 200 parts by mass or less, and more preferably 100 parts by mass or less, relative to 100 parts by weight of the acrylic resin, from the viewpoint of further improving adhesion by setting the weight-average molecular weight of the acrylic resin layer within the preferred range described below.

[0076] Examples of radical polymerization initiators include acetophenone-based compounds, benzophenone-based compounds, acylphosphine oxide-based compounds, oxime ester-based compounds, benzoin-based compounds, biimidazole-based compounds, α-diketone-based compounds, titanocene-based compounds, polynuclear quinone-based compounds, xanthone-based compounds, thioxanthone-based compounds, triazine-based compounds, ketal-based compounds, azo-based compounds, peroxides, 2,3-dialkyldione-based compounds, disulfide-based compounds, thiuram compounds, and fluoroamine-based compounds. Two or more of these may be contained. Among these, compounds selected from acetophenone-based compounds, benzophenone-based compounds, acylphosphine oxide-based compounds, thioxanthone-based compounds, peroxides, disulfide-based compounds, and azo compounds are preferred. More specific examples include acetophenone, benzophenone, thioxanthone, benzoyl peroxide, diphenyl disulfide, 4-benzoyl-4-methylphenyl ketone, benzyl methoxyethyl acetal, 4,4-azobisisobutyronitrile, etc. Two or more of these may be contained.

[0077] The content of the radical polymerization initiator in the resin composition for the acrylic resin layer is preferably 0.10% by mass or more, and on the other hand, 10% by mass or less.

[0078] The acid value of the acrylic resin layer in the laminate of the present invention is preferably 50 mgKOH / g or more, more preferably 100 mgKOH / g or more, and even more preferably 120 mgKOH / g or more, from the viewpoints of accelerating the curing reaction of the cured material layer, further improving adhesion through interaction with the polar groups possessed by the cured material layer, and further suppressing peeling of the cured material layer. On the other hand, the acid value of the acrylic resin layer is preferably 230 mgKOH / g or less, more preferably 200 mgKOH / g or less, and even more preferably 180 mgKOH / g or less, from the viewpoints of suppressing swelling of the acrylic resin layer due to moisture absorption and further suppressing peeling of the resin composition forming the cured material layer during development. Here, the acid value of the acrylic resin layer is the acid value measured by the following method. First, the cured material layer adjacent to the acrylic resin layer is removed using a polishing device such as a cross-section polisher. Then, the exposed acrylic resin layer is scraped off from the substrate and placed in chloroform. Next, the solution is heated and stirred at 40°C for 12 hours, filtered to remove foreign matter, and the solvent is removed using an evaporator to obtain a powder. The obtained powder is measured in accordance with the neutralization titration method in Section 3.1 of the test method of JIS K 0070:1992.

[0079] The hydroxyl value of the acrylic resin layer in the laminate of the present invention is preferably 10 mgKOH / g or more, more preferably 30 mgKOH / g or more, and even more preferably 50 mgKOH / g or more, from the viewpoints of promoting the curing reaction of the cured material layer, further improving adhesion through interaction with the polar groups possessed by the cured material layer, and further suppressing peeling of the cured material layer. On the other hand, the hydroxyl value of the acrylic resin layer is preferably 150 mgKOH / g or less, more preferably 120 mgKOH / g or less, and even more preferably 100 mgKOH / g or less, from the viewpoints of suppressing swelling of the acrylic resin layer due to moisture absorption during development and further suppressing peeling of the resin composition forming the cured material layer during development. Here, the hydroxyl value of the acrylic resin layer is the hydroxyl value measured by the following method. A powder is obtained in the same manner as in the case of the acid value described above, and the acid value is measured in accordance with the neutralization titration method of Test Method Section 7.1 of JIS K 0070:1992.

[0080] The weight-average molecular weight of the acrylic resin layer is preferably 8,000 or more, more preferably 30,000 or more, and even more preferably 70,000 or more, from the viewpoints of suppressing cohesive failure, further improving adhesion, and further suppressing peeling of the cured material layer, as well as from the viewpoint of further suppressing peeling of the resin composition forming the cured material layer during development. On the other hand, from the viewpoint of suppressing cracking during the curing process, the weight-average molecular weight of the acrylic resin layer is preferably 200,000 or less, more preferably 150,000 or less, and even more preferably 100,000 or less. Here, the weight-average molecular weight of the acrylic resin layer refers to a weight-average molecular weight measured by the following method. First, the cured material layer adjacent to the acrylic resin layer is removed using a polishing device such as a cross-section polisher. Then, the exposed acrylic resin layer is scraped off from the substrate, mixed with an organic solvent such as tetrahydrofuran, and stirred for 12 hours. Next, the solution is filtered to remove foreign matter, and the polystyrene equivalent value is measured using gel permeation chromatography (GPC).

[0081] The thickness of the acrylic resin layer is preferably 0.01 μm or more, more preferably 0.50 μm or more, and even more preferably 2.0 μm or more, from the viewpoints of suppressing the elution of salt components, which are polymerization inhibitors, from the substrate and their incorporation into the resin composition during cationic polymerization of the resin composition that forms the cured layer, promoting the cationic polymerization reaction of the resin composition, and further improving adhesion. On the other hand, the thickness of the acrylic resin layer is preferably 20 μm or less, more preferably 10 μm or less, and even more preferably 5 μm or less, from the viewpoints of suppressing swelling due to moisture absorption during development and further suppressing peeling of the resin composition that forms the cured layer during development.

[0082] The resin composition for the acrylic resin layer may further contain additives such as a sensitizer, a silane coupling agent, a surfactant, and a solvent, as necessary. The solvent is preferably one that dissolves the components constituting the resin composition, and examples thereof include those exemplified as solvents for the resin composition that forms the cured product layer. Two or more of these may be contained.

[0083] <Method for producing laminate> The laminate of the present invention can be obtained, for example, by forming an acrylic resin layer on a substrate using the resin composition for the acrylic resin layer described above, and then applying and curing a resin composition containing the aforementioned (A) polyimide resin, (B) oxetane compound, and (C) photocationic polymerization initiator onto the acrylic resin layer. When the acrylic resin layer is a cured product of the resin composition, it is preferable to form the cured product layer after forming the acrylic resin layer by curing the resin composition.

[0084] Examples of methods for forming the acrylic resin layer include a method in which the aforementioned resin composition for the acrylic resin layer is applied to the entire surface of a substrate, dried by heating, and cured. Examples of methods for applying the resin composition include a screen printing method and a method using a coater such as a bar coater, a roll coater, a die coater, or a blade coater. The thickness of the applied film can be adjusted by the number of applications, the mesh size of the screen, the viscosity of the resin composition, etc.

[0085] The drying temperature and drying time in the heat drying can be appropriately selected depending on the composition of the resin composition.

[0086] Examples of methods for forming the cured material layer include a method in which a resin composition for the cured material layer is applied onto an acrylic resin layer, heated and dried to form a film, and then the coating film is exposed to actinic radiation through a mask having a desired pattern, and if necessary, developed to form a coating film pattern, followed by heating to cure. Heating causes a thermal crosslinking reaction and a cationic polymerization reaction to proceed, curing the resin composition and forming a cured material layer.

[0087] Examples of actinic rays used for exposure include ultraviolet rays, visible light, electron beams, X-rays, etc. In the present invention, it is preferable to use i-rays (365 nm), h-rays (405 nm), or g-rays (436 nm) from a mercury lamp.

[0088] After the exposure, it is preferable to carry out a development step in which the exposed portion is removed from the coating film using a developer. Examples of the developer include those exemplified as developers in WO 2021 / 200327.

[0089] Development can be carried out by spraying the developer onto the coating surface, puddling the developer onto the coating surface, immersing the coating in the developer, or immersing the coating in the developer and applying ultrasonic waves, etc. The development conditions, such as the development time and the temperature of the developer in the development step, may be any conditions that allow the exposed area to be removed and a pattern to be formed.

[0090] After development, it is preferable to perform a rinse treatment to wash away the remaining developer with water. The rinse treatment may be performed by adding alcohols such as ethanol and isopropyl alcohol, or esters such as ethyl lactate and propylene glycol monomethyl ether acetate to water.

[0091] If necessary, a baking treatment may be carried out before development. This may improve the resolution of the developed pattern and increase the tolerance for development conditions. The baking temperature is preferably in the range of 50 to 180°C, more preferably in the range of 60 to 120°C. The baking time is preferably from 5 seconds to several hours.

[0092] After forming a pattern by development, unreacted cationic polymerizable compounds and cationic polymerization initiators remain in the coating film of the resin composition. Therefore, these may thermally decompose during the thermal crosslinking reaction, generating gas. To avoid this, it is preferable to irradiate the entire surface of the resin composition coating after pattern formation with the above-mentioned exposure light to generate acid from the cationic polymerization initiator. By doing so, the reaction of the unreacted cationic polymerizable compounds proceeds during the thermal crosslinking reaction, and the generation of gas resulting from thermal decomposition can be suppressed.

[0093] The heating temperature for heat curing is preferably 120°C to 300°C. Thermal crosslinking can improve the heat resistance and chemical resistance of the cured layer. This heat treatment method can be selected by selecting a temperature and gradually increasing the temperature, or by selecting a temperature range and continuously increasing the temperature for 5 minutes to 5 hours.

[0094] <Scintillator Panel> The scintillator panel of the present invention is a scintillator panel having the laminate of the present invention, and has cells on a substrate, the cells being partitioned by partition walls made of a cured product layer, and a phosphor layer in each cell. By using the laminate of the present invention, partition walls with a high aspect ratio can be easily formed. Furthermore, by having such partition walls, the brightness of the scintillator panel can be improved. Furthermore, since the surface smoothness of the partition walls is excellent, the light extraction efficiency of the phosphor can be improved, and the brightness can be improved.

[0095] <Partitions> Partitions are provided to form at least partitioned spaces (cells). Therefore, grid-shaped partitions are preferred for scintillator panels. The photoelectric conversion element that receives light emitted from the scintillator panel has pixels arranged in a grid pattern. By matching the size and pitch of the pixels of the photoelectric conversion element with the size and pitch of the cells of the scintillator panel, each pixel of the photoelectric conversion element can be associated with each cell of the scintillator panel. This allows for a highly sharp image to be obtained.

[0096] The partition walls are preferably made of the cured material layer of the laminate of the present invention. By providing partition walls made of the cured material layer with a high aspect ratio in the laminate of the present invention, the loading amount of the phosphor in the phosphor layer can be increased, thereby improving brightness.

[0097] The height of the partition walls is preferably 100 μm or more. By making the height of the partition walls 100 μm or more, the amount of phosphor filling can be increased, and brightness can be further improved. The height of the partition walls is more preferably 200 μm or more. On the other hand, the height of the partition walls is preferably 3,000 μm or less. By making the height of the partition walls 3,000 μm or less, absorption of emitted light by the phosphor itself can be suppressed, and brightness can be further improved. The height of the partition walls is more preferably 1,000 μm or less.

[0098] The distance between adjacent partition walls is preferably 40 μm or more, and more preferably 1,000 μm or less.

[0099] The aspect ratio of the barrier rib height to the barrier rib central width (height / central width) is preferably 5.0 or more, which allows for a larger phosphor filling amount and further improved brightness. The aspect ratio is more preferably 12 or more, more preferably 14 or more, and even more preferably 15 or more. On the other hand, the aspect ratio is preferably 100 or less, which allows for improved barrier rib strength. The aspect ratio is more preferably 50 or less.

[0100] The height, spacing and central width of the partition walls can be measured in the same manner as the height L1, spacing L2 and central width L3 of the cured material layer in the present invention described above.

[0101] As a method for adjusting the aspect ratio to the above range, there can be mentioned a method in which the components constituting the resin composition used for forming the partition walls and the contents thereof are adjusted to the preferred ranges described below.

[0102] Hereinafter, embodiments of the scintillator panel of the present invention will be described with reference to the drawings. Note that the drawings are schematic. Furthermore, the present invention is not limited to the embodiments described below.

[0103] FIG. 2 is a cross-sectional view schematically illustrating a radiation detector member including a scintillator panel according to the present invention. The radiation detector member 4 includes a scintillator panel 5 and an output substrate 6. The scintillator panel 5 includes a substrate 3, an acrylic resin layer 2, partition walls 16, and phosphor layers 7 within cells defined by the partition walls 16. A metal reflective layer 12 is formed on the surface of the partition walls 16, and an organic protective layer 13 is provided on the surface of the metal reflective layer 12. The phosphor layer 7 contains phosphors 14 and a binder resin 15. The output substrate 6 includes an output layer 10 and a photoelectric conversion layer 9 having a photodiode, which are disposed in this order on a substrate 11. A barrier layer 8 may be provided on the photoelectric conversion layer 9. The light-emitting surface of the scintillator panel 5 and the photoelectric conversion layer 9 of the output substrate 6 are preferably bonded or adhered to each other via the barrier layer 8. Light emitted from the phosphor layer 7 reaches the photoelectric conversion layer 9, where it is photoelectrically converted and output. Each of these components is described below.

[0104] <Metallic Reflective Layer> In the scintillator panel of the present invention, it is preferable that the partition wall has a reflective layer containing a metal (hereinafter referred to as a "metallic reflective layer") on its surface. The metallic reflective layer may be provided on at least a part of the partition wall. The metallic reflective layer has a high reflectivity even when it is a thin film. Therefore, by providing a thin metallic reflective layer, the loading amount of the phosphor is less likely to decrease, and the brightness of the scintillator panel is further improved. Examples of metallic reflective layers include those exemplified as metallic reflective layers in WO 2019 / 181444.

[0105] <Protective Layer> The scintillator panel of the present invention preferably has a protective layer on the surface of the metal reflective layer. Even when the metal reflective layer is made of an alloy or the like that has poor resistance to discoloration in the atmosphere, the provision of the protective layer can reduce discoloration, suppress a decrease in the reflectance of the metal reflective layer due to a reaction between the metal reflective layer and the phosphor layer, and further improve brightness.

[0106] The protective layer may be either an inorganic protective layer or an organic protective layer, or may be a combination of an inorganic protective layer and an organic protective layer.

[0107] <Inorganic Protective Layer> The inorganic protective layer is suitable as a protective layer because it has low water vapor permeability. Examples of the inorganic protective layer include those exemplified as inorganic protective layers in WO 2019 / 181444.

[0108] <Organic protective layer> The organic protective layer is preferably formed from a polymer compound having excellent chemical durability, and preferably contains, for example, polysiloxane or amorphous fluororesin as a main component. Examples of the organic protective layer include those exemplified as organic protective layers in WO 2019 / 181444, and examples of the polysiloxane and amorphous fluororesin include those exemplified as materials constituting the organic protective layer in WO 2021 / 200327.

[0109] <Phosphor Layer> The scintillator panel of the present invention has a phosphor layer in each cell defined by partition walls.

[0110] The phosphor layer absorbs the energy of incident radiation such as X-rays and emits electromagnetic waves with wavelengths in the range of 300 nm to 800 nm, i.e., light in the range from ultraviolet light to infrared light, with a focus on visible light. The light emitted from the phosphor layer undergoes photoelectric conversion in the photoelectric conversion layer and is output as an electrical signal through the output layer. The phosphor layer preferably contains a phosphor and a binder resin.

[0111] <Phosphor> Examples of the phosphor include those exemplified as phosphors in WO 2021 / 200327. From the viewpoint of high luminous efficiency, the phosphor is preferably a terbium-activated rare earth oxysulfide phosphor.

[0112] <Binder Resin> Examples of the binder resin include those exemplified as binder resins in WO 2021 / 200327.

[0113] The binder resin is preferably in contact with the protective layer. In this case, it is sufficient that the binder resin is in contact with at least a portion of the protective layer. This makes it difficult for the phosphor to fall out of the cell in the scintillator panel. Note that the binder resin may be filled in the cell with almost no voids, as shown in FIG. 1, or may be filled with voids.

[0114] As described above, the scintillator panel of the present invention provides a high brightness image.

[0115] <Method for manufacturing scintillator panel> The method for manufacturing a scintillator panel of the present invention preferably includes, for example, a partition wall forming step of forming an acrylic resin layer and partition walls on a substrate to separate cells by the method for manufacturing the laminate of the present invention described above, a reflective layer forming step of forming a metal reflective layer on the surface of the partition walls as needed, and a filling step of filling the cells separated by the partition walls with a phosphor. Each step will be described below. In the following description, details that are common to those described in the embodiment of the scintillator panel described above will be omitted as appropriate. Furthermore, the partition wall forming step is common to the method for manufacturing the laminate of the present invention described above, and therefore will not be described here.

[0116] When a metal reflective layer, an inorganic protective layer, and / or an organic protective layer is provided on the surface of the partition wall, examples of the method for forming these include the methods exemplified as the formation steps in WO 2019 / 181444 and WO 2021 / 200327.

[0117] <Electronic Component> The electronic component of the present invention has the laminate of the present invention. The cured product layer in the laminate of the present invention can be used as an insulating film or a protective film constituting the electronic component. By using the laminate of the present invention, an insulating film or a protective film with a high aspect ratio can be easily formed.

[0118] Examples of electronic components include active components having semiconductors such as transistors, diodes, integrated circuits (ICs), and memories, and passive components such as resistors, capacitors, and inductors. Electronic components using semiconductors are also called semiconductor devices or semiconductor packages.

[0119] The cured product layer in the laminate of the present invention is suitably used in electronic components, for example, as a passivation film for semiconductor devices, a surface protective film for semiconductor elements and TFTs (Thin Film Transistors), an interlayer insulating film such as an interlayer insulating film between rewirings in multilayer wiring for high-density packaging, an insulating film or protective film for touch panel displays, and an insulating layer for organic electroluminescent devices.

[0120] As an example of the method for manufacturing electronic components of the present invention, a semiconductor device manufacturing method using a redistribution layer (RDL) first process is described. A barrier metal such as Ti is formed on a substrate such as a glass substrate or a silicon wafer by sputtering, a Cu seed (seed layer) is further formed on top of that by sputtering, and then Cu electrode pads are formed by plating. Next, an acrylic resin layer is formed over the entire surface of the substrate on which the electrode pads have been formed by the method described above. A cured layer-forming resin composition containing (A) a polyimide resin, (B) an oxetane compound, and (C) a photocationic polymerization initiator is then coated and dried on top of that. Next, if necessary, the coating film is exposed to UV light through a desired pattern mask, and then immersed in a 0.5% by mass potassium hydroxide aqueous solution for development, forming the desired coating film pattern. The coating film pattern is then heat-treated to form a cured layer. This cured layer becomes an insulating film. Next, a seed layer is again formed by sputtering, and Cu metal wiring (redistribution) is formed by plating. Thereafter, the seed layer process through the metal wiring formation process are repeated to form a multilayer wiring structure. Next, the resin composition for forming the cured product layer is applied, patterned, and heat-treated to harden it to form an insulating film. Then, Cu posts are formed on the metal wiring in the openings of the insulating film using a plating method. The pitch of the Cu posts and the pitch of the conductive portions of the semiconductor chip are made equal. That is, the pitch of the conductive portions of the semiconductor chip is finer than the pitch of the electrode pads, and each rewiring layer constituting the multilayer wiring structure gradually becomes finer from the electrode pads to the Cu posts, thereby multiplying the wiring. In the multilayer wiring structure, the thickness of adjacent insulating films also becomes the same or thinner as they approach the semiconductor chip. Next, the semiconductor chip is connected to the Cu posts via solder bumps. This electrically connects the electrode pads and the semiconductor chip via the metal wiring and solder bumps. The semiconductor chip is then encapsulated with an encapsulating resin to form a semiconductor package, and the support substrate and the rewiring layer are peeled off to separate the semiconductor package. In this manner, a semiconductor device having a multi-layer wiring structure can be obtained using the RDL first process.

[0121] <Inductor> The inductor of the present invention has the laminate of the present invention, an insulating film, and a coil. The insulating film is the cured material layer of the present invention. By using the laminate of the present invention, an insulating film with a high aspect ratio can be easily formed.

[0122] 3 is a cross-sectional view showing a schematic diagram of an inductor according to the present invention. Inductor 17 has coil 19 and insulating film 18 that maintains insulation between coils 19, with resin layers 20 sandwiched between them on the top and bottom of substrate 21. Inductor 17 also has magnetic material 23 sandwiched between insulating films 22, and the entire structure is sealed with molded resin 24.

[0123] By using the cured material layer in the laminate of the present invention as the insulating film 18, sufficient insulating properties can be exhibited even when the width W of the insulating film 18 is small. Therefore, the cross-sectional area of ​​the wiring of the coil 19 can be increased, and the inductance can be increased.

[0124] Furthermore, the thickness T of the insulating film 18 is preferably 40 μm or more, and more preferably 80 μm or more, from the viewpoint of increasing the cross-sectional area of ​​the coil 19. On the other hand, the thickness T of the insulating film 18 is preferably 300 μm or less, and more preferably 200 μm or less, from the viewpoint of reducing the film stress.

[0125] The aspect ratio of the insulating film 18, which is the thickness T divided by the width W, is preferably 4 or more, and more preferably 8 or more, from the viewpoint of improving the wiring density of the coil 19. On the other hand, the aspect ratio of the insulating film 18 is preferably 30 or less, and more preferably 20 or less, from the viewpoint of maintaining insulation properties.

[0126] The present invention will be described in more detail below with reference to Examples and Comparative Examples. The compounds used in the Examples and Comparative Examples were synthesized by the following methods.

[0127] Synthesis Example 1: Synthesis of Acrylic Resin 1 A reaction vessel equipped with a stirrer, reflux condenser, thermometer, and nitrogen gas inlet tube was charged with 150 mol parts of propylene glycol monomethyl ether acetate as a solvent, 25 mol parts of methyl methacrylate, 25 mol parts of styrene, and 50 mol parts of methacrylic acid as raw monomers, and 4 mol parts of 2,2'-azobis(2-methylbutyronitrile) as a polymerization initiator. Dropwise polymerization was carried out at 140°C for 1.5 hours with reflux and stirring, and the mixture was then kept at 140°C for 1 hour to obtain a copolymer. Next, 0.55 equivalents of glycidyl methacrylate relative to the carboxy groups of the obtained copolymer were added to the reaction vessel, and the mixture was stirred at 80°C for 5 hours to allow an addition reaction, yielding an acrylic resin having ethylenically unsaturated groups and hydrophilic groups (carboxy groups and hydroxyl groups). The obtained acrylic resin was evaluated using the methods described below, and the results are shown in Table 1.

[0128] (Synthesis Examples 2 to 15: Synthesis of Acrylic Resins 2 to 15) Acrylic resins 2 to 15 were obtained in the same manner as for resin 1, except that the types and compositions of raw material monomers were changed as shown in Tables 1 and 2. The obtained resins were evaluated by the methods described below, and the results are shown in Tables 1 and 2.

[0129] The abbreviations in Tables 1 and 2 are as follows: St: styrene, MMA: methyl methacrylate, MAA: methacrylic acid, GMA: glycidyl methacrylate, PGMEA: propylene glycol monomethyl ether acetate, HEMA: hydroxyethyl methacrylate, ABN-E: 2,2'-azobis(2-methylbutyronitrile).

[0130]

[0131]

[0132] Synthesis Example 16: Synthesis of Polyimide Resin A-1 Under a dry nitrogen stream, 29.30 g (0.08 mol) of 2,2-bis(3-amino-4-hydroxyphenyl)hexafluoropropane (hereinafter abbreviated as "BAHF") (manufactured by Tokyo Chemical Industry Co., Ltd.) was added to 80 g of γ-butyrolactone (hereinafter abbreviated as "GBL") (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.), and the mixture was stirred and dissolved at 120°C. Next, 30.03 g (0.1 mol) of acid anhydride "RIKACID" (registered trademark) TDA-100 (hereinafter abbreviated as "TDA-100") (manufactured by New Japan Chemical Co., Ltd.) was added together with 20 g of GBL, and the mixture was stirred at 120°C for 1 hour, and then at 200°C for 4 hours to obtain a reaction solution. Next, the reaction solution was poured into 3 L of water, and a white precipitate was precipitated. The precipitate was collected by filtration, washed three times with water, and then dried in a vacuum dryer at 80°C for 5 hours to obtain a polyimide resin A-1 having a weight average molecular weight of 4,000 and a basic functional group equivalent of 1,000 g / eq or more.

[0133] Synthesis Example 17: Synthesis of Polyimide Resin A-2 Under a dry nitrogen stream, 32.96 g (0.09 mol) of BAHF was added to 80 g of GBL and stirred and dissolved at 120 ° C. Next, 30.03 g (0.1 mol) of TDA-100 was added together with 20 g of GBL, and the mixture was stirred at 120 ° C. for 1 hour, and then stirred at 200 ° C. for 4 hours to obtain a reaction solution. Next, the reaction solution was poured into 3 L of water to precipitate a white precipitate. This precipitate was collected by filtration, washed three times with water, and then dried in a vacuum dryer at 80 ° C. for 5 hours to obtain a polyimide resin A-2 having a weight average molecular weight of 8,000 and a basic functional group equivalent of 1,000 g / eq or more.

[0134] Synthesis Example 18: Synthesis of polyamideimide resin A'-3 BAHF (18.3 g, 0.05 mol) (manufactured by Tokyo Chemical Industry Co., Ltd.) was dissolved in 100 mL of acetone (manufactured by Tokyo Chemical Industry Co., Ltd.) and propylene oxide (17.4 g, 0.3 mol) (manufactured by Fujifilm Wako Pure Chemical Industries Co., Ltd.), and the solution was cooled to -15°C. To this solution, a solution of 3-nitrobenzoyl chloride (20.4 g, 0.11 mol) (manufactured by Tokyo Chemical Industry Co., Ltd.) dissolved in 100 mL of acetone (manufactured by Tokyo Chemical Industry Co., Ltd.) was added dropwise. After completion of the addition, the mixture was stirred at -15°C for 4 hours to react, and then the temperature was returned to room temperature. The precipitated white solid was filtered off and dried in vacuo at 50°C.

[0135] 30 g of the obtained white solid was placed in a 300 mL stainless steel autoclave and dispersed in 250 mL of methyl cellosolve (Tokyo Chemical Industry Co., Ltd.), and 2 g of 5 mass % palladium on carbon was added. Hydrogen was introduced into the mixture using a balloon, and the mixture was stirred at room temperature to carry out a reduction reaction. After approximately 2 hours, it was confirmed that the balloon was no longer deflating, and stirring was stopped. After stirring was completed, the mixture was filtered to remove the palladium compound catalyst, and the mixture was concentrated using a rotary evaporator to obtain hydroxyl group-containing diamine compound (a).

[0136] Under a dry nitrogen stream, 31.4 g (0.08 mol) of a hydroxyl group-containing diamine compound (a) was added to 80 g of GBL (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) and stirred at 120 ° C. Next, 30.0 g (0.1 mol) of TDA-100 (manufactured by New Japan Chemical Co., Ltd.) was added together with 20 g of GBL, and the mixture was stirred at 120 ° C. for 1 hour, and then at 200 ° C. for 4 hours to obtain a reaction solution. Next, the reaction solution was poured into 3 L of water to precipitate a white precipitate. This precipitate was collected by filtration, washed three times with water, and then dried in a vacuum dryer at 80 ° C. for 5 hours to obtain polyamideimide resin A'-3 having a weight average molecular weight of 5,000 and a basic functional group equivalent of 1,000 g / eq or more.

[0137] Synthesis Example 19 Synthesis of Oxetane Compound B-1a 90.0 g (0.01 mol) of novolak resin (number average molecular weight 900) (manufactured by Meiwa Chemical Industry Co., Ltd.) was dissolved in 100 mL of dimethyl sulfoxide (manufactured by FUJIFILM Wako Pure Chemical Industries, Ltd.). After nitrogen substitution, 60.0 g of a 49% by mass aqueous potassium hydroxide solution (manufactured by FUJIFILM Wako Pure Chemical Industries, Ltd.) was added and stirred at 90°C for 1 hour. Next, with stirring, 60.5 g (0.5 mol) of 3-(chloromethyl)-3-methyloxetane (manufactured by Tokyo Chemical Industry Co., Ltd.) was slowly added dropwise using a dropping funnel. The mixture was then stirred at 90°C for 5 hours to allow the reaction to proceed, and the reaction solution was then poured into 1 L of water to precipitate a white precipitate. The precipitate was collected by filtration, washed three times with water, and then dried in a vacuum dryer at 80°C for 5 hours to obtain an oxetane compound B-1a (a water-insoluble compound that does not satisfy the general formula (1), does not have a polyalkylene glycol chain, and has an average of nine oxetanyl groups per molecule).

[0138] Other raw materials used in the examples and comparative examples are listed below.

[0139] (Radical Polymerization Initiator) BPO: benzoyl peroxide (manufactured by Tokyo Chemical Industry Co., Ltd.).

[0140] (Polymerizable Monomers) M-1: 2-methacryloyloxyethyl succinate (manufactured by Tokyo Chemical Industry Co., Ltd.) M-2: dipentaerythritol hexaacrylate (manufactured by Tokyo Chemical Industry Co., Ltd.).

[0141] (Silane Coupling Agent) S-1: KBM-403 (manufactured by Shin-Etsu Chemical Co., Ltd.).

[0142] (A') Other Resins A'-4: "Maruka Linker" (registered trademark) M (manufactured by Maruzen Petrochemical Co., Ltd.), a resin of polyparahydroxystyrene, weight average molecular weight 4,000, and basic functional group equivalent of 1,000 g / eq or more.

[0143] (B) Oxetane Compound B-1b: Oxetane compound B-1b obtained by separating the low molecular weight component of OXT-191 (manufactured by Toagosei Co., Ltd.) by GPC, having an average of six oxetanyl groups per molecule and represented by general formula (1), R １ is polysilicate, R ２ is an ethyl group, and does not have a structure represented by general formula (2). Water-insoluble compound B-1c: OXT-191 (manufactured by Toagosei Co., Ltd.), which has an average of 12 oxetanyl groups per molecule and is represented by general formula (1), and １ is polysilicate, R ２ is an ethyl group, and does not have a structure represented by general formula (2). Water-insoluble compound B-1d: A water-insoluble compound having no polyalkylene glycol chain, which is obtained by separating the polymer component of OXT-191 (manufactured by Toagosei Co., Ltd.) by GPC, has an average of 18 oxetanyl groups per molecule, and is represented by general formula (1), and R １ is polysilicate, R ２ is an ethyl group, and does not have a structure represented by general formula (2). Water-insoluble compound having no polyalkylene glycol chain B-2: OXIPA (manufactured by Ube Industries, Ltd.), a water-insoluble compound having no polyalkylene glycol chain.

[0144] (C) Photocationic Polymerization Initiator C-1: CPI-410S (manufactured by San-Apro Co., Ltd.), an aromatic sulfonium salt.

[0145] (D) Epoxy Compounds D-1: "TEPIC" (registered trademark)-VL (manufactured by Nissan Chemical Industries, Ltd.), a trifunctional epoxy compound having no polyalkylene glycol chain, a water-insoluble compound. D-2: "DENACOL" (registered trademark) EX-171 (manufactured by Nagase ChemteX Corporation), a monofunctional epoxy compound having a polyethylene glycol chain, a number-average molecular weight of 770, a water-soluble compound. D-3: "DENACOL" EX-861 (manufactured by Nagase ChemteX Corporation), a bifunctional epoxy compound having a polyethylene glycol chain, a number-average molecular weight of 1,100, a water-soluble compound.

[0146] Next, the evaluation methods used in the examples and comparative examples will be described.

[0147] <Weight-average molecular weight of resin> The weight-average molecular weight (M ｗ The viscosity was measured as a polystyrene equivalent value by gel permeation chromatography (GPC). Tetrahydrofuran was used as the solvent for GPC measurement.

[0148] <Acid Value and Hydroxyl Value of Acrylic Resin> The acid values ​​of the acrylic resins obtained in Synthesis Examples 1 to 15 were measured in accordance with the neutralization titration method in Section 3.1 of the test method of JIS K 0070:1992. In addition, the hydroxyl values ​​were measured in accordance with the neutralization titration method in Section 7.1 of the test method of JIS K 0070:1992.

[0149] <Weight-average molecular weight of acrylic resin layer> An acrylic resin layer formed in the same manner as in <Formation of acrylic resin layer> in each Example and Comparative Examples 3 and 4 was scraped off, mixed with tetrahydrofuran, and stirred for 12 hours. Next, the solution was filtered to remove foreign matter, and then the weight-average molecular weight (M ｗ Tetrahydrofuran was used as the solvent for GPC measurement.

[0150] <Acid Value and Hydroxyl Value of Acrylic Resin Layer> An acrylic resin layer formed in the same manner as in <Formation of Acrylic Resin Layer> in each Example and Comparative Examples 3 and 4 was scraped off and placed in chloroform. Next, this solution was heated and stirred at 40°C for 12 hours, filtered to remove foreign matter, and the solvent was removed using an evaporator to obtain a powder. The acid value and hydroxyl value of the obtained powder were measured according to the neutralization titration method in Sections 3.1 and 7.1 of the test method of JIS K 0070:1992.

[0151] <Thickness of Acrylic Resin Layer> The thickness of the acrylic resin layers obtained in each of Examples 1 to 43 and Comparative Examples 3 and 4 was measured using a constant pressure thickness measuring device (manufactured by Teclock Corporation) in accordance with JIS K 6732:1996.

[0152] <Crack Resistance> In each Example and Comparative Example, the varnish coating film prepared for forming the partition walls after drying, and the film after exposure and heating or after exposure were each visually observed, and the observation area was 100 cm ２ The crack resistance was evaluated based on the total number of cracks generated in the test piece according to the following criteria: 4: No cracks observed 3: 1 or more but less than 25 cracks 2: 25 or more but less than 100 cracks 1: 100 or more cracks.

[0153] <Developability> In each example and comparative example, the developability was evaluated based on the time taken for the unexposed area to completely dissolve during development according to the following criteria: 4: Less than 10 minutes 3: 10 minutes or more but less than 20 minutes 2: 20 minutes or more but less than 30 minutes 1: 30 minutes or more.

[0154] <Adhesion during development> In each example and comparative example, upon completion of development, 50 locations within a plane of 100 mm length x 100 mm width were randomly selected, and the interface between the partition wall and the substrate was visually observed to evaluate the adhesion according to the following criteria: A: No peeling was observed B: Peeling was observed in 1 to 10 locations C: Peeling was observed in 11 to 20 locations D: Peeling was observed in 21 to 40 locations E: Peeling was observed in 41 to 50 locations.

[0155] <Adhesion after curing> In each example and comparative example, after the curing step, 50 locations within a plane of 100 mm length x 100 mm width were randomly selected, and the interface between the partition wall and the substrate was visually observed, and the adhesion was evaluated according to the following criteria: A: No new peeling was observed B: New peeling was observed in 1 to 10 locations C: New peeling was observed in 11 to 20 locations D: New peeling was observed in 21 to 40 locations E: New peeling was observed in 41 to 50 locations

[0156] <Resolution and Aspect Ratio> A cross section of the grid-shaped partition walls formed in each Example and Comparative Example was exposed by cleaving, and three partition walls were randomly selected from those corresponding to the smallest openings where no distortion, clogging, or residue was observed in the pattern, among those corresponding to mask openings with line widths of 12 μm, 15 μm, and 20 μm. The central widths and heights of the partition walls were measured at a magnification of 200 times using a scanning electron microscope S2400 (manufactured by Hitachi, Ltd.), and the average values ​​for each were calculated. The average central width was defined as the resolution, and the ratio of the height to the central width (height / central width) was defined as the aspect ratio.

[0157] <Relative Brightness> A radiation detector was fabricated by aligning the scintillator panels obtained in each Example and Comparative Example at the center of the sensor surface of an X-ray detector PaxScan 2520V (manufactured by Varex) so that the cells corresponded one-to-one to the pixels of the sensor, and fixing the edges of the substrate with adhesive tape. X-rays from an X-ray emitter L9181-02 (manufactured by Hamamatsu Photonics K.K.) were irradiated onto this detector under conditions of a tube voltage of 50 kV and a distance between the X-ray tube and the detector of 30 cm, to obtain an image. In the obtained image, the average value of the digital values ​​of 256 x 256 pixels at the center of the light-emitting position of the scintillator panel was measured as brightness, and the value relative to the brightness of Comparative Example 2, which was set to 100, was calculated as the relative brightness.

[0158] Example 1 Formation of Acrylic Resin Layer Acrylic resin 1 obtained in Synthesis Example 1, polymerizable monomer M-1, radical polymerization initiator BPO, and silane coupling agent S-1 were weighed out in the amounts shown in Table 3 and placed in a plastic container, and 230 g of 3-methoxy-3-methyl-1-butanol was added and stirred for 30 minutes using a hybrid mixer to obtain a resin composition. The obtained resin composition was applied to the entire surface of a glass substrate measuring 125 mm in length, 125 mm in width, and 0.50 mm in thickness using a die coater, and then heated and cured at 180°C for 1 hour in a hot air oven to form an acrylic resin layer.

[0159] <Formation of Partition Walls> 10 g of (A) polyimide resin A-1 obtained in Synthesis Example 16 as a polyimide resin, 10 g of (B) oxetane compound B-1a obtained in Synthesis Example 19 as an oxetane compound, 0.10 g of (C) photocationic polymerization initiator C-1, and 2.0 g of (D) epoxy compound D-3 were weighed and dissolved in GBL. The amount of GBL added was adjusted so that the solids concentration was 60 mass %, with components other than GBL considered as solids. Thereafter, the mixture was pressure-filtered using a filter with a retention particle size of 1 μm to obtain a photosensitive polyimide varnish.

[0160] A photosensitive polyimide varnish was applied onto the acrylic resin layer formed on the substrate by the above-described method using a die coater so that the thickness after thermal crosslinking and curing would be 350 μm, and then dried to obtain a coating film of the photosensitive polyimide varnish.

[0161] Next, the coating film of the photosensitive polyimide varnish was exposed to 5,000 mJ / cm using an ultra-high pressure mercury lamp through a chrome mask having a grid-like opening with a pitch of 200 μm and line widths of 12 μm, 15 μm, and 20 μm. ２ The film was exposed to an exposure dose of 100°C for 90 minutes using a hot air oven. After exposure, post-exposure baking was performed using a hot air oven. The exposed and heated coating film was developed in a 0.5% by mass aqueous potassium hydroxide solution at 30°C, and the unexposed portions were removed to obtain a lattice pattern. The obtained lattice pattern was heated in air at 200°C for 60 minutes to be thermally crosslinked and cured, thereby forming lattice partition walls.

[0162] <Fabrication of Scintillator Panel> <Formation of Metal Reflective Layer and Inorganic Protective Layer> The formed grid-shaped partition walls were sputtered using a commercially available sputtering device with APC (manufactured by Furuya Metal Co., Ltd.), a silver alloy containing palladium and copper, as a sputtering target to form a metal reflective layer. Sputtering was performed by placing a glass plate near the partition wall substrate under conditions such that the metal thickness on the glass plate was 300 nm. After forming the metal reflective layer, SiN was formed as an inorganic protective layer in the same vacuum batch. The inorganic protective layer was formed under conditions such that the thickness on the glass substrate was 100 nm.

[0163] <Formation of Organic Protective Layer> One part by mass of amorphous fluorine-containing resin "CYTOP" (registered trademark) CTL-809M was mixed with one part by mass of fluorine-based solvent CT-SOLV180 (manufactured by AGC Inc.) to prepare a resin solution.

[0164] The obtained resin solution was vacuum-printed onto the partition walls on which the metal reflective layer and the inorganic protective layer had been formed, then dried at 90° C. for 1 hour and further heated at 190° C. for 1 hour to form an organic protective layer. The cross section of the partition wall was exposed using a triple ion milling device EMTIC3X (manufactured by LEICA), and images were taken and measured using a field emission scanning electron microscope (FE-SEM) Merlin (manufactured by Zeiss). The thickness of the organic protective layer on the side surface at the center in the height direction of the partition wall was 1 μm.

[0165] <Formation of phosphor layer> A phosphor paste was prepared by mixing 10 parts by mass of phosphor powder GOS:Tb (Tb-doped gadolinium oxysulfide) with 5 parts by mass of a 10% by mass binder resin solution prepared by dissolving binder resin "Ethocel" (registered trademark) 7cp (manufactured by The Dow Chemical Company) in benzyl alcohol (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.). The average particle diameter D50 of the phosphor measured using a particle size distribution analyzer MT3300 (manufactured by Nikkiso Co., Ltd.) was 11 μm.

[0166] The obtained phosphor paste was vacuum-printed onto a partition wall having a metal reflective layer, an inorganic protective layer, and an organic protective layer formed thereon so that the volume fraction of the phosphor was 65%, and then dried at 150°C for 15 minutes to form a phosphor layer, thereby obtaining a scintillator panel.

[0167] Examples 2 to 13 Acrylic resin layers and partition walls were formed to produce scintillator panels in the same manner as in Example 1, except that in <Formation of Acrylic Resin Layer>, acrylic resins shown in Tables 3 and 4 were used instead of acrylic resin 1 obtained in Synthesis Example 1.

[0168] <Examples 14 to 19> In <Formation of Acrylic Resin Layer>, an acrylic resin layer and partition walls were formed in the same manner as in Example 1, except that the thickness of the acrylic resin layer was changed as shown in Table 4.

[0169] Comparative Example 1 An acrylic resin layer and partition walls were formed in the same manner as in Example 1, except that the step of forming an acrylic resin layer was not carried out, to produce a scintillator panel.

[0170] <Examples 20 to 26> Acrylic resin layers and partition walls were formed, and scintillator panels were produced in the same manner as in Example 1, except that in <Formation of Acrylic Resin Layer>, the types and blending amounts of the acrylic resin and polymerizable monomer were changed as shown in Table 5.

[0171] Example 27 An acrylic resin layer and partition walls were formed in the same manner as in Example 1, except that in <Formation of Acrylic Resin Layer>, no silane coupling agent was added, to produce a scintillator panel.

[0172] Example 28 An acrylic resin layer and barrier ribs were formed in the same manner as in Example 1, except that no epoxy compound was added in the <Formation of Barriers>, to produce a scintillator panel.

[0173] Examples 29 to 32 Acrylic resin layers and partition walls were formed in the same manner as in Example 1, except that in <Formation of partition walls>, an oxetane compound shown in Table 6 was used instead of the oxetane compound B-1a obtained in Synthesis example 16, and scintillator panels were produced.

[0174] <Examples 33 to 38> Acrylic resin layers and partition walls were formed in the same manner as in Example 31, except that in <Formation of Acrylic Resin Layer>, the types of acrylic resin and polymerizable monomer were changed as shown in Table 6, to produce scintillator panels.

[0175] Examples 39 and 40 Acrylic resin layers and partition walls were formed in the same manner as in Example 31, except that in <Formation of partition walls>, the type of epoxy compound was changed as shown in Table 7, to prepare scintillator panels.

[0176] Examples 41 and 42 Acrylic resin layers and partition walls were formed in the same manner as in Example 1, except that in <Formation of partition walls>, the type of epoxy compound was changed as shown in Table 7, to prepare scintillator panels.

[0177] Example 43 An acrylic resin layer and partition walls were formed in the same manner as in Example 1, except that in <Formation of partition walls>, the polyimide resin A-1 obtained in Synthesis Example 16 was replaced with the polyimide resin A-2 obtained in Synthesis Example 17, and a scintillator panel was produced.

[0178] <Comparative Example 2> An acrylic resin layer and partition walls were formed, and a scintillator panel was produced in the same manner as in Example 1, except that <Formation of acrylic resin layer> was not performed, and that A'-4 was used as the other resin instead of the polyimide resin A-1 obtained in Synthesis Example 16.

[0179] Comparative Example 3 An acrylic resin layer and barrier ribs were formed in the same manner as in Example 1, except that in the <Formation of barrier ribs>, no oxetane compound was added, and a scintillator panel was produced.

[0180] Comparative Example 4 An acrylic resin layer and partition walls were formed in the same manner as in Example 1, except that in <Formation of partition walls>, A′-3 obtained in Synthesis Example 18 was used as the other resin instead of polyimide resin A-1, and a scintillator panel was produced.

[0181] The main configurations and evaluation results of each of the examples and comparative examples are shown in Tables 3 to 7.

[0182]

[0183]

[0184]

[0185]

[0186]

[0187] REFERENCE SIGNS LIST 1 Hardened material layer 2 Acrylic resin layer 3 Substrate 4 Radiation detector member 5 Scintillator panel 6 Output substrate 7 Phosphor layer 8 Diaphragm layer 9 Photoelectric conversion layer 10 Output layer 11 Substrate 12 Metal reflective layer 13 Organic protective layer 14 Phosphor 15 Binder layer 16 Diaphragm 17 Inductor 18 Insulating film 19 Coil 20 Resin layer 21 Substrate 22 Insulating film 23 Magnetic material 24 Molding resin L1 Height L2 Spacing L3 Center width W Width of insulating film T Thickness of insulating film

Claims

1. A laminate having, on a substrate, a cured layer made of a cured product of a resin composition containing (A) a polyimide resin, (B) an oxetane compound, and (C) a photocationic polymerization initiator, and having, between the substrate and the cured layer, an acrylic resin layer adjacent to the substrate and the cured layer.

2. The laminate according to claim 1, wherein the acid value of the acrylic resin layer is 50 mgKOH / g or more and 230 mgKOH / g or less.

3. The laminate according to claim 1 or 2, wherein the hydroxyl value of the acrylic resin layer is 10 mgKOH / g or more and 150 mgKOH / g or less.

4. The laminate according to claim 1 or 2, wherein the weight average molecular weight of said acrylic resin layer is 8,000 or more and 200,000 or less.

5. The laminate according to claim 1 or 2, wherein the oxetane compound (B) includes a compound (B-1) having four or more oxetanyl groups.

6. The laminate according to claim 5, wherein the compound (B-1) having four or more oxetanyl groups has a structure represented by the following general formula (1): In the above general formula (1), R １ represents an n-valent group having a siloxane bond. ２ represents a hydrogen atom or a monovalent organic group having 1 to 6 carbon atoms, and n is in the range of 4 to 30.

7. The laminate according to claim 1 or 2, wherein the resin composition further contains (D) an epoxy compound.

8. The laminate according to claim 1 or 2, wherein the (B) oxetane compound and / or the (D) epoxy compound has a polyalkylene glycol chain.

9. A scintillator panel having the laminate according to claim 1 or 2, wherein the scintillator panel has cells on the substrate, the cells being partitioned by partition walls made of the cured material layer, and the cells each having a phosphor layer.

10. An electronic component comprising the laminate of claim 1 or 2.

11. The electronic component according to claim 10, wherein the substrate of said laminate is a silicon substrate, a silicon carbide substrate or a gallium nitride substrate.

12. An inductor having an insulating film and a coil, comprising the laminate of claim 1 or 2 and a coil, wherein the insulating film is a hardened layer of the laminate.

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