Photosensitive resin composition film, hardened product, scintillator panel using the same, and semiconductor device

Abstract

A photosensitive resin composition film containing (A) a resin, (B) an epoxy compound and / or an oxetane compound, and (C) a photocationic polymerization initiator, wherein a transmittance Tα (%) per unit film thickness at a wavelength of 405 nm of one surface, a transmittance Tβ (%) per unit film thickness at a wavelength of 405 nm of the other surface satisfy the following formula (1), Tα > Tβ (1) and a content rate C10 (mass %) of the (C) photocationic polymerization initiator at a depth of 10% from the surface of which the transmittance per unit film thickness at a wavelength of 405 nm becomes Tα (%) and a content rate C90 (mass %) of the (C) photocationic polymerization initiator at a depth of 90% from the surface satisfy the following formula (2) with respect to the thickness of the photosensitive resin composition film.0.050 ≦ C10 / C90 ≦ 0.85 (2). A photosensitive resin composition film capable of forming a pattern with a high aspect ratio is provided.

Description

Technical Field

[0001] This invention relates to a photosensitive resin composition film, a cured material, a method for manufacturing the same, a scintillator panel using the same, and a semiconductor device. Background Technology

[0002] In medical fields, or industrial applications such as structural inspection or baggage inspection, digital radiation detection devices such as flat panel detectors (FPDs) are used. In indirect conversion FPDs, 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), which emit light upon X-ray irradiation. A sensor (photoelectric conversion layer) with a thin-film transistor (TFT) or charge-coupled device (CCD) converts the light emitted from the scintillator panel into an electrical signal, thus converting the X-ray information into digital image information. However, a problem exists in scintillator panels where light emitted from the radioactive phosphor is scattered within the phosphor layer, resulting in reduced image sharpness.

[0003] Therefore, in order to reduce the effect of light scattering, a method of filling the space divided by the isolation wall with phosphor has been proposed. Furthermore, as a technology to solve the problem of brightness reduction caused by the isolation wall, a scintillator panel has been proposed, comprising a substrate, an isolation wall formed on the substrate, and a scintillator layer with phosphor divided by the isolation wall, wherein the isolation wall comprises one or more compounds (P) selected from the group consisting of polyimide, polyamide, polyamide-imide, and polybenzoxazole (for example, see Patent Document 1).

[0004] On the other hand, when scintillator panels are used in industrial applications such as food or electronic components, during online inspection, the brightness of the scintillator panel tends to decrease over time due to continuous irradiation with high-energy X-rays. To address this issue, a scintillator panel has been proposed comprising a substrate and a scintillator layer containing a phosphor, wherein the scintillator layer contains an adhesive resin having a π-conjugated structure consisting of seven or more atoms, the glass transition point of the adhesive resin is 30°C to 430°C, and the film thickness of the scintillator layer is 50 μm to 800 μm (for example, see Patent Document 2).

[0005] Existing technical documents

[0006] Patent documents

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

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

[0009] The problem that the invention aims to solve

[0010] While these technologies can improve the brightness of scintillator panels, particularly in industrial applications, increasing the phosphor content requires thicker phosphor layers and thinner spacer walls. This background necessitates spacer walls with higher aspect ratios. Furthermore, in applications other than spacer walls in scintillator panels, the use of resin compositions to form patterns with high aspect ratios is also required. However, with existing known resin compositions, it is difficult to form patterns such as spacer walls with the high aspect ratios required in the aforementioned context.

[0011] Therefore, in view of the problems of the prior art, the present invention aims to provide a photosensitive resin composition film capable of forming patterns with a high aspect ratio.

[0012] Technical means to solve the problem

[0013] [1] A photosensitive resin composition film comprising (A) a resin, (B) an epoxy compound and / or an oxetane compound, and (C) a photocationic polymerization initiator, wherein the transmittance Tα (%) of one surface at a wavelength of 405 nm and the transmittance Tβ (%) of the other surface at a wavelength of 405 nm satisfy the following formula (1).

[0014] Tα>Tβ(1)

[0015] The content of the (C) photocationic polymerization initiator at a depth of 10% from the surface of the side where the transmittance per unit film thickness at wavelength 405 nm is Tα (%), relative to the thickness of the photosensitive resin composition film, C10 (mass%), and the content of the (C) photocationic polymerization initiator at a depth of 90% from the surface, satisfy the following formula (2).

[0016] 0.050≦C10 / C90≦0.85(2)

[0017] [2] The photosensitive resin composition film according to [1] has a first film and a second film, the first film comprising a first photosensitive resin composition containing (A) resin, (B) epoxy compound and / or oxetane compound, and (C) photocationic polymerization initiator, the second film comprising a second photosensitive resin composition containing (A) resin, (B) epoxy compound and / or oxetane compound, and (C) photocationic polymerization initiator, wherein the content of (C) photocationic polymerization initiator in the first photosensitive resin composition is different from the content of (C) photocationic polymerization initiator in the second photosensitive resin composition.

[0018] [3] A photosensitive resin composition film according to [1] or [2], wherein the resin (A) contains polyimide, polyamide, polyamide-imide and / or polybenzoxazole.

[0019] [4] A curable material is formed by curing a photosensitive resin composition containing (A) a resin, (B) an epoxy compound and / or an oxetane compound, and (C) a photocationic polymerization initiator, wherein the transmittance T'α (%) of one surface at a wavelength of 405 nm and the transmittance T'β (%) of the other surface at a wavelength of 405 nm satisfy the following formula (3).

[0020] T'α>T'β(3)

[0021] The height H (μm) is 100 μm or more.

[0022] [5] According to the hardener described in [4], the width L0 (μm) of the surface of the hardener on the side where the transmittance per unit thickness at wavelength 405 nm is T'α (%) and the width L100 (μm) of the surface of the hardener on the side where the transmittance per unit thickness at wavelength 405 nm is T'β (%) satisfy the following formula (4).

[0023] L0 / L100≦0.90(4)

[0024] [6] According to the hardener described in [4] or [5], when the width of the surface of the side from which the transmittance per unit thickness at wavelength 405 nm of the hardener is T'α (%) is set to a depth of n% relative to the height H (μm) of the hardener is set to Ln, the following equation (5) is satisfied in the range of n being 0% to 99%.

[0025] {L(n+1)-Ln} / (L100-L0)<0.10(5)

[0026] [7] The hardened material according to any one of [4] to [6], wherein the width L0 (μm) of the surface of the hardened material on the side where the transmittance per unit thickness at wavelength 405 nm is T'α (%), the width L100 (μm) of the side where the transmittance per unit thickness at wavelength 405 nm is T'β (%), and the height H (μm) satisfy the following formula (7).

