Resin composition, cured product, scintillator panel, and sensor

Abstract

Provided is a resin composition capable of forming a pattern having a high aspect ratio. A resin composition containing (A) a resin, (B) an oxetane compound, and a photocationic polymerization initiator, the (A) resin containing a resin having an alkali-soluble group, and the (B) oxetane compound containing (B-1) a compound having four or more oxetane groups.

Description

Technical Field

[0001] The invention relates to a resin composition, a cured product, a scintillator panel and a sensor. Background Art

[0002] In the medical field, structural inspection, baggage inspection and other industrial applications, digital radiation detection devices such as flat panel detectors (FPD) are used. In the indirect conversion FPD, a scintillator panel is used to convert X-rays into visible light. The scintillator panel has a phosphor layer (scintillator layer) containing phosphors such as gadolinium oxysulfide (GOS), and the phosphor emits light when irradiated with X-rays. The scintillator panel converts the light emitted from the scintillator panel into an electrical signal by using a sensor (photoelectric conversion layer) having a thin film transistor (TFT) or a charge coupled device (CCD), thereby converting the X-ray information into digital image information. However, in the scintillator panel, there is a problem that the light emitted from the radiation phosphor is scattered in the phosphor layer, and the sharpness of the obtained image is reduced.

[0003] Therefore, in order to reduce the influence of light scattering, a method of filling a phosphor in a space partitioned by a partition wall is proposed. Furthermore, as a technology to solve the problem of brightness reduction caused by a partition wall, a scintillator panel is proposed, which has a substrate, a partition wall formed on the substrate, and a scintillator layer having a phosphor partitioned by the partition wall, wherein the partition wall contains one or more compounds (P) selected from polyimide, polyamide, polyamideimide and polybenzoxazole (for example, refer to Patent Document 1).

[0004] On the other hand, in industrial applications such as food and electronic components, there is a tendency for brightness to decrease over time due to continuous irradiation of high-energy X-rays during online inspection. In response to this, a scintillator panel has been proposed, which has a substrate and a scintillator layer containing a phosphor, wherein the scintillator layer contains a binder resin having a π-conjugated system structure composed of 7 or more atoms, and the glass transition temperature of the binder resin is 30 to 430° C., and the film thickness of the scintillator layer is 50 to 800 μm (see, for example, Patent Document 2).

[0005] Prior art literature

[0006] Patent Literature

[0007] Patent Document 1: International Publication No. 2021 / 200327

[0008] Patent Document 2: International Publication No. 2022 / 024860 Summary of the invention

[0009] However, in particular, in industrial applications, in order to increase the amount of phosphors for irradiating high-energy X-rays, it is required to thicken the phosphor layer and thin the partition walls. Due to such a background, a partition wall with a higher aspect ratio is required. However, it is difficult for conventionally known resin compositions to form patterns such as partition walls with a high aspect ratio required due to the background.

[0010] Therefore, in view of the above-mentioned problems in the prior art, an object of the present invention is to provide a resin composition, a cured product, a scintillator panel, and a sensor capable of forming a pattern with a high aspect ratio.

[0011] A resin composition according to one embodiment of the present invention that solves the above-mentioned problems is a resin composition comprising (A) a resin, (B) an oxetane compound, and a photocationic polymerization initiator, wherein the (A) resin comprises a resin having an alkali-soluble group, and the (B) oxetane compound comprises (B-1) a compound having 4 or more oxetane groups.

[0012] Moreover, a cured product according to one embodiment of the present invention that solves the above-mentioned problems is a cured product obtained by curing the above-mentioned resin composition.

[0013] Furthermore, a scintillator panel according to one embodiment of the present invention for solving the above-mentioned problems is a scintillator panel including a substrate, partition walls formed on the substrate, and phosphor layers in cells partitioned by the partition walls, wherein the partition walls are formed of the above-mentioned cured product.

[0014] In addition, an inductor according to one aspect of the present invention for solving the above-mentioned problems is an inductor including an insulating film and a coil, wherein the insulating film is the above-mentioned cured product.

[0015] Brief description of the attached figure

[0016] Figure 1 It is a cross-sectional view schematically showing a radiation detector member including a scintillator panel according to one embodiment of the present invention.

[0017] Figure 2 It is schematically indicated Figure 1 An enlarged cross-sectional view of a substrate and partition wall portion of a radiation detector member shown.

[0018] Figure 3 It is a cross-sectional view schematically showing the structure of an inductor according to one embodiment of the present invention. DETAILED DESCRIPTION

[0019] The resin composition of one embodiment of the present invention comprises (A) a resin, (B) an oxetane compound, and a photocationic polymerization initiator. The (A) resin comprises a resin having an alkali-soluble group. The (B) oxetane compound comprises (B-1) a compound having 4 or more oxetane groups (hereinafter sometimes referred to as "(B-1) oxetane compound").

[0020] (A) The resin has the function of maintaining the shape of the resin composition and improving the processability. (B) The oxetane compound is cured by cationic polymerization. In particular, among various oxetane compounds, by selecting (B-1) a compound having 4 or more oxetane groups with excellent curability, the resin composition can form a pattern with a high aspect ratio with high resolution. In the resin composition, as the (B) oxetane compound, an oxetane compound having 1 to 3 oxetane groups may also be contained together with the (B-1) oxetane compound.

[0021] The resin composition of the present embodiment preferably further contains (C) an epoxy compound. In addition, the resin composition contains a photocationic polymerization initiator. The (C) epoxy compound has the effect of improving the adhesion to the substrate when the resin composition is formed on the substrate. By containing a photocationic polymerization initiator, the resin composition is irradiated with light, and the photocationic polymerization initiator generates an acid, thereby polymerizing the (B) oxetane compound and showing negative photosensitivity that is insoluble in a developer. Pattern formation based on negative photosensitivity is a pattern formed by the exposure portion of photocrosslinking, so that a pattern with excellent mechanical properties can be formed.

[0022] <(A) Resin>

[0023] Resin is acrylic resin, styrene resin, phenolic resin, epoxy resin, polyester, polyvinyl alcohol, polyamide, polyimide, polyamide-imide, polybenzoxazole etc.Resin can contain two or more of these resins.Wherein, resin is preferably polyamide, polyimide, polyamide-imide, polybenzoxazole.By using them as resin, resin composition can improve the mechanical properties of the cured product obtained, form a pattern with higher aspect ratio.Resin is more preferably polyimide, polybenzoxazole.

[0024] The weight average molecular weight of the (A) resin is preferably 1000 or more, more preferably 2000 or more. In addition, the weight average molecular weight of the resin is preferably 20000 or less, more preferably 10000 or less. By making the weight average molecular weight of the (A) resin be 1000 or more, the resin composition can improve film forming properties. On the other hand, by making the weight average molecular weight of the (A) resin be 20000 or less, the resin composition can improve solubility during development. It should be noted that the weight average molecular weight of the (A) resin in the present embodiment is measured by gel permeation chromatography (GPC method) and calculated in terms of polystyrene.

[0025] From the perspective of cationic polymerizability, the resin (A) preferably has substantially no basic functional groups such as amino groups that can be inhibitory groups for cationic polymerization. By substantially having no inhibitory groups for cationic polymerization, the resin composition can improve cationic polymerizability and form a pattern with a higher aspect ratio. Here, "substantially having no" specifically means that the equivalent weight of the basic functional group is 1000 g / eq or more.

[0026] (A) The resin contains a resin having an alkali-soluble group. Thus, the resin composition can obtain appropriate solubility when developed with an alkali developer, and can improve the contrast between the exposed portion and the unexposed portion. Alkali-soluble groups are, for example, phenolic hydroxyl groups, carboxyl groups, silanol groups, sulfonic groups, etc. (A) The resin may also have two or more of these alkali-soluble groups. Among them, the alkali-soluble group is preferably a phenolic hydroxyl group. Resins having phenolic hydroxyl groups are, for example, polyhydroxyphenyl acrylate, polyhydroxyphenyl methacrylate, polyparahydroxystyrene, polyamides having phenolic hydroxyl groups, polyimides, polyamide-imides, polybenzoxazoles, etc. (A) The resin may also contain two or more of these resins having phenolic hydroxyl groups.

[0027] The polyamide, polyimide, polyamideimide, and polybenzoxazole having a phenolic hydroxyl group preferably have 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'-bis(trifluoromethyl)-5,5'-dihydroxy-4,4'-diaminobiphenyl, bis(3-amino-4-hydroxyphenyl)fluorene, and 2,2'-bis(trifluoromethyl)-5,5'-dihydroxybenzidine, and compounds in which a portion of hydrogen atoms of these aromatic rings or hydrocarbons are substituted with an alkyl group or a fluoroalkyl group having 1 to 10 carbon atoms, a halogen atom, or the like. The polyamide, polyimide, polyamideimide, and polybenzoxazole having a phenolic hydroxyl group may have two or more diamine residues having a phenolic hydroxyl group. In addition, the polyamide, polyimide, polyamideimide, and polybenzoxazole having an alkali-soluble group may further have a diamine residue not having a phenolic hydroxyl group.

[0028] The content of (A) resin in the resin combination of the present embodiment is preferably more than 15 mass % in solid component, more preferably more than 25 mass %. In addition, the content of (A) resin in the resin combination is preferably less than 70 mass % in solid component, more preferably less than 60 mass %. By making the content of (A) resin more than 15 mass %, the mechanical properties and thermal properties of the cured product formed by curing the resin combination can be improved. On the other hand, by containing (A) resin below 70 mass %, the resin combination can suppress the developing residue during development.

[0029] <(B) Oxetane Compound>

[0030] The resin composition of the present embodiment contains (B) an oxetane compound. (B) The oxetane compound is, for example, 3-methyl-3-hydroxymethyloxetane, 3-ethyl-3-hydroxymethyloxetane, 2-ethylhexyl (3-ethyl-3-oxetane methyl) ether, 2-hydroxyethyl (3-ethyl-3-oxetane methyl) ether, 2-hydroxypropyl (3-ethyl-3-oxetane methyl) ether, 1,4-bis [(3-ethyl-3-oxetane methyloxy) methyl] benzene, oxetane silsesquioxane, phenolic resin oxetane (フェノールノボラックオキセタン), OXT-191 (trade name, Toagosei (Strain) system), etc. The resin composition may also contain two or more of these (B) oxetane compounds. In the present embodiment, the compound having an oxetane group is classified as (B) an oxetane compound even if it is a resin or a compound having an epoxy group.

[0031] The resin composition of the present embodiment is characterized in that, among these, (B-1) contains a compound having more than 4 oxetane groups. As described above, by selecting a compound having more than 4 oxetane groups (B-1) with excellent curability as (B) oxetane compound, the resin composition can form a pattern with a high aspect ratio. If a resin composition containing only a compound having less than 4 oxetane groups as (B) oxetane compound forms a high pattern, the resolution becomes insufficient and the aspect ratio becomes insufficient. (B-1) oxetane compound is, for example, oxetane silsesquioxane, linear phenolic resin oxetane, OXT-191 (trade name, Toa Synthetic (Strain) system), etc. The resin composition can also contain more than 2 kinds of (B-1) oxetane compounds among these. The number of oxetane groups in 1 molecule is preferably more than 7. Thus, the curability of the resin composition is further improved, and a pattern with a higher aspect ratio can be formed. On the other hand, the number of oxetane groups in one molecule is preferably less than 20. Thus, the resin composition can suppress the generation of cracks during pattern processing. The oxetane compound having oxetane groups of 7 or more and 20 or less in one molecule is, for example, OXT-191 (trade name, manufactured by Toagosei Co., Ltd.).

[0032] (B-1) The compound having four or more oxetanyl groups preferably has a structure represented by the following general formula (1).

[0033] [Chemical formula 1]

[0034]

[0035] 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, preferably a range of 7 to 20.

[0036] R 1 It has a siloxane bond. Since the siloxane bond is hydrolyzed by an alkaline developer, it can obtain appropriate solubility when developed with an alkaline developer, thereby improving the contrast between the exposed part and the unexposed part. 1 Silicates and polysilicates are preferred.

[0037] Composition R 2 The organic group is preferably an alkyl group such as a methyl group or an ethyl group. The alkyl group may be substituted by a halogen such as a fluorine group. When the alkyl group has a substituent, the alkyl group is preferably a perfluoroalkyl group such as a trifluoromethyl group or a pentafluoroethyl group. 2 The resin composition has a hydrogen atom or a monovalent organic group having 1 to 6 carbon atoms, and has excellent solubility in an alkaline developer, thereby improving developability.

[0038] Examples of the oxetane compound having a structure represented by the general formula (1) include oxetane silsesquioxane and OXT-191 (trade name, manufactured by Toagosei Co., Ltd.).

[0039] The oxetane compound having a structure represented by the above general formula (1) more preferably has a structure represented by the following general formula (2).

[0040] [Chemical formula 2]

[0041]

[0042] In the above general formula (2), R 2 With R in the general formula (1) 2 m is a repetition number, which represents an integer greater than 1.

[0043] In general formula (2), the resin composition can improve heat resistance by having a silicate structure in which four oxygen atoms are bonded to silicon. In addition, since the resin composition has a large number of siloxane bonds, the contrast between the exposed portion and the unexposed portion can be further improved by hydrolysis with an alkaline developer.

[0044] Examples of the oxetane compound having the structure represented by the general formula (2) include OXT-191 (trade name, manufactured by Toagosei Co., Ltd.).

[0045] The content of (B-1) oxetane compound in the resin combination of the present embodiment is relative to the content 100 mass parts of (A) resin, preferably more than 30 mass parts, more preferably more than 50 mass parts. In addition, the content of (B-1) oxetane compound is relative to the content 100 mass parts of (A) resin, preferably less than 160 mass parts, more preferably less than 130 mass parts. By making the content of (B-1) oxetane compound more than 30 mass parts, the curability of resin combination is further improved, and a pattern with a higher aspect ratio can be formed. On the other hand, by making the content of (B-1) oxetane compound less than 160 mass parts, the resin combination can improve the resolution during pattern processing.

[0046] <(C) Epoxy Compound>

[0047] The resin composition of the present embodiment preferably further contains (C) an epoxy compound. Examples of the (C) epoxy compound include aromatic epoxy compounds, alicyclic epoxy compounds, aliphatic epoxy compounds, etc. The resin composition may contain two or more of these (C) epoxy compounds.

[0048] The aromatic epoxy compound is, for example, glycidyl ether of monovalent or polyvalent phenol (phenol, bisphenol A, novolac resin, and compounds which are alkylene oxide adducts thereof) having at least one aromatic ring.

[0049] The alicyclic epoxy compound is, for example, a compound obtained by epoxidizing a compound having at least one cyclohexene or cyclopentene ring with an oxidizing agent (such as 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate).

[0050] Aliphatic epoxy compounds include, for example, polyglycidyl ethers of aliphatic polyols or oxyalkylene adducts thereof (1,4-butanediol diglycidyl ether, 1,6-hexanediol diglycidyl ether, etc.), polyglycidyl esters of aliphatic polybasic acids (tetrahydrophthalic acid diglycidyl ether, etc.), and epoxides of long-chain unsaturated compounds (epoxidized soybean oil, epoxidized polybutadiene, etc.).

[0051] At least one of the (B) oxetane compound and the (C) epoxy compound preferably has a polyalkylene glycol chain. By having a highly flexible polyalkylene glycol chain, the resin composition can suppress the occurrence of cracks in the film or cured product after drying.

[0052] From the viewpoint of compatibility with the (A) resin, the number average molecular weight of the compound having a polyalkylene glycol chain is preferably 300 to 4000. By making the number average molecular weight above 300, the resin composition can further improve the compatibility and flexibility of the (A) resin and the compound having a polyalkylene glycol chain, and further suppress the generation of cracks. On the other hand, by making the number average molecular weight below 4000, the resin composition can appropriately suppress the epoxy / oxetane equivalent, further improve the curability, and form a pattern with a higher aspect ratio. The chemical structure of the compound having a polyalkylene glycol chain can be analyzed by combining 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 carbon number of the alkylene group in the repeating unit of the polyalkylene glycol chain is preferably 2 to 6, more preferably 2. When the carbon number of the alkylene group is within the above range, the resin composition has excellent solubility in an alkaline developer and can improve developability.

[0054] In addition, the number of epoxy groups and oxetane groups in at least any one of the (B) oxetane compound or (C) epoxy compound having a polyalkylene glycol chain is preferably 2 or more. Thus, the resin composition can further improve curability and form a pattern with a higher aspect ratio. The (B) oxetane compound is, for example, bis[(3-ethyloxetane-3-yl)methoxy]polyethylene glycol, and as the (C) epoxy compound, for example, polyethylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether, etc.

[0055] (B) The oxetane compound and (C) The 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 or the (C) epoxy compound is preferably a water-soluble compound that dissolves in 900 parts by mass of water at 20°C within 1 minute for 100 parts by mass of the compound. Specifically, at least one of the (B) oxetane compound or the (C) epoxy compound is 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 ether, etc.

[0056] The total content of (B) oxetane compound and (C) epoxy compound in the resin composition of the present embodiment is preferably 50 parts by mass or more, and more preferably 70 parts by mass or more, relative to 100 parts by mass of the content of (A) resin. In addition, the total content of (B) oxetane compound and (C) epoxy compound is preferably 170 parts by mass or less, and more preferably 140 parts by mass or less, relative to 100 parts by mass of the content of (A) resin. By making their total content 50 parts by mass or more, the resin composition can suppress the generation of cracks in the coating film. On the other hand, by making their total content 170 parts by mass or less, the resin composition can suppress the performance of the viscosity of the coating film.

[0057] <Photocationic polymerization initiator>

[0058] The photocationic polymerization initiator generates acid by light, and generates cationic polymerization. Examples of the photocationic polymerization initiator include aromatic iodonium salts, aromatic sulfonium salts, aromatic borates, and the like. The resin composition may also contain two or more of these photocationic polymerization initiators. Among them, the photocationic polymerization initiator is preferably an aromatic sulfonium salt, such as diphenyl[(phenylsulfanyl)phenyl]sulfonium=hexafluorophosphate, diphenyl[4-(phenylsulfanyl)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, CPI-410B (trade names, all manufactured by San-apro (KK)), and the like.

[0059] The content of the photocationic polymerization initiator in the resin composition of the present embodiment is preferably 0.3 mass parts or more relative to 100 mass parts of the content of the (A) resin. Thus, the resin composition can further improve the curability and form a pattern with a higher aspect ratio. On the other hand, relative to 100 mass parts of the content of the (A) resin, the content of the photocationic polymerization initiator is preferably less than 10 mass parts. Thus, the resin composition can improve stability.

[0060] <Other ingredients>

[0061] In the resin composition of the present embodiment, together with (B) epoxy compound and (C) oxetane compound, cationic polymerizable compounds other than these may also be contained. Cationic polymerizable compounds other than (B) epoxy compound and (C) oxetane compound are, for example, olefinic unsaturated compounds, bicyclic orthoesters, spiro orthocarbonates, spiro orthoesters, etc. The resin composition may also contain two or more cationic polymerizable compounds other than (B) epoxy compound and (C) oxetane compound.

[0062] Examples of olefinic unsaturated compounds include aliphatic monovinyl ethers, aromatic monovinyl ethers, polyfunctional vinyl ethers, styrene, and cationic 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 cationic polymerizable nitrogen-containing monomers include N-vinylcarbazole and N-vinylpyrrolidone.

[0063] Examples of the bicyclic orthoesters include 1-phenyl-4-ethyl-2,6,7-trioxabicyclo[2.2.2]octane and 1-ethyl-4-hydroxymethyl-2,6,7-trioxabicyclo-[2.2.2]octane.

[0064] Examples of the spiro orthocarbonate include 1,5,7,11-tetraoxaspiro[5.5]undecane and 3,9-dibenzyl-1,5,7,11-tetraoxaspiro[5.5]undecane.

[0065] Examples of the spirocyclic orthoesters include 1,4,6-trioxaspiro[4.4]nonane, 2-methyl-1,4,6-trioxaspiro[4.4]nonane, 1,4,6-trioxaspiro[4.5]decane, and the like.

[0066] As required, the resin composition of the present embodiment may further contain additives such as sensitizers and surfactants, inorganic particles, solvents, etc. The solvent is preferably a solvent that dissolves the components constituting the resin composition, such as ethers such as ethylene glycol monoethyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, ethylene glycol dimethyl ether, ethylene glycol diethyl ether, ethylene glycol dibutyl ether, ethylene glycol monoethyl ether acetate, propylene glycol monomethyl ether acetate, propyl acetate, butyl acetate, isobutyl acetate, 3-methoxybutyl acetate, 3-methyl-3-methoxybutyl acetate, 3-methyl-2-butanol, 3-methyl-3-methoxybutanol, alcohols such as diacetone alcohol, N,N-dimethylformamide, N,N-dimethylacetamide, dimethyl sulfoxide, γ-butyrolactone, etc. The resin composition may also contain two or more solvents in these.

[0067] The method for producing the resin composition of the present embodiment is, for example, a method of adding (A) to (B) and, if necessary, (C) an epoxy compound, a solvent, other additives, and the like, followed by stirring.

[0068] The resin composition of the present embodiment can be processed into various shapes such as a varnish shape or a film shape for use.

[0069] <Cured product>

[0070] Next, a cured product according to an embodiment of the present invention is described. The cured product according to this embodiment is a cured product obtained by curing the above-mentioned resin composition. The cured product according to this embodiment can be used, for example, for surface protective films of semiconductor elements or sensor devices, interlayer insulating films, MEMS (micro-electromechanical systems), and partition walls of scintillator panels.

[0071] The method for producing the cured product of the present embodiment is, for example, a method of irradiating (exposing) a chemical ray on a resin composition coating film, developing it as needed to form a pattern, and then heating it to cure it. The resin composition is cured by heat curing, a thermal crosslinking reaction, and a cationic polymerization reaction in the case of containing a photo-induced cationic polymerization initiator. The chemical ray used in the exposure is, for example, ultraviolet rays, visible rays, electron rays, X-rays, etc. The heating temperature is preferably 120°C to 300°C.

[0072] <Scintillator panel>

[0073] A scintillator panel of one embodiment of the present invention comprises a substrate, a partition wall formed on the substrate, and a phosphor layer in a unit partitioned by the partition wall. The partition wall is formed by a cured product of the above embodiment. By using the resin composition of the above embodiment, the scintillator panel can easily form a partition wall with a high aspect ratio. In addition, by having the partition wall, the scintillator panel can improve the brightness. In addition, since the surface smoothness of the partition wall is excellent, the scintillator panel can improve the light extraction efficiency of the phosphor and improve the brightness.

[0074] Hereinafter, an embodiment of the scintillator panel of the present embodiment will be described using the drawings. It should be noted that the drawings are schematic diagrams. In addition, the present embodiment is not limited to the embodiments described below.

[0075] Figure 1 A cross-sectional view schematically shows a component for a radiation detector including a scintillator panel of the present embodiment. The component 1 for a radiation detector has a scintillator panel 2 and an output substrate 3. The scintillator panel 2 has a substrate 4, a partition wall 5, and a phosphor layer 6 in a unit partitioned by the partition wall 5. A metal reflection layer 11 is formed on the surface of the partition wall 5, and an organic protective layer 12 is provided on the surface thereof. The phosphor layer 6 contains a phosphor 13 and a binder resin 14. The output substrate 3 has an output layer 9 and a photoelectric conversion layer 8 having a photodiode on the substrate 10 in sequence. A diaphragm layer 7 may also be provided on the photoelectric conversion layer 8. The light output surface of the scintillator panel 2 and the photoelectric conversion layer 8 of the output substrate 3 are preferably bonded or closely adhered via the diaphragm layer 7. The light emitted from the phosphor layer 6 reaches the photoelectric conversion layer 8 and is photoelectrically converted and output. Each of them is described below.

[0076] <Substrate>

[0077] The material constituting the substrate is preferably a material having radiation transmittance. The material constituting the substrate is, for example, a material exemplified as a material constituting the substrate in International Publication No. 2021 / 200327. Among them, the material constituting the substrate is preferably a polymer material having high radiation transmittance and high surface smoothness. The polymer material is preferably polyester such as polyethylene terephthalate and polyethylene naphthalate, polyamide, polyimide, etc.

[0078] In the case of a substrate formed of a polymer material, the thickness of the substrate is preferably 3.0 mm or less.

[0079] <Next door>

[0080] The partition wall is provided at least to form the separated space (unit). Therefore, in the scintillator panel, by making the size and spacing of the pixels of the photoelectric conversion element arranged in a grid shape consistent with the size and spacing of the unit of the scintillator panel, each pixel of the photoelectric conversion element can correspond to each unit of the scintillator panel. Thus, a high-sharp image can be obtained.

[0081] The partition wall is preferably formed by the cured product of the present embodiment. By having a partition wall formed by the cured product of the resin composition of the present embodiment, the scintillator panel can improve the brightness. It is believed that its principle mainly lies in the following aspects. By using the resin composition of the above embodiment, the scintillator panel can easily form a partition wall with a high aspect ratio. Therefore, the scintillator panel can increase the filling amount of the phosphor in the phosphor layer, thereby improving the brightness.

[0082] Figure 2 It is schematically indicated Figure 1 The enlarged cross-sectional view of the substrate and partition wall portion of the radiation detector member shown. The partition wall 5 on the substrate 4 has a trapezoidal cross-sectional shape with a height L1, a bottom width L3, and a top width L4 at a spacing L2. The width of the partition wall at the half of the height L1 is set as the middle width L5.

[0083] The height L1 of the partition wall is preferably 100 μm or more, more preferably 200 μm or more. By setting L1 to 100 μm or more, the scintillator panel can increase the phosphor filling amount, thereby further improving the brightness. On the other hand, the height L1 of the partition wall is preferably 3000 μm or less, more preferably 1000 μm or less. By setting L1 to 3000 μm or less, the scintillator panel can suppress the absorption of the luminous light generated by the phosphor itself, thereby further improving the brightness.

[0084] The interval L2 between adjacent partition walls is preferably 40 μm or more, more preferably 1000 μm or less. The bottom width L3 of the partition wall is preferably 3 μm or more, preferably 150 μm or less. The top width L4 of the partition wall 5 is preferably 3 μm or more, preferably 30 μm or less.

[0085] The aspect ratio (L1 / L5) of the height L1 of the partition wall relative to the width L5 of the middle portion of the partition wall is preferably 5.0 or more. Thus, the scintillator panel can increase the filling amount of the phosphor to further improve the brightness. The aspect ratio (L1 / L5) is more preferably 12 or more, more preferably 14 or more, and further preferably 15 or more. On the other hand, the aspect ratio (L1 / L5) is preferably 100 or less, more preferably 50 or less. Thus, the scintillator panel can improve the strength of the partition wall.

[0086] The height L1 of the partition wall, the interval L2 between adjacent partition walls, the bottom width L3, the top width L4 and the middle width L5 can be measured by observing the cross section exposed by cutting a cross section perpendicular to the substrate or by a grinding device such as a CROSS SECTION POLISHER using a scanning electron microscope. Here, the width of the partition wall at the contact portion between the partition wall and the substrate is set to L3. In addition, the width of the top of the partition wall is set to L4, and the width of the middle of the position of half the height L1 is set to L5. Each length L1 to L5 is calculated by averaging the measured values ​​of the three randomly selected partition walls.

[0087] The method for adjusting the aspect ratio (L1 / L5) to the above range is preferably a method for forming the partition wall from the resin composition of the present embodiment, and more preferably the components and contents constituting the resin composition are adjusted to the above preferred range.

[0088] <Metal reflective layer>

[0089] In the scintillator panel of this embodiment, the partition wall preferably has a reflective layer containing metal (hereinafter referred to as "metal reflective layer") on its surface. The metal reflective layer only needs to be provided on at least a portion of the partition wall. The metal reflective layer has a high reflectivity even if it is a thin film. Therefore, by providing a metal reflective layer as a thin film, the filling amount of the phosphor is difficult to reduce, and the brightness of the scintillator panel is further improved. The metal reflective layer is, for example, a layer exemplified as a metal reflective layer in International Publication No. 2019 / 181444.

[0090] <Protective layer>

[0091] The scintillator panel of this embodiment preferably has a protective layer on the surface of the metal reflective layer. Even when the metal reflective layer uses an alloy that lacks resistance to discoloration in the atmosphere, the protective layer can reduce discoloration. As a result, the scintillator panel can suppress the reduction in reflectivity of the metal reflective layer caused by the reaction between the metal reflective layer and the phosphor layer, and the brightness is further improved.

[0092] The protective layer may be any of an inorganic protective layer and an organic protective layer. The protective layer may be a laminate of an inorganic protective layer and an organic protective layer.

[0093] <Inorganic protective layer>

[0094] The inorganic protective layer is suitable as a protective layer because of its low water vapor permeability. The inorganic protective layer is, for example, a layer exemplified as an inorganic protective layer in International Publication No. 2019 / 181444.

[0095] <Organic protective layer>

[0096] The organic protective layer is preferably formed of a polymer compound having excellent chemical durability, and preferably contains polysiloxane or amorphous fluororesin as a main component. The organic protective layer is, for example, a layer exemplified as an organic protective layer in International Publication No. 2019 / 181444. Polysiloxane and amorphous fluororesin are, for example, substances exemplified as materials constituting the organic protective layer in International Publication No. 2021 / 200327.

[0097] <Phosphor Layer>

[0098] The scintillator panel of the present embodiment includes a phosphor layer in cells partitioned by partition walls.

[0099] The phosphor layer absorbs the energy of incident X-rays and other radiation and emits electromagnetic waves with a wavelength range of 300nm to 800nm, that is, light ranging from ultraviolet light to infrared light with visible light as the center. The light emitted by the phosphor layer is photoelectrically converted in the photoelectric conversion layer and output as an electrical signal through the output layer. The phosphor layer preferably has a phosphor and a binder resin.

[0100] <Phosphor>

[0101] The phosphor is, for example, a substance exemplified as a phosphor in International Publication No. 2021 / 200327. From the viewpoint of high luminous efficiency, the phosphor is preferably a terbium-activated rare earth oxysulfide-based phosphor.

[0102] <Binder resin>

[0103] The binder resin is, for example, one exemplified as the binder resin in International Publication No. 2021 / 200327.

[0104] The binder resin is preferably in contact with the protective layer. In this case, the binder resin only needs to be in contact with at least a portion of the protective layer. As a result, the phosphor of the scintillator panel is unlikely to fall off from the unit. Figure 1 As shown, the binder resin may be filled in the cells with almost no gaps or may be filled with gaps.

[0105] As described above, according to the scintillator panel of this embodiment, a high-brightness image can be obtained.

[0106] <Method for Manufacturing Scintillator Panel>

[0107] A method for manufacturing a scintillator panel according to an embodiment of the present invention preferably includes, for example, a step of forming a partition wall on a substrate to separate cells; a step of forming a reflective layer to form a metal reflective layer on the surface of the partition wall as needed; and a step of filling a fluorescent body in the cells separated by the partition wall. The partition wall contains the cured product of the above embodiment. Each step is described below. It should be noted that in the following description, matters common to those described in the embodiment of the scintillator panel described above are appropriately omitted.

[0108] <Partitioning Wall Formation Step>

[0109] The partition forming process of the resin composition using the present embodiment is described. On the surface of the substrate, the resin composition of the above embodiment is applied in whole or in part to obtain a coating film. The method of applying the resin composition is, for example, a method using a coating machine such as a bar coater, a roller coater, a die coater, a scraper coater, etc. The thickness of the coating film can be adjusted by the number of coatings, the mesh size of the screen, the viscosity of the resin composition, etc.

[0110] Next, a pattern is formed by the resin composition coating film formed by the above method. When the resin composition is photosensitivity, the resin composition coating film is exposed by irradiating chemical rays through a mask having a desired pattern. The chemical rays used in the exposure are, for example, ultraviolet rays, visible rays, electron rays, X-rays, etc. In this embodiment, the chemical rays preferably use i-line (365nm), h-line (405nm), and g-line (436nm) of a mercury lamp.

[0111] After exposure, the exposed portion is removed with a developer. The developer may be, for example, one exemplified as a developer in International Publication No. 2021 / 200327.

[0112] The development can be carried out by spraying the developer onto the coating surface; filling the coating surface with the developer; immersing in the developer; or immersing and applying ultrasonic waves. The development conditions such as the development time and the temperature of the developer in the development step can be any conditions as long as the exposed part can be removed to form a pattern.

[0113] After development, the image is preferably rinsed with water, and may be rinsed by adding alcohols such as ethanol and isopropyl alcohol, or esters such as ethyl lactate and propylene glycol monomethyl ether acetate to water.

[0114] In addition, baking treatment can be performed before development as needed. As a result, the resolution of the pattern after development is sometimes improved, and the allowable range of the development conditions is increased. The baking treatment temperature is preferably in the range of 50 to 180° C., and more preferably in the range of 60 to 120° C. The time is preferably 5 seconds to several hours.

[0115] After pattern formation, unreacted cationic polymerizable compounds and cationic polymerization initiators remain in the coating film of the photosensitive resin composition. Therefore, during the thermal crosslinking reaction described later, they may be thermally decomposed to generate gas. In order to avoid this, it is preferred to irradiate the entire surface of the resin composition film after pattern formation with the above-mentioned exposure light, and generate acid from the cationic polymerization initiator in advance. Thus, during the thermal crosslinking reaction, the reaction of the unreacted cationic polymerizable compounds is carried out, and the generation of gas from thermal decomposition can be suppressed.

[0116] After development, a heat crosslinking reaction is performed by applying a temperature of 120°C to 300°C to cure the resin composition and obtain a partition wall. By crosslinking, heat resistance and chemical resistance can be improved. The heat treatment method can be selected from the following methods: a method of selecting a temperature and heating in stages; a method of selecting a certain temperature range, continuously heating, and implementing it for 5 minutes to 5 hours.

[0117] In the manufacturing method of the scintillator panel of the present embodiment, the substrate when the partition wall is formed can be used as the substrate of the scintillator panel, or the partition wall can be peeled off from the substrate and then placed on the substrate for use. The method of peeling off the partition wall from the substrate can use a known method such as a method of providing a peeling auxiliary layer between the substrate and the partition wall.

[0118] When the surface of the partition wall has a metal reflective layer, an inorganic protective layer and / or an organic protective layer, their formation methods are, for example, the methods exemplified as their formation steps in International Publication No. 2019 / 181444 and International Publication No. 2021 / 200327.

[0119] <Semiconductor Components>

[0120] The cured product of one embodiment of the present invention can be suitably used in a semiconductor element, particularly an inductor having an insulating film and a coil, and the cured product of this embodiment is used as an insulating film. The resin composition of the above embodiment can be easily formed into a pattern with a high aspect ratio, and therefore is preferably used in an inductor as a semiconductor element having a cured product with a high aspect ratio.

[0121] Figure 3 The inductor 15 schematically shows a cross-sectional view of the structure of the inductor of the present embodiment. The inductor 15 has a coil 17 and an insulating film 16 for insulating the coil 17 via a resin layer 18 above and below a substrate 19. Furthermore, the inductor 15 has a magnetic agent 21 via an insulating film 20 and is sealed by a molding resin 22.

[0122] The cured product of the above embodiment is preferably used as the insulating film 16. By using the cured product of the above embodiment as the insulating film 16, the inductor 15 can exhibit sufficient insulation even when the pattern width W of the insulating film 16 is small. Therefore, the inductor 15 can increase the cross-sectional area of ​​the wiring of the coil 17 and improve the inductance.

[0123] From the viewpoint of further increasing the cross-sectional area of ​​coil 17, thickness T of insulating film 16 is preferably 40 μm or more, more preferably 80 μm or more. From the viewpoint of reducing film stress, thickness T of insulating film 16 is preferably 300 μm or less, more preferably 200 μm or less.

[0124] From the viewpoint of increasing the wiring density of the coil 17, the aspect ratio obtained by dividing the film thickness of the insulating film 16 by the pattern width is preferably 4 or more, more preferably 8 or more. On the other hand, from the viewpoint of maintaining insulation, the aspect ratio of the insulating film 16 is preferably 30 or less, more preferably 20 or less.

[0125] An embodiment of the present invention has been described above. The present invention is not particularly limited to the above embodiment. It should be noted that the above embodiment is an embodiment mainly for describing the invention having the following configurations.

[0126] (1) A resin composition comprising (A) a resin, (B) an oxetane compound, and a photocationic polymerization initiator, wherein the (A) resin comprises a resin having an alkali-soluble group, and the (B) oxetane compound comprises (B-1) a compound having four or more oxetane groups.

[0127] (2) The resin composition according to (1), wherein the (B-1) compound having 4 or more oxetane groups has a structure represented by the following general formula (1):

[0128] [Chemical formula 3]

[0129]

[0130] (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 range of 4 to 30. )

[0131] (3) The resin composition according to (1) or (2), further comprising (C) an epoxy compound.

[0132] (4) The resin composition according to any one of (1) to (3), wherein at least one of the (B) oxetane compound and the (C) epoxy compound has a polyalkylene glycol chain.

[0133] (5) The resin composition according to (4), wherein the weight average molecular weight of the polyalkylene glycol chain is 300 to 4,000.

[0134] (6) The resin composition according to any one of (1) to (5), wherein the content of the (B-1) compound having four or more oxetane groups is 30 to 160 parts by mass based on 100 parts by mass of the (A) resin.

[0135] (7) A cured product obtained by curing the resin composition according to any one of (1) to (6).

[0136] (8) A scintillator panel comprising a substrate, partition walls formed on the substrate, and a phosphor layer in a cell partitioned by the partition walls, wherein the partition walls are formed of the cured product according to (7).

[0137] (9) The scintillator panel according to (8), wherein a height L1 of the partition walls is 100 μm or more.

[0138] (10) The scintillator panel according to (8) or (9), wherein an aspect ratio (L1 / L5) of a height L1 of the partition wall to a width L5 of a middle portion of the partition wall is 5.0 or more.

[0139] (11) An inductor comprising an insulating film and a coil, wherein the insulating film is the cured product according to (7).

[0140] Example

[0141] The present invention will be described in further detail below with reference to Examples and Comparative Examples. The compounds used in each of the Examples and Comparative Examples were synthesized by the following method.

[0142] <Synthesis Example 1: Synthesis of Polyimide A-1>

[0143] Under a dry nitrogen stream, 29.30 g (0.08 mol) of 2,2-bis(3-amino-4-hydroxyphenyl)hexafluoropropane (hereinafter referred to as "BAHF") (manufactured by Tokyo Chemical Industry Co., Ltd.) was added to 80 g of γ-butyrolactone (hereinafter referred to as "GBL") (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.), and dissolved by stirring at 120° C. Next, 30.03 g (0.1 mol) of acid anhydride "Rikasid" (registered trademark) TDA-100 (hereinafter referred to as "TDA-100") (manufactured by Shin Nippon Rika Co., Ltd.) was added together with 20 g of GBL, and 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. The precipitate was collected by filtration, washed with water three times, and then dried in a vacuum dryer at 80° C. for 5 hours to obtain a polyimide A-1 having a weight average molecular weight of 4,000 and a basic functional group equivalent of 1,000 g / eq or more.

[0144] <Synthesis Example 2: Synthesis of Polyimide A-2>

[0145] Under a dry nitrogen stream, 32.96 g (0.09 mol) of BAHF was added to 80 g of GBL, and the mixture was stirred and dissolved at 120° C. Subsequently, 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. Subsequently, the reaction solution was poured into 3 L of water to precipitate a white precipitate. The precipitate was collected by filtration, washed with water three times, and then dried in a vacuum dryer at 80° C. for 5 hours to obtain a polyimide A-2 having a weight average molecular weight of 8000 and a basic functional group equivalent of 1000 g / eq or more.

[0146] <Synthesis Example 3: Synthesis of polyamide-imide A-3>

[0147] 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, Ltd.), and cooled to -15°C. A solution obtained by dissolving 3-nitrobenzoyl chloride (20.4 g, 0.11 mol) (manufactured by Tokyo Chemical Industry Co., Ltd.) in 100 mL of acetone (manufactured by Tokyo Chemical Industry Co., Ltd.) was added dropwise thereto. After completion of the dropwise addition, the mixture was stirred at -15°C for 4 hours to react, and then returned to room temperature. The precipitated white solid was separated by filtration and vacuum dried at 50°C.

[0148] 30 g of the obtained white solid was placed in a 300 mL stainless steel autoclave, dispersed in 250 mL of methyl cellosolve (manufactured by Tokyo Chemical Industry Co., Ltd.), and 2 g of 5 mass % palladium-carbon was added. Hydrogen was introduced into the mixture using a balloon, and the mixture was stirred at room temperature to perform a reduction reaction. After about 2 hours, it was confirmed that the balloon would not shrink any further, and stirring was stopped. After the stirring was completed, the palladium compound as a catalyst was removed by filtration, and the mixture was concentrated using a rotary evaporator to obtain a hydroxyl-containing diamine compound (a).

[0149] Under a dry nitrogen stream, 31.4 g (0.08 mol) of a hydroxyl-containing diamine compound (a) was added to 80 g of GBL (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.), and the mixture was stirred at 120°C. Subsequently, 30.0 g (0.1 mol) of TDA-100 (manufactured by Shin Nippon Chemical Co., Ltd.) 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. Subsequently, the reaction solution was poured into 3 L of water to precipitate a white precipitate. The precipitate was collected by filtration, washed with water 3 times, and then dried in a vacuum dryer at 80°C for 5 hours to obtain a polyamide-imide A-3 having a weight average molecular weight of 5000 and a basic functional group equivalent of 1000 g / eq or more.

[0150] <Synthesis Example 4: Synthesis of Oxetane Compound B-1a>

[0151] 90.0 g (0.01 mol) of novolac resin (number average molecular weight 900) (produced by Meiwa Chemicals Co., Ltd.) was dissolved in 100 mL of dimethyl sulfoxide (produced by Fujifilm Wako Pure Chemicals Co., Ltd.), and after nitrogen substitution, 60.0 g of a 49 mass % potassium hydroxide aqueous solution (produced by Fujifilm Wako Pure Chemicals Co., Ltd.) was added, and stirred at 90° C. for 1 hour. Then, 60.5 g (0.5 mol) of 3-(chloromethyl)-3-methyloxetane (produced by Tokyo Chemical Industry Co., Ltd.) was slowly added dropwise using a dropping funnel while stirring. Then, after stirring at 90° C. for 5 hours to react, the reaction solution was poured into 1 L of water to precipitate a white precipitate. The precipitate was collected by filtration, washed three times with water, and dried in a vacuum dryer at 80°C for 5 hours to obtain an oxetane compound B-1 having an average of 9 oxetane groups in one molecule (a water-insoluble compound that does not satisfy the general formula (1) and does not have a polyalkylene glycol chain).

[0152] <Synthesis Example 5: Synthesis of Epoxy Compound C-5>

[0153] After dissolving 20.0 g (0.005 mol) of polyethylene glycol (number average molecular weight 4000) (manufactured by Tokyo Chemical Industry Co., Ltd.) and 13.4 g (0.15 mol) of epichlorohydrin (manufactured by Tokyo Chemical Industry Co., Ltd.) in 200 mL of toluene (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.), 6.0 g (0.15 mol) of sodium hydroxide (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) was added, and stirred at 50 degrees for 7 hours to react. After cooling to room temperature, the reaction solution was washed 3 times with distilled water and once with saturated brine, and the organic layer was extracted. The solvent was distilled off using an evaporator, and dried in a vacuum dryer at 80°C for 5 hours to obtain a bifunctional epoxy compound (C-5) (number average molecular weight 4200) having a polyethylene glycol chain.

[0154] In addition, the raw materials used in Examples and Comparative Examples are as follows.

[0155] (A) Resin

[0156] A-4: "Marukalinka" (registered trademark) M (manufactured by Maruzen Petrochemical Co., Ltd.), polyparahydroxystyrene, resin having a weight average molecular weight of 4000 and a basic functional group equivalent of 1000 g / eq or more

[0157] A-5: A product obtained by adding 0.4 equivalent of glycidyl methacrylate to the carboxyl group of a copolymer of methacrylic acid / methyl methacrylate / styrene = 40 / 40 / 30 (mass ratio), weight average molecular weight 43,000, acid value 100 mgKOH / g

[0158] (B) Oxetane compounds

[0159] B-1b: R represented by the general formula (1) having an average of 6 oxetane groups, obtained by separating and collecting the low molecular weight components of OXT-191 (manufactured by Toagosei Co., Ltd.) by GPC 1 For polysilicate, R 2 A water-insoluble compound having an ethyl group and no polyalkylene glycol chain

[0160] B-1c: OXT-191 (manufactured by Toagosei Co., Ltd.), having an average of 12 oxetane groups, and R represented by the general formula (1): 1 For polysilicate, R 2 A water-insoluble compound having an ethyl group and no polyalkylene glycol chain

[0161] B-1d: A polymer component of OXT-191 (manufactured by Toagosei Co., Ltd.) separated by GPC and obtained by separating the polymer component by using the following formula (1): 1 For polysilicate, R 2 A water-insoluble compound having an ethyl group and no polyalkylene glycol chain

[0162] B-2: OXIPA (manufactured by Ube Industries, Ltd.), a water-insoluble compound having no polyalkylene glycol chain

[0163] (C) Epoxy compounds

[0164] C-1: "TEPIC" (registered trademark)-VL (manufactured by Nissan Chemical Co., Ltd.), a trifunctional epoxy compound having no polyalkylene glycol chain, a water-insoluble compound

[0165] C-2: "DENACOL" (registered trademark) EX-171 (manufactured by Nagase ChemteX Co., Ltd.), monofunctional epoxy compound having a polyethylene glycol chain, number average molecular weight 770, water-soluble compound

[0166] C-3: "DENACOL" EX-861 (manufactured by Nagase ChemteX Co., Ltd.), a bifunctional epoxy compound having a polyethylene glycol chain, a number average molecular weight of 1100, a water-soluble compound

[0167] C-4: "DENACOL" EX-850 (manufactured by Nagase ChemteX Co., Ltd.), bifunctional epoxy compound having a polyethylene glycol chain, number average molecular weight 220, water-soluble compound

[0168] C-6: "DENACOL" (registered trademark) EX-931 (manufactured by Nagase ChemteX Co., Ltd.) bifunctional epoxy compound having a polypropylene glycol chain, number average molecular weight 1000, water-insoluble compound

[0169] (D) Photocationic polymerization initiator

[0170] CPI-410S (manufactured by San-apro Co., Ltd.), aromatic sulfonium salt

[0171] (other)

[0172] Photosensitive monomer M-1: trimethylolpropane triacrylate

[0173] Photosensitive monomer M-2: Tetrapropylene glycol dimethacrylate

[0174] Photopolymerization initiator: 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)butanone-1 (manufactured by BASF Corporation)

[0175] Inhibitor: 1,6-Hexanediol-bis[(3,5-di-tert-butyl-4-hydroxyphenyl) propionate]

[0176] Ultraviolet absorber solution: Sudan IV (manufactured by Tokyo Ohka Industry Co., Ltd.), γ-butyrolactone 0.3 mass% solution

[0177] Viscosity modifier: FLOWNON EC121 (manufactured by Kyoei Chemical Co., Ltd.)

[0178] Low softening point glass powder: SiO2 27 mass%, B2O3 31 mass%, ZnO 6 mass%, Li2O 7 mass%, MgO 2 mass%, CaO 2 mass%, BaO 2 mass%, Al2O3 23 mass%, refractive index (ng) 1.56, glass softening temperature 588 ° C, thermal expansion coefficient 70 × 10 -7 (K -1 ), average particle size 2.3 μm

[0179] The water solubility of the (B) oxetane compound and the (C) epoxy compound was determined by placing 1.0 g of each compound in 9.0 g of water and stirring at 20° C. for 1 minute. The presence of insoluble matter was visually observed, and compounds without insoluble matter were considered water-soluble.

[0180] Next, the evaluation method in each of the Examples and Comparative Examples will be described.

[0181] <Viscosity>

[0182] In each of the Examples and Comparative Examples, a finger was pressed on the surface of the dried varnish coating film produced during the formation of the partition walls, and evaluation was performed based on the following evaluation criteria.

[0183] (Evaluation Criteria)

[0184] A: No stickiness was found.

[0185] B: Slight stickiness was observed, but the resin composition did not adhere to the fingers.

[0186] C: Stickiness was observed, and the resin composition adhered to fingers.

[0187] <Crack resistance>

[0188] In each of the Examples and Comparative Examples, the dried varnish coating film produced in the formation of the partition walls and the film after exposure / heating or after exposure were visually observed, and the observation area was 100 cm 2 The total number of cracks that occurred was taken as the total value, and the crack resistance was evaluated according to the following criteria.

[0189] (Evaluation Criteria)

[0190] 4: No cracks were found.

[0191] 3: The number of cracks is 1 or more and less than 25.

[0192] 2: The number of cracks is 25 or more and less than 100.

[0193] 1: The number of cracks is 100 or more.

[0194] <Developability>

[0195] In each of the Examples and Comparative Examples, the developability was evaluated based on the following criteria according to the time until the unexposed portion was completely dissolved during development.

[0196] (Evaluation Criteria)

[0197] 4: The time until the unexposed part is completely dissolved during development is less than 10 minutes.

[0198] 3: The time until the unexposed portion is completely dissolved during development is 10 minutes or more and less than 20 minutes.

[0199] 2: The time until the unexposed portion is completely dissolved during development is 20 minutes or more and less than 30 minutes.

[0200] 1: The time until the unexposed portion is completely dissolved during development is 30 minutes or more.

[0201] <Adhesion>

[0202] In each of Examples and Comparative Examples, the interface between the partition wall and the substrate was visually observed upon completion of development, and the adhesion was evaluated based on the following criteria.

[0203] (Evaluation Criteria)

[0204] A: No peeling was observed.

[0205] B: Partial peeling was observed.

[0206] C: Overall peeling was observed.

[0207] <Resolution>

[0208] For the lattice-shaped partition walls formed in each embodiment and comparative example, the cross-section was exposed by cutting. For each embodiment and comparative examples 1 to 2, among the partition walls corresponding to the mask openings with line widths of 12μm, 15μm, and 20μm, three partition walls were randomly selected from the partition walls corresponding to the smallest opening in which no blockage or residue was found in the pattern. For comparative example 3, three partition walls were randomly selected from the formed partition walls. For the above-selected partition walls, the middle width L5 was measured at a magnification of 200 times using a scanning electron microscope S2400 (manufactured by Hitachi, Ltd.), and the average value was calculated.

[0209] <Aspect Ratio>

[0210] For the grid-shaped partition walls formed in each embodiment and comparative example, for each of the three partition walls whose middle width L5 was measured in the above-mentioned <Resolution> evaluation, the same magnified observation is performed, the height L1 is measured, and the average value is calculated. Based on the average value of the height L1 and the average value of the middle width L5 calculated in the above-mentioned <Resolution> evaluation, the aspect ratio (L1 / L5) is calculated.

[0211] <Relative brightness>

[0212] The scintillator panels obtained in each embodiment and comparative example were aligned and arranged in a one-to-one correspondence between the units and the pixels of the sensor at the center of the sensor surface of the X-ray detector PaxScan 2520V (manufactured by Varex), and the ends of the substrate were fixed with tape to produce a radiation detector. The detector was irradiated with X-rays from an X-ray irradiation device L9181-02 (manufactured by Hamamatsu Photonics Co., Ltd.) under the conditions of a tube voltage of 50 kV and a distance of 30 cm between the X-ray tube and the detector to obtain an image. In the obtained image, the average value of the digital values ​​of 256×256 pixels at the center of the light-emitting position of the scintillator panel was measured as the brightness, and the relative value when the brightness of Comparative Example 2 was set to 100 was calculated as the relative brightness.

[0213] <Example 1>

[0214] <Preparation of varnish>

[0215] 10 g of polyimide A-1 obtained in Synthesis Example 1 as (A) resin, 12 g of oxetane B-1a obtained in Synthesis Example 4 as (B) oxetane compound, and 0.10 g of CPI-410S as a photocationic polymerization initiator were weighed and dissolved in GBL. The amount of GBL added was adjusted so that the solid content concentration was 60% by mass, with components other than GBL as solid components. Then, pressure filtration was performed using a filter with a retention particle size of 1 μm to obtain a photosensitive polyimide varnish.

[0216] <Formation of partition wall>

[0217] A PET film with a length of 125 mm × a width of 125 mm × a thickness of 0.25 mm was used as a substrate. A photosensitive polyimide varnish was applied to the surface of the substrate using a die coater so that the thickness after thermal crosslinking and curing was 350 μm, and dried to obtain a coating film of the photosensitive polyimide varnish.

[0218] Next, the chromium mask having a grid-shaped opening with a pitch of 200 μm and line widths of 12 μm, 15 μm, and 20 μm was used to irradiate the sample at 5000 mJ / cm using an ultra-high pressure mercury lamp. 2The coating film of the photosensitive polyimide varnish was exposed to an exposure amount of . After exposure, a hot air oven was used to perform post-exposure heating at 100° C. for 90 minutes. The exposed / heated coating film was developed in a 0.5 mass % potassium hydroxide aqueous solution at 30° C. to remove the unexposed portion to obtain a grid-like pattern. The obtained grid-like pattern was heated in air at 200° C. for 60 minutes to be thermally crosslinked and cured to form a grid-like partition wall.

[0219] <Fabrication of Scintillator Panel>

[0220] <Formation of Metal Reflective Layer and Inorganic Protective Layer>

[0221] For the formed lattice-shaped partition wall, APC (manufactured by Furuya Metal) which is a silver alloy containing palladium and copper is sputtered as a sputtering target using a commercially available sputtering device to form a metal reflective layer. Sputtering is carried out under the condition that a glass plate is arranged near the partition wall substrate and the metal thickness on the glass plate becomes 300nm. After the metal reflective layer is formed, SiN is formed as an inorganic protective layer in the same vacuum batch. At this time, the inorganic protective layer is formed under the condition that the thickness on the glass substrate becomes 100nm.

[0222] <Formation of Organic Protective Layer>

[0223] For 1 part by mass of the amorphous fluorine-containing resin "CYTOP" (registered trademark) CTL-809M, 1 part by mass of the fluorine-based solvent CT-SOLV180 (AGC (co., Ltd.)) was mixed to prepare a resin solution. The obtained resin solution was vacuum printed on the partition wall formed with the metal reflective layer and the inorganic protective layer, dried at 90°C for 1 hour, and then heated at 190°C for 1 hour to form an organic protective layer. The cross section of the partition wall was exposed using a three-ion beam milling device EMTIC3X (manufactured by LEICA), and the thickness of the organic protective layer on the side of the central part of the height direction of the partition wall measured by field emission scanning electron microscope (FE-SEM) Merlin (manufactured by Zeiss) was 1 μm.

[0224] <Phosphor>

[0225] Commercially available GOS:Tb (gadolinium oxysulfide doped with Tb) phosphor powder was used as it is. The average particle size D50 measured by a particle size distribution analyzer MT3300 (manufactured by Nikkiso Co., Ltd.) was 11 μm.

[0226] <Binder Resin for Phosphor Layer>

[0227] The raw materials used for preparing the binder resin of the phosphor layer are as follows.

[0228] Binder resin: ETHOCEL (registered trademark) 7cp (manufactured by Dow Chemical Co., Ltd.)

[0229] Solvent: benzyl alcohol (manufactured by FUJIFILM Wako Pure Chemical Industries, Ltd.).

[0230] <Formation of Phosphor Layer>

[0231] A phosphor paste was prepared by mixing 10 parts by mass of a phosphor GOS:Tb (gadolinium oxysulfide doped with Tb) with 5 parts by mass of a binder resin solution having a concentration of 10% by mass, wherein a binder resin "ETHOCEL" (registered trademark) 7 cp (manufactured by Dow Chemical) was dissolved in benzyl alcohol (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.). The average particle size D50 of the phosphor measured using a particle size distribution measuring device MT3300 (manufactured by Nikkiso Co., Ltd.) was 11 μm.

[0232] The obtained phosphor paste was vacuum printed on the partitions formed with the metal reflective layer, the inorganic protective layer and the organic protective layer so that the volume fraction of the phosphor was 65%, and dried at 150° C. for 15 minutes to form a phosphor layer and obtain a scintillator panel.

[0233] <Examples 2 to 19, Comparative Examples 1 to 2>

[0234] Partition walls and a scintillator panel were prepared in the same manner as in Example 1, except that the types and addition amounts (parts by mass) of the (A) resin, the (B) oxetane compound, and the (C) epoxy compound were changed as described in Tables 1 and 2.

[0235] <Comparative Example 3>

[0236] 4 parts by mass of the photosensitive monomer M-1, 6 parts by mass of the photosensitive monomer M-2, 24 parts by mass of the photosensitive polymer, 6 parts by mass of the photopolymerization initiator, 0.2 parts by mass of the polymerization inhibitor and 12.8 parts by mass of the ultraviolet absorber solution were dissolved in 38 parts by mass of GBL (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) by heating at 80° C. to obtain a photosensitive resin composition.

[0237] After adding 50 parts by mass of a low-softening-point glass powder to 50 parts by mass of the obtained photosensitive resin composition, the mixture was kneaded using a three-roll kneader to obtain a paste containing the glass powder.

[0238] <Formation of partition wall>

[0239] As a substrate, a soda glass plate with a length of 125 mm × a width of 125 mm × a thickness of 0.7 mm was used. A paste containing glass powder was applied to the surface of the substrate using a die coater so that the thickness after thermal crosslinking and curing was 350 μm, and dried to obtain a coating film of the paste containing glass powder.

[0240] Next, the chromium mask having a grid-shaped opening with a pitch of 200 μm and a line width of 10 μm was used to irradiate the sample at 300 mJ / cm using an ultra-high pressure mercury lamp. 2 The coating film of the paste containing glass powder was exposed to an exposure amount of . The exposed coating film was developed in a 0.5 mass % ethanolamine aqueous solution at 30° C. to remove the unexposed portion to obtain a grid-like pre-firing pattern. The obtained grid-like pre-firing pattern was fired in air at 580° C. for 15 minutes to form a grid-like partition wall mainly composed of glass.

[0241] A scintillator panel was produced in the same manner as in Example 1 using the obtained partition wall substrate.

[0242] Tables 1 and 2 show the results of evaluation by the above-mentioned methods for each of the Examples and Comparative Examples.

[0243] [Table 1]

[0244]

[0245] [Table 2]

[0246]

[0247] Explanation of symbols

[0248] 1 Radiation detector components

[0249] 2Scintillator Panel

[0250] 3 output substrate

[0251] 4 substrates

[0252] 5 Next door

[0253] 6 Phosphor layer

[0254] 7. Diaphragm layer

[0255] 8 Photoelectric conversion layer

[0256] 9Output Layer

[0257] 10 substrates

[0258] 11Metal reflective layer

[0259] 12Organic protective layer

[0260] 13 Phosphor

[0261] 14 Adhesive resin

[0262] 15 Sensors

[0263] 16 Insulation film

[0264] 17 Coil

[0265] 18 resin layer

[0266] 19 substrates

[0267] 20 Insulation film

[0268] 21 Magnetic Materials

[0269] 22 Molding resin

[0270] L1 partition wall height

[0271] L2 The distance between adjacent partition walls

[0272] L3 Bottom width of partition wall

[0273] L4 top width of partition wall

[0274] L5 Middle width of the partition wall

[0275] TInsulation film thickness

[0276] WInsulation film pattern width

Claims

1. A resin composition comprising (A) a resin, (B) an oxetane compound, and a photocationic polymerization initiator, The (A) resin includes a resin having an alkali-soluble group, The (B) oxetane compound includes (B-1) a compound having four or more oxetane groups.

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

3. The resin composition according to claim 1 or 2, wherein The composition further comprises (C) an epoxy compound.

4. The resin composition according to any one of claims 1 to 3, wherein At least one of the (B) oxetane compound and the (C) epoxy compound has a polyalkylene glycol chain.

5. The resin composition according to claim 4, wherein The weight average molecular weight of the polyalkylene glycol chain is 300 to 4000.

6. The resin composition according to any one of claims 1 to 5, wherein The content of the compound (B-1) having four or more oxetane groups is 30 to 160 parts by mass based on 100 parts by mass of the resin (A). 7 . A cured product obtained by curing the resin composition according to claim 1 .

8. A scintillator panel comprising a substrate, partition walls formed on the substrate, and a phosphor layer in a cell partitioned by the partition walls. The partition wall is formed of the cured product according to claim 7.

9. The scintillator panel according to claim 8, wherein: The height L1 of the partition wall is 100 μm or more.

10. The scintillator panel according to claim 8 or 9, wherein: An aspect ratio (L1 / L5) of a height L1 of the partition wall to a width L5 of a middle portion of the partition wall is 5.0 or more. 11 . An inductor comprising an insulating film and a coil, wherein the insulating film is the cured product according to claim 7 .

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