[0027] H / {(L0+L100) / 2}>16.0(7)

[0028] [8] The hardened product according to any one of [4] to [7], wherein the resin (A) contains polyimide, polyamide, polyamide-imide and / or polybenzoxazole.

[0029] [9] A method for manufacturing a photosensitive resin composition film, comprising: a method for manufacturing a photosensitive resin composition film according to any one of [1] to [3], the method comprising: a step of forming a first film using a first photosensitive resin composition containing (A) resin, (B) epoxy compound and / or oxetane compound, and (C) photocationic polymerization initiator; and a step of forming a second film on the first film using a second photosensitive resin composition containing (A) resin, (B) epoxy compound and / or oxetane compound, and (C) photocationic polymerization initiator, wherein the content of (C) photocationic polymerization initiator in the first photosensitive resin composition is different from the content of (C) photocationic polymerization initiator in the second photosensitive resin composition.

[0030]

[10] A method for manufacturing a hardened material, comprising: an exposure step of exposing a photosensitive resin composition film according to any one of [1] to [3] in an image-like manner; and a development step of removing unexposed portions using a developing solution.

[0031]

[11] A scintillator panel having: a substrate; an isolation wall formed on the substrate; and a phosphor layer located in units divided by the isolation wall, wherein the isolation wall comprises a hardened material according to any one of [4] to [8].

[0032]

[12] A semiconductor device having a semiconductor element and an insulating film, wherein the insulating film comprises a hardened material according to any one of [4] to [8].

[0033] The effects of the invention

[0034] The photosensitive resin composition film according to the present invention can easily form patterns with a high aspect ratio. Attached Figure Description

[0035] [ Figure 1 [Illustrated cross-sectional view] is a schematic cross-sectional view of a component for a radiation detector including the scintillator panel of the present invention.

[0036] [ Figure 2 [Illustrative] is a schematic representation. Figure 1 The enlarged cross-sectional view of the substrate and isolation wall portion of the component for the radiation detector shown.

[0037] [ Figure 3 [Illustrated] is a cross-sectional view schematically showing the structure of an inductor as one embodiment of the semiconductor device of the present invention. Detailed Implementation

[0038] The photosensitive resin composition film of the first aspect of the present invention contains (A) a resin, (B) an epoxy compound and / or an oxetane compound, and (C) a photocationic polymerization initiator. The (A) resin serves to maintain the shape of the photosensitive resin composition film and improve processability. By containing the (B) epoxy compound and / or oxetane compound and the (C) photocationic polymerization initiator, under light irradiation, the (C) photocationic polymerization initiator generates acid, thereby hardening the (B) epoxy compound and / or oxetane compound through cationic polymerization, exhibiting negative photosensitivity that is insoluble in the developer. Regarding the formation of the negative photosensitivity pattern, since the pattern is formed in the photocrosslinked exposure section, a pattern with excellent mechanical properties can be formed. On the other hand, the thicker the negative photosensitive resin composition film, the more the exposure amount attenuates to the bottom, thus the formed pattern tends to become an inverted cone shape. The inverted cone shape pattern has a small contact area with the substrate, and there is a tendency for reduced adhesion to the substrate. Therefore, existing negative-type photosensitive resin composition films struggle to achieve patterns with high aspect ratios. The photosensitive resin composition film of the present invention, by exposing from the surface side with high transmittance and suppressing the attenuation of exposure reaching the bottom, can achieve patterns with high aspect ratios.

[0039] <(A) Resin>

[0040] Examples of resins include acrylic resins, styrene-based resins, phenolic resins, epoxy resins, polyesters, polyvinyl alcohol, polyamides, polyimides, polyamide-imides, and polybenzoxazoles. Two or more of these resins may also be included. Among these, resins selected from polyamides, polyimides, polyamide-imides, and polybenzoxazoles are preferred, as they improve the mechanical properties of the cured product formed by curing the photosensitive resin composition film, resulting in a pattern with a higher aspect ratio and a more conical shape. Resins selected from polyimides and polybenzoxazoles are more preferred.

[0041] The weight-average molecular weight of (A) resin is preferably 1,000 or more and 20,000 or less. Setting the weight-average molecular weight of (A) resin to 1,000 or more improves the film-forming properties of the photosensitive resin composition. The weight-average molecular weight of (A) resin is more preferably 2,000 or more. On the other hand, setting the weight-average molecular weight of (A) resin to 20,000 or less improves the solubility of the photosensitive resin composition film relative to the developer. The weight-average molecular weight of (A) resin is more preferably 10,000 or less. Furthermore, the weight-average molecular weight of (A) resin in this invention is determined using gel permeation chromatography (GPC) and calculated using polystyrene conversion.

[0042] From the viewpoint of cationic polymerization, (A) resin is preferably free of basic functional groups such as amino groups that could potentially hinder cationic polymerization. By being free of such hindering groups, cationic polymerization can be improved, resulting in patterns with a higher aspect ratio. Here, "substantially free" specifically means that the equivalent of basic functional groups is 1,000 g / eq or more.

[0043] (A) The resin preferably has alkali-soluble groups, and the photosensitive resin composition film has moderate solubility relative to the alkaline developer, thus improving the contrast between the exposed and unexposed areas. Examples of alkali-soluble groups include phenolic hydroxyl groups, carboxyl groups, silanol groups, sulfonyl groups, etc. Two or more of these may also be present. Among these, phenolic hydroxyl groups are preferred. Examples of resins containing phenolic hydroxyl groups include polyhydroxyphenyl acrylate, polyhydroxyphenyl methacrylate, poly(p-hydroxystyrene), or polyamides, polyimides, polyamide-imides, polybenzoxazoles, etc., which contain phenolic hydroxyl groups. Two or more of these may also be present.

[0044] Polyamides, polyimides, polyamide-imides, and polybenzoxazoles having phenolic hydroxyl groups are preferably compounds containing diamine residues having phenolic hydroxyl groups. Examples of diamine residues having phenolic hydroxyl groups include: 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'-di-trifluoromethyl-5,5'-dihydroxy-4,4'-diaminobiphenyl, bis(3-amino-4-hydroxyphenyl)fluorene, 2,2'-bis(trifluoromethyl)-5,5'-dihydroxybenzidine, and other aromatic diamines, or compounds derived from compounds obtained by substituting a portion of the hydrogen atom of the aromatic ring or hydrocarbon of these diamines with an alkyl or fluoroalkyl group having 1 to 10 carbon atoms, a halogen atom, or the like. It may also contain two or more of these residues, and may further contain diamine residues that do not have phenolic hydroxyl groups.

[0045] The content of (A) resin in the photosensitive resin composition film of the present invention is preferably 15% to 70% by mass of the solid components. By containing 15% or more of (A) resin, the mechanical and thermal properties of the cured product formed by curing the photosensitive resin composition film can be improved. The content of (A) resin is more preferably 25% by mass or more. On the other hand, by containing 70% or less of (A) resin, developing residues in the photosensitive resin composition film can be suppressed. The content of (A) resin is more preferably 60% or less by mass. Here, "solid components" refers to all components included in the composition except for the solvent.

[0046] <(B) Epoxides and / or oxetanes>

[0047] In this invention, compounds having an epoxy group or an oxetine group, regardless of their molecular weight, are classified as (B) epoxy compounds and / or oxetine compounds.

[0048] Examples of epoxy compounds include aromatic epoxy compounds, alicyclic epoxy compounds, and aliphatic epoxy compounds. They may also contain two or more of these types.

[0049] Examples of aromatic epoxy compounds include glycidyl ethers of monovalent or polyvalent phenols (phenol, bisphenol A, phenolic varnish, and compounds obtained by alkyl epoxide adducts of these) having at least one aromatic ring.

[0050] Examples of alicyclic epoxide compounds include compounds obtained by epoxidizing a compound having at least one cyclohexene or cyclopentene ring using an oxidizing agent (such as 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexane carboxylate).

[0051] Examples of aliphatic epoxide compounds include: polyglycidyl ethers of aliphatic polyols or epoxide adducts (such as 1,4-butanediol diglycidyl ether, 1,6-hexanediol diglycidyl ether), polyglycidyl esters of aliphatic polyacids (such as diglycidyl tetrahydrophthalate), and epoxides of long-chain unsaturated compounds (such as epoxidized soybean oil and epoxidized polybutadiene).

[0052] Examples of oxetane compounds include: 3-methyl-3-hydroxymethyloxetane, 3-ethyl-3-hydroxymethyloxetane, 2-ethylhexyl(3-ethyl-3-oxetanebutylmethyl) ether, 2-hydroxyethyl(3-ethyl-3-oxetanebutylmethyl) ether, 2-hydroxypropyl(3-ethyl-3-oxetanebutylmethyl) ether, 1,4-bis[(3-ethyl-3-oxetanebutylmethoxy)methyl]benzene, oxetanebutylsilsesquioxane, phenolic varnish oxetane, and OXT-191 (trade name, manufactured by Toa Gosei Corporation). Two or more of these compounds may also be contained.

[0053] Oxycyclobutane compounds are preferably those having two or more oxycyclobutyl groups, as they exhibit excellent curing properties and can form patterns with a higher aspect ratio. More preferably, oxycyclobutane compounds have four or more oxycyclobutyl groups, and even more preferably, they have seven or more oxycyclobutyl groups. Examples of oxycyclobutane compounds having four or more oxycyclobutyl groups include: oxycyclobutylsilsesquioxane, phenolic varnish oxycyclobutane, and OXT-191 (trade name, manufactured by Toa Gosei Corporation). On the other hand, oxycyclobutane compounds are preferably those having twenty or fewer oxycyclobutyl groups, which can suppress the formation of cracks during pattern processing. Examples of oxycyclobutane compounds having seven or more and twenty or fewer oxycyclobutyl groups include OXT-191 (trade name, manufactured by Toa Gosei Corporation).

[0054] The oxocyclic butyl compound is preferably having the structure represented by the following general formula (1).

[0055] [Chemistry 1]

[0056]

[0057] In the general formula (1), R 1 Represents an n-valent group with a siloxane bond. R 2 It represents 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.

[0058] R 1It contains siloxane bonds. These siloxane bonds are hydrolyzed by alkaline developing solutions, thus the photosensitive resin composition film has moderate solubility relative to alkaline developing solutions, thereby improving the contrast between exposed and unexposed areas. As R... 1 Preferably, it is a silicate or polysilicate.

[0059] As a component of R 2 The organic group is preferably an alkyl group such as methyl or ethyl. The alkyl group may also be substituted with halogens such as fluorine; in the case of substituents, perfluoroalkyl groups such as trifluoromethyl or pentafluoroethyl are preferred. Through R... 2 It is a monovalent organic group consisting of hydrogen atoms or carbon atoms from 1 to 6. The photosensitive resin composition film has excellent solubility relative to alkaline developing solutions, which can improve developing properties.

[0060] Examples of oxetane compounds having the structure represented by the general formula (1) include oxetane, oxetane-butylsilsesquioxane, OXT-191 (trade name, manufactured by Toa Synthetic Co., Ltd.), etc.

[0061] The oxetane compound and epoxy compound preferably have polyalkylene glycol chains. The presence of highly flexible polyalkylene glycol chains helps suppress the formation of cracks in the dried photosensitive resin composition film or cured product. When containing two or more oxetane compounds and epoxy compounds, it is preferable that at least a portion of them have polyalkylene glycol chains.

[0062] From the viewpoint of compatibility with resin (A), the number average molecular weight of the oxetane compound and / or epoxy compound having polyalkylene glycol chains is preferably 300 to 4,000. Setting the number average molecular weight to 300 or higher further improves compatibility and flexibility with resin (A), and further suppresses crack formation. On the other hand, setting the number average molecular weight to 4,000 or lower moderately suppresses the epoxy / oxetane equivalent, further improving curability and forming patterns with a higher aspect ratio. The chemical structure of the compound having polyalkylene glycol chains can be analyzed using 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 polyalkylene glycol chains can be determined by gel permeation chromatography (GPC).

[0063] From a hydrophilicity point of view, the number of carbon atoms in the repeating unit of the polyalkylene glycol chain is preferably 2 to 6, more preferably 2. By setting the number of carbon atoms in the alkylene group within this range, the solubility relative to the alkaline developer is excellent, and the developability of the photosensitive resin composition film can be improved.

[0064] The number of epoxy groups and oxetyl groups in the oxetane compound and / or epoxy compound having a polyalkylene glycol chain is preferably 2 or more, which can further improve the curability of the photosensitive resin composition film and form a pattern with a higher aspect ratio. Examples of the oxetane compound include bis-[(3-ethyloxetane-3-yl)methoxy]polyethylene glycol. Examples of the epoxy compound include polyethylene glycol diglycidyl ether and polypropylene glycol diglycidyl ether.

[0065] From the viewpoint of solubility in aqueous developing solutions during development, oxetane compounds and epoxy compounds are preferably water-soluble compounds. Specifically, at least one of the oxetane compound and / or epoxy compound is preferably a water-soluble compound that dissolves in 900 parts by weight of water at 20°C for less than 1 minute relative to 100 parts by weight of the compound. Examples of water-soluble oxetane compounds and / or epoxy compounds include, for example: 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.

[0066] Relative to 100 parts by weight of resin (A), the total content of (B) oxobutane compound and epoxy compound in the photosensitive resin composition film of the present invention is preferably 50 to 170 parts by weight. By setting this total content to 50 parts by weight or more, cracking of the photosensitive resin composition film can be suppressed. More preferably, this total content is 70 parts by weight or more. On the other hand, by setting this total content to 170 parts by weight or less, the tackiness of the photosensitive resin composition film can be suppressed. More preferably, this total content is 140 parts by weight or less.

[0067] <(C) Photocationic Polymerization Initiator>

[0068] (C) Photocationic polymerization initiators generate acid through photopolymerization, leading to cationic polymerization. Examples of (C) photocationic polymerization initiators include aromatic sulfonates, aromatic sulfonates, and aromatic borates. Two or more of these may also be included. Among these, aromatic sulfonates are preferred. Specifically, examples include diphenyl[(phenylmercapto)phenyl]sulfonium-hexafluorophosphate, diphenyl[4-(phenylthio)phenyl]sulfonium-hexafluoroantimonate (V), diphenyl[4-(phenylmercapto)phenyl]sulfonium-trifluorotris(pentafluoroethane-1-yl)phosphate, diphenyl[(phenylmercapto)phenyl]sulfonium-tetra(pentafluorophenyl)borate, CPI-310B, CPI-310FG, CPI-410S, and CPI-410B (trade names, all manufactured by San-Apro (stock)). Among these, aromatic sulfonates such as CPI-410S, diphenyl[(phenylmercapto)phenyl]sulfonium=hexafluorophosphate, and diphenyl[4-(phenylmercapto)phenyl]sulfonium=trifluoridetri(pentafluoroethane-1-yl)phosphate are preferred in terms of being less prone to coloring, easier to maintain high transmittance, and having high cationic polymerization reactivity that allows for the formation of patterns with higher aspect ratios.

[0069] Relative to 100 parts by weight of resin (A), the content of photocationic polymerization initiator (C) in the photosensitive resin composition film of the present invention is preferably 0.1 parts by weight or more, which can further improve the curability of the photosensitive resin composition film and form a pattern with a higher aspect ratio. On the other hand, relative to 100 parts by weight of resin (A), the content of photocationic polymerization initiator (C) is preferably 10 parts by weight or less, which can improve the stability of the photosensitive resin composition film.

[0070] <Other Ingredients>

[0071] The photosensitive resin composition film of the present invention may also contain cationic polymeric compounds other than those in (B) epoxy compound and / or oxetane compound. Examples of cationic polymeric compounds other than (B) epoxy compound and / or oxetane compound include: vinyl unsaturated compounds, bicyclic orthoesters, spirocyclic orthocarbonates, spirocyclic orthoesters, etc. Two or more of these may also be contained.

[0072] Examples of vinyl unsaturated compounds include: aliphatic monovinyl ethers, aromatic monovinyl ethers, polyfunctional vinyl ethers, styrene derivatives, 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 styrene derivatives include: styrene, α-methylstyrene, p-methoxystyrene, and tert-butoxystyrene. Examples of cationic polymerizable nitrogen-containing monomers include: N-vinylcarbazole and N-vinylpyrrolidone.

[0073] Examples of 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.

[0074] Examples of spirocyclic orthocarbonates include 1,5,7,11-tetraoxaspiro[5.5]undecane and 3,9-dibenzyl-1,5,7,11-tetraoxaspiro[5.5]undecane.

[0075] Examples of 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, etc.

[0076] The photosensitive resin composition film of the present invention may also contain additives such as sensitizers and surfactants, or inorganic particles, as needed.

[0077] <Photosensitive Resin Composition Film>

[0078] Regarding the photosensitive resin composition film of the present invention, the transmittance Tα (%) of one surface at a wavelength of 405 nm and the transmittance Tβ (%) of the other surface at a wavelength of 405 nm satisfy the following formula (1), that is, the transmittance of one surface is different from that of the other surface. Here, the transmittance of the surface with higher transmittance per unit thickness at a wavelength of 405 nm is defined as Tα, and the transmittance of the surface with lower transmittance per unit thickness at a wavelength of 405 nm is defined as Tβ. Here, in the present invention, "transmittance per unit thickness" is defined as the transmittance per 20 μm. That is, the transmittance per unit thickness of the surface is the transmittance measured in the width direction near one surface and near the other surface of a 20 μm wide sample cut from the photosensitive resin composition film.

[0079] Tα>Tβ(1).

[0080] As described above, photosensitive resin composition films with negative photosensitivity tend to exhibit a tendency to attenuate the amount of light reaching the bottom as the film thickness increases. In this invention, by exposing the film from the surface on the side with a transmittance per unit film thickness of 405 nm (hereinafter sometimes referred to as the "high transmittance side surface") to the other surface (the bottom) (hereinafter sometimes referred to as the "low transmittance side surface"), a high exposure level can be maintained, thereby forming a pattern with a high aspect ratio. Here, in this invention, the transmittance of ultraviolet light is defined as the transmittance of ultraviolet light at a wavelength of 405 nm, which is a representative wavelength, generally used for exposure. The difference between Tα (%) and Tβ (%) is preferably 0.5% or more, more preferably 2% or more.

[0081] Examples of photosensitive resin composition films that satisfy formula (1) include those with transmittance that changes continuously from one surface to the other, or those with transmittance that changes in stages. Among these, the form with continuously changing transmittance is more preferred from the viewpoint of making the shape of the cured material smooth.

[0082] Here, regarding the determination of transmittance Tα (%) and transmittance Tβ (%), three randomly selected locations from the photosensitive resin composition film were cut with a width of 20 μm perpendicular to the surface, yielding samples with a thickness of 20 μm. For these samples, the transmittance in the thickness direction was measured near one surface and another surface of the varnish coating film using a microspectrophotometer, and the average value was calculated. From this, the transmittance Tα (%) and transmittance Tβ (%) could be determined.

[0083] As a method to make the transmittance Tα (%) and transmittance Tβ (%) satisfy formula (1), for example, a method of varying the concentration of the compound that absorbs light with a wavelength of 405 nm along the film thickness direction can be listed. More specifically, preferred forms described later can be listed, such as a photosensitive resin composition film that satisfies formula (2) described later.

[0084] The photosensitive resin composition film of the present invention preferably has a content of (C) photocationic polymerization initiator C10 (mass%) at a depth of 10% from the high transmittance side surface and a content of (C) photocationic polymerization initiator C90 (mass%) at a depth of 90% from the high transmittance side surface, which satisfies the following formula (2).

[0085] 0.050≦C10 / C90≦0.85(2).

[0086] Here, C10 is an indicator of the content of (C) photocationic polymerization initiator on the high-transmittance side surface, and C90 is an indicator of the content of (C) photocationic polymerization initiator on the low-transmittance side surface. (C) photocationic polymerization initiators readily absorb light at a wavelength of 405 nm; therefore, the smaller C10 is relative to C90, the larger Tα is relative to Tβ, resulting in patterns with a higher aspect ratio. Furthermore, the higher the content of (C) photocationic polymerization initiator, the higher the sensitivity and the coarser the pattern; therefore, by increasing C90 relative to C10, it is easier to form a conical pattern. Therefore, C10 / C90 is preferably 0.85 or less. On the other hand, by moderately increasing C10, the curability of the photosensitive resin composition film can be further improved, resulting in patterns with a higher aspect ratio. C10 / C90 is preferably 0.050 or more, more preferably 0.20 or more, more preferably 0.30 or more, and even more preferably 0.45 or more.

[0087] Examples of forms that satisfy equation (2) include those where the content of the photocationic polymerization initiator (C) changes continuously from one surface to the other, or those where the content of the photocationic polymerization initiator (C) changes in stages. From the viewpoint of making the shape of the hardened material smooth, a form where the content changes continuously is more preferred.

[0088] Here, C10 and C90 can be determined by the following method. First, for a 10 cm × 10 cm photosensitive resin composition film, 100 mg portions of each sample are collected from the high-transmittance side surface and the low-transmittance side surface, respectively, at depths of approximately 10% and 90% from the high-transmittance side surface, using a file. The chemical structure of the (C) photocationic polymerization initiator contained in the sample is determined by combining NMR, FT-IR, and HPLC / MS. After adding 0.5 mL of acetonitrile to each 10 mg sample, the mixture is sonicated for 60 minutes and then centrifuged at 20,000 g for 15 minutes. A portion of the supernatant after centrifugation is transferred to a small brown glass vial for quantitative analysis of the anionic components derived from the (C) photocationic polymerization initiator by HPLC. The total content of anions and cations derived from the (C) photocationic polymerization initiator is calculated based on the content of the anionic components, from which C10 and C90 can be determined. Furthermore, given that the structure of the (C) photocationic polymerization initiator is known, the content of the (C) photocationic polymerization initiator can be calculated based on the known structure and the quantitative analysis results obtained using HPLC.

[0089] As a method to make C10 and C90 satisfy formula (2), for example, it is preferable to make the photosensitive resin composition film a laminate of multiple photosensitive resin composition films with different contents of (C) photocationic polymerization initiator. More specifically, methods for manufacturing photosensitive resin composition films by preferred manufacturing methods described later can be listed.

[0090] The photosensitive resin composition film of the present invention preferably comprises a first film and a second film. The first film comprises a first photosensitive resin composition containing (A) resin, (B) epoxy compound and / or oxetane compound, and (C) photocationic polymerization initiator. The second film comprises a second photosensitive resin composition containing (A) resin, (B) epoxy compound and / or oxetane compound, and (C) photocationic polymerization initiator. The content of (C) photocationic polymerization initiator in the first photosensitive resin composition differs from the content of (C) photocationic polymerization initiator in the second photosensitive resin composition. By having a first film and a second film with different contents of (C) photocationic polymerization initiator, the content of (C) photocationic polymerization initiator can be easily adjusted to a desired range. In both the first and second membranes, the ratio of the content of (C) photocationic polymerization initiator in the membrane with a lower content to the content of (C) photocationic polymerization initiator in the membrane with a higher content is preferably 0.050 or more, more preferably 0.20 or more, further preferably 0.30 or more, and even more preferably 0.45 or more. On the other hand, this ratio is preferably 0.85 or less, more preferably 0.75 or less.

[0091] The photosensitive resin composition film of the present invention may also have a protective film on its surface to protect the surface from pollutants such as dust or dirt in the atmosphere. Examples of such protective films include polyolefin films and polyester films. Preferably, the protective film has low adhesion to the photosensitive resin composition film.

[0092] From the viewpoint of forming patterns with a higher aspect ratio, the thickness of the photosensitive resin composition film of the present invention is preferably 100 μm or more. On the other hand, from the viewpoint of suppressing film thickness deviation, the thickness of the photosensitive resin composition film of the present invention is preferably 1,000 μm or less.

[0093] Next, a method for manufacturing the photosensitive resin composition film of the present invention will be described. The photosensitive resin composition film of the present invention can be obtained, for example, by mixing (A) resin, (B) epoxy compound and / or oxetane compound, (C) photocationic polymerization initiator, and solvents and other components as needed to prepare a photosensitive resin composition liquid (varnish), coating it on a support, and then drying it as needed.

[0094] As a solvent, solvents that dissolve the components constituting the photosensitive resin composition are preferred, such as propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, 3-methyl-3-methoxybutyl acetate, acetone, 3-methyl-3-methoxybutanol, N-methyl-2-pyrrolidone, N,N-dimethylacetamide, γ-butyrolactone, etc. Two or more of these may also be used.

[0095] Filtration can also be performed using filter paper or a filter before applying the varnish. As a filtration method, pressure filtration is preferred, and as a filter, a filter that retains particles with a diameter of 0.4 μm to 50 μm is preferred.

[0096] Examples of supports include polyethylene terephthalate (PET) films, polyphenylene sulfide (PPS) films, and polyimide films. The thickness of the support is preferably 10 μm to 100 μm. The support can also undergo surface treatment to adjust its adhesion or peelability to the photosensitive resin composition film. Examples of surface treatment agents include silicones, silane coupling agents, aluminum chelating agents, and polyurea.

[0097] Methods for applying varnish to a support include, for example, screen printing, rotary coating using a rotator, spray coating, and coating methods using coating machines such as bar coaters, roller coaters, die coaters, scraper coaters, calender coaters, meniscus coaters, gravure coaters, and slot die coaters.

[0098] Examples of drying devices include hot air ovens, heating plates, and infrared ovens. The drying temperature and time are preferably set within a range suitable for solvent evaporation and for the photosensitive resin composition film to reach an uncured or semi-cured state. Specifically, the drying temperature is preferably 50°C to 150°C, and the drying time is preferably 1 minute to several hours. The drying temperature can also be increased in stages; for example, drying can be performed at 70°C, 80°C, and 90°C for 1 minute to several tens of minutes respectively.

[0099] In this invention, it is preferable to stack multiple photosensitive resin composition films with different contents of (C) photocationic polymerization initiator, which can easily make C10 and C90 satisfy the stated formula (2). More specifically, it is preferable to have the following steps: forming a first film using a first photosensitive resin composition containing (A) resin, (B) epoxy compound and / or oxetane compound, and (C) photocationic polymerization initiator; and forming a second film on the first film using a second photosensitive resin composition containing (A) resin, (B) epoxy compound and / or oxetane compound, and (C) photocationic polymerization initiator, wherein the content of (C) photocationic polymerization initiator in the first photosensitive resin composition is different from the content of (C) photocationic polymerization initiator in the second photosensitive resin composition. The ratio of the content of (C) photocationic polymerization initiator in the first photosensitive resin composition to the content of (C) photocationic polymerization initiator in the second photosensitive resin composition is preferably 0.050 or more, more preferably 0.20 or more, more preferably 0.30 or more, and even more preferably 0.45 or more. On the other hand, the ratio is preferably 0.85 or less, more preferably 0.75 or less.

[0100] As a method for forming a second film on a first film, examples include coating a second photosensitive resin composition liquid (varnish) onto the first film after its formation and then drying it; or hot-pressing the first and second films separately. When the photosensitive resin composition film is formed using the former method, the concentration of the (C) photocationic polymerization initiator continuously changes around the interface due to the diffusion of the components at the interface between the first and second films. Therefore, when the photosensitive resin composition film is exposed and developed to form a pattern, step differences at the interface can be suppressed. The pattern formed by the photosensitive resin composition film suppresses interface step differences, thus, for example, when used as an insulating wall for a scintillator panel described later, reflectivity can be improved, further increasing the brightness of the scintillator panel. Furthermore, when used as an insulating layer for a semiconductor device or electronic component described later, the tightness of contact with coil wiring can be improved, and the temperature cycling durability of the semiconductor device or electronic component can be improved.

[0101] In the former method, the drying time of the first film is preferably about 30 minutes to 1.5 hours. The drying time of the second film is preferably longer. By extending the drying time of the second film, the (C) photocationic polymerization initiator diffuses further at the interface between the first and second films, thus further suppressing the step difference at the interface. The drying time of the second film is preferably 1 hour or more, more preferably 2 hours or more, and even more preferably 3 hours or more. On the other hand, from the viewpoint of improving the development speed, the drying time of the second film is preferably 6 hours or less, more preferably 5 hours or less.

[0102] <Hardened material>

[0103] The second embodiment of the present invention is a cured product obtained by curing a photosensitive resin composition containing (A) resin, (B) epoxy compound and / or oxetane compound, and (C) photocationic polymerization initiator. Preferably, the photosensitive resin composition is a composition constituting the photosensitive resin composition film of the present invention.

[0104] The cross-sectional shape of the hardened material of the present invention is preferably trapezoidal.

[0105] In the cured material of the present invention, the transmittance T'α (%) of one surface at a wavelength of 405 nm and the transmittance T'β (%) of the other surface at a wavelength of 405 nm satisfy the following formula (3). Here, the transmittance of the surface with higher transmittance per unit thickness at a wavelength of 405 nm is defined as T'α, and the transmittance of the surface with lower transmittance per unit thickness at a wavelength of 405 nm is defined as T'β. Furthermore, sometimes the surface with transmittance of T'α (%) at a wavelength of 405 nm is described as the "high transmittance side surface," and the surface with transmittance of T'β (%) at a wavelength of 405 nm is described as the "low transmittance side surface." Here, in the present invention, "transmittance per unit thickness" is defined as the transmittance per 20 μm. That is, the transmittance per unit film thickness of the surface is the transmittance measured in the width direction near one surface and the other surface of a 20 μm wide sample cut from the hardened material.

[0106] T'α>T'β(3).

[0107] Under normal curing conditions, the transmittance relationship between the two surfaces before curing is consistent with that after curing. Therefore, if the cured material satisfies equation (3), it satisfies equation (1) in the state before curing. Thus, when a pattern is formed by exposing and developing a photosensitive resin composition film, a high exposure level can be maintained from the high transmittance side surface to the bottom, thereby forming a pattern with a high aspect ratio. Here, in this invention, the transmittance of ultraviolet light is defined as the transmittance of ultraviolet light at a wavelength of 405 nm, which is a representative wavelength, from ultraviolet light generally used for exposure. The difference between Tα' (%) and T'β (%) is preferably 0.5% or more, more preferably 2.0% or more.

[0108] Examples of forms that satisfy equation (3) include those where the transmittance changes continuously from one surface to the other, or those where the transmittance changes in stages. Among these, the form where the transmittance changes continuously is more preferred from the viewpoint of making the shape of the hardened material smooth.

[0109] Here, the transmittance T'α (%) and transmittance T'β (%) can be measured in the same way as the transmittance Tα (%) and transmittance Tβ (%) of the photosensitive resin composition film.

[0110] As a method for making T'α (%) and T'β (%) satisfy the formula (3), a preferred method is to form a hardened material from a photosensitive resin composition film of the preferred form of the present invention.

[0111] From the viewpoint of producing a hardened object with a higher aspect ratio, the height H (μm) of the hardened object of the present invention is preferably 100 μm or more.

[0112] Furthermore, the hardened material of the present invention preferably has a width L0 (μm) of the high transmittance side surface and a width L100 (μm) of the low transmittance side surface that satisfies the following formula (4). L0 / L100 is less than 1, which means that the cross-sectional shape of the hardened material is a positive cone shape.

[0113] L0 / L100≦0.90(4)

[0114] The L0 / L100 ratio is preferably 0.70 or higher, and more preferably 0.75 or higher. On the other hand, the L0 / L100 ratio is more preferably 0.85 or lower.

[0115] The preferred hardener of the present invention is the surface of the side where the transmittance per unit thickness at a wavelength of 405 nm is T'α (%), and the width of the hardener at a depth of n% relative to the height H (μm) of the hardener is set as Ln, satisfying the following equation (5) in all ranges from 0% to 99% of n. The smaller the maximum value of the absolute value of {L(n+1)-Ln} / (L100-L0) in the range of n from 0% to 99% (hereinafter, sometimes referred to as "maximum rate of change of width"), the smaller the variation of the width of the hardener in the depth direction, which means that the step difference at the interface of the hardener is further suppressed.

[0116] {L(n+1)-Ln} / (L100-L0)<0.10(5)

[0117] Furthermore, for the same reason, the hardened material of the present invention preferably satisfies the following formula (6).

[0118] {L(n+1)-Ln} / (L100-L0)>-0.10(6)

[0119] The maximum rate of change of width is more preferably less than 0.060, and even more preferably less than 0.040.

[0120] The hardened material of the present invention preferably has a width L0 (μm) of the high transmittance side surface, a width L100 (μm) of the low transmittance side surface, and a height H (μm) that satisfy the following formula (7). H / {(L0+L100) / 2} represents the aspect ratio of the hardened material of the present invention, and the larger the aspect ratio, the larger the aspect ratio.

[0121] H / {(L0+L100) / 2}>16.0 (7).

[0122] The aspect ratio is more preferably 18.0 or more, more preferably greater than 18.0, more preferably 19.5 or more, and even more preferably greater than 19.5.

[0123] Here, the width L0 (μm) of the high transmittance side surface, the width L100 (μm) of the low transmittance side surface, and the height H (μm) can be determined as follows: For three randomly selected parts from the hardened material, cut a section perpendicular to the surface and perpendicular to the long side, or grind it using a grinding device such as a cross-section polisher. For the exposed section, observe it under a scanning electron microscope, measure L0, L100, and H respectively, and calculate their average values.

[0124] As a method for making the width L0 of the high transmittance side surface and the width L100 of the low transmittance side surface satisfy the above formula (4), for example, it is preferred to form a hardened material from a photosensitive resin composition film of the preferred form of the present invention.

[0125] As a method for satisfying the equations (5) and (6) at a depth of n% relative to the height H (μm) of the hardened material from the surface on the side that becomes T'α (%), a preferred method is, for example, to form a hardened material from a photosensitive resin composition film of the preferred form of the present invention obtained by the preferred manufacturing method.

[0126] As a method for satisfying the formula (7) for the width L0 of the high transmittance side surface, the width L100 of the low transmittance side surface, and the height H, a preferred method is, for example, the method of forming a hardened material from a photosensitive resin composition film of the preferred form of the present invention.

[0127] The hardened material of the present invention can be preferably used, for example, as an insulating film for semiconductor devices, a scintillator panel isolation wall, electronic components, etc., as described later.

[0128] <Method for manufacturing hardened material>

[0129] Next, the method for manufacturing the cured product of the present invention will be described. The cured product of the present invention is obtained, for example, by patterning and then curing a photosensitive resin composition containing (A) resin, (B) epoxy compound and / or oxetane compound, (C) photocationic polymerization initiator, and solvents or other components as needed.

[0130] As a curing method, irradiation (exposure) with chemical rays is preferred. If necessary, further heating can be performed after exposure. Heating allows for curing via a thermal crosslinking reaction and a cationic polymerization reaction with a (C) photocationic polymerization initiator.

[0131] The preferred method for pattern processing includes: an exposure step, in which the photosensitive resin composition film of the present invention is exposed in an image-like manner; and a development step, in which unexposed portions are removed using a developing solution.

[0132] First, the photosensitive resin composition film is exposed in an image-like manner. Specifically, in the exposure step, the photosensitive resin composition film is exposed to chemical rays through a mask having the desired pattern. Examples of chemical rays used in the exposure include ultraviolet light, visible light, electron beams, and X-rays. In this invention, i-rays (365 nm), h-rays (405 nm), or g-rays (436 nm) from a mercury lamp are preferably used.

[0133] Next, in the developing process, the unexposed areas are removed using a developing solution.

[0134] Development can be performed by spraying the developer onto the surface of the photosensitive resin composition film, applying the developer to the surface of the photosensitive resin composition film, immersing the photosensitive resin composition film in the developer, or immersing and applying ultrasound. The development conditions, such as the development time or steps and the temperature of the developer, are only required to remove the exposed areas and form a pattern. Examples of developers include those described in International Publication No. 2021 / 200327.

[0135] Preferably, rinsing with water is performed after development. Alternatively, alcohols such as ethanol and isopropyl alcohol, esters such as ethyl lactate and propylene glycol monomethyl ether acetate, can be added to the water for rinsing.

[0136] Alternatively, baking may be performed before development, if necessary. This can sometimes improve the resolution of the developed pattern and increase the allowable range of development conditions. The baking temperature is preferably in the range of 50°C to 180°C, more preferably in the range of 60°C to 120°C. The baking time is preferably from 5 seconds to several hours.

[0137] After patterning, unreacted (B) epoxy compounds and / or oxetane compounds or (C) photocationic polymerization initiators remain in the photosensitive resin composition film. Therefore, these can sometimes undergo thermal decomposition during the thermal crosslinking reaction described later, generating gases. To avoid this, it is preferable to irradiate the entire surface of the patterned photosensitive resin composition film with the exposure light, generating acid from the (C) photocationic polymerization initiator. By proceeding in this manner, the unreacted (B) epoxy compounds and / or oxetane compounds react during the thermal crosslinking reaction described later, suppressing the generation of gases that are a source of thermal decomposition.

[0138] Preferably, after development, a thermal crosslinking reaction is performed at a temperature of 120°C to 300°C, thereby curing the photosensitive resin composition to form a cured product. Crosslinking improves the heat resistance and chemical resistance of the obtained cured product. The heat treatment method can be selected from: a method of selecting a temperature and gradually increasing the temperature, or a method of continuously increasing the temperature within a certain range while performing the process for 5 minutes to 5 hours.

[0139] <Scintillator Panel>

[0140] The scintillator panel of the present invention comprises: a substrate; isolation walls formed on the substrate; and phosphor layers filled into units defined by the isolation walls, the isolation walls comprising the hardened material of the present invention. Preferably, the isolation walls are arranged in a direction substantially perpendicular to the substrate to form the units. The phosphor layers present in each unit are divided by the isolation walls. According to the hardened material of the present invention, isolation walls with a high aspect ratio can be formed. The high aspect ratio of the isolation walls allows for an increase in the amount of phosphor filled into the units, thereby improving the brightness of the scintillator panel.

[0141] Hereinafter, embodiments of the scintillator panel of the present invention will be described using the accompanying drawings. Furthermore, the drawings are schematic. Additionally, the present invention is not limited to the embodiments described below.

[0142] Figure 1This is a schematic cross-sectional view of a radiation detector component incorporating the scintillator panel of the present invention. The radiation detector component 1 includes a scintillator panel 2 and an output substrate 3. The scintillator panel 2 includes a substrate 4, an isolation wall 5, and phosphor layers 6 within units divided by the isolation wall 5. A metal reflective layer 11 is formed on the surface of the isolation wall 5, and an organic protective layer 12 is disposed on its surface. The phosphor layer 6 includes a phosphor 13 and an adhesive resin 14. The output substrate 3 has an output layer 9 and a photoelectric conversion layer 8 with a photodiode sequentially disposed on a substrate 10. A diaphragm layer 7 may also be disposed on the photoelectric conversion layer 8. The light-emitting surface of the scintillator panel 2 and the photoelectric conversion layer 8 of the output substrate 3 are preferably bonded or closely connected via the diaphragm layer 7. Light emitted from the phosphor layer 6 reaches the photoelectric conversion layer 8, undergoes photoelectric conversion, and is output. The following will describe each component separately.

[0143] <Substrate>

[0144] The material constituting the substrate is preferably radiolucent. Examples of materials constituting the substrate include those described in International Publication No. 2021 / 200327. Among these, polymeric materials with high radiolucentness and high surface smoothness are preferred. Examples of preferred polymeric materials include polyesters such as polyethylene terephthalate and polyethylene naphthalate, polyamides, and polyimides.

[0145] In the case of a substrate containing a polymer material, the thickness of the substrate is preferably 3.0 mm or less.

[0146] <Isolation Wall>

[0147] Isolation walls are provided to form at least divided spaces (units). Therefore, in the scintillator panel, the size and spacing of the pixels of the photoelectric conversion elements arranged in a grid pattern are made consistent with the size and spacing of the units of the scintillator panel, thereby enabling each pixel of the photoelectric conversion element to correspond to each unit of the scintillator panel. As a result, high-resolution images can be obtained.

[0148] The isolation wall is preferably a hardened material containing the present invention. By including an isolation wall with a high aspect ratio containing the hardened material of the present invention, the amount of phosphor filling in the cell can be increased, thereby improving brightness.

[0149] Figure 2 It is a schematic representation Figure 1 The diagram shows an enlarged cross-sectional view of the substrate and isolation wall portion of a component used in a radiation detector. The vertical direction is... Figure 1Conversely, the isolation wall 5 on the substrate 4 has a trapezoidal cross-sectional shape with a height H', a top width L'0, and a bottom width L'100, arranged at intervals P. Here, the height H', top width L'0, and bottom width L'100 of the isolation wall correspond to the height H, the width L0 of the high transmittance side surface, and the width L100 of the low transmittance side surface of the hardened material of the present invention, respectively.

[0150] The height H' of the isolation wall is preferably 100 μm or more. By setting H' to 100 μm or more, the phosphor filling amount can be increased, further improving the brightness. H' is more preferably 200 μm or more. On the other hand, the height H' of the isolation wall is preferably 3,000 μm or less. By setting H' to 3,000 μm or less, the absorption of emitted light by the phosphor itself can be suppressed, further improving the brightness. H' is more preferably 1,000 μm or less.

[0151] The spacing P between adjacent isolation walls is preferably 40 μm or more, more preferably 1,000 μm or less. The bottom width L'100 of the isolation wall is preferably 3 μm or more, and more preferably 150 μm or less. The top width L'0 of the isolation wall 5 is preferably 3 μm or more, and more preferably 30 μm or less.

[0152] The aspect ratio (H' / ((L'0+L'100) / 2)) expressed as the ratio of the height H' of the isolation wall to the average of the top width L'0 and bottom width L'100 of the isolation wall is preferably 16 or more, more preferably greater than 16.0, which can increase the amount of phosphor filling and further improve the brightness. The aspect ratio is more preferably 18 or more, more preferably greater than 18.0, and even more preferably 19.5 or more, and even more preferably greater than 19.5. On the other hand, the aspect ratio is preferably 100 or less, which can improve the strength of the isolation wall. The aspect ratio is more preferably 50 or less.

[0153] The height H' of the partition wall, the spacing P between adjacent partition walls, the bottom width L'100, and the top width L'0 can be measured as follows: A scanning electron microscope is used to observe the cross-section exposed by cutting it in a direction perpendicular to the substrate and perpendicular to its long side, or by using a polishing device such as a cross-section polisher. Here, the width of the partition wall at the contact point with the substrate is set as L'100. Additionally, the width of the topmost part of the partition wall is set as L'0. The lengths H', L'0, L'100, and P are calculated by averaging the measurements of the partition walls at three randomly selected locations.

[0154] As a method for ensuring that the aspect ratio of the isolation wall is within the aforementioned range, a method of forming the isolation wall from the photosensitive resin composition film of the present invention is preferred, and a method of using the photosensitive resin composition film of the preferred form described above is even more preferred.

[0155] <Metal Reflective Layer>

[0156] In the scintillator panel of the present invention, the isolation wall preferably has a reflective layer containing metal (hereinafter referred to as "metal reflective layer") on its surface. The metal reflective layer need only be provided on at least a portion of the isolation wall. Even if the metal reflective layer is a thin film, it has high reflectivity. Therefore, by providing a metal reflective layer as a thin film, the reflectivity of the isolation wall can be increased without reducing the phosphor filler content, thereby further improving the brightness of the scintillator panel. Examples of metal reflective layers can be cited, for instance, in International Publication No. 2019 / 181444.

[0157] <Protective Layer>

[0158] The scintillator panel of the present invention preferably has a protective layer on the surface of the metal reflective layer. As the metal reflective layer, an alloy or the like, which lacks resistance to discoloration in the atmosphere, is preferably used. However, even in this case, by providing a protective layer, discoloration of the metal reflective layer can be reduced. It is believed that the decrease in reflectivity of the metal reflective layer caused by the reaction between the metal reflective layer and the phosphor layer can be suppressed. Therefore, the brightness of the scintillator panel is further improved.

[0159] As a protective layer, either an inorganic or an organic protective layer can be used preferably. Alternatively, inorganic and organic protective layers can be layered together and used in combination.

[0160] <Inorganic Protective Layer>

[0161] Inorganic protective layers are preferred as protective layers due to their low permeability to water vapor. Examples of inorganic protective layers can be cited in International Publication No. 2019 / 181444.

[0162] <Organic Protective Layer>

[0163] The organic protective layer is preferably formed from a polymeric compound with excellent chemical durability, and for example, preferably contains polysiloxane or amorphous fluoropolymer as the main component. Examples of organic protective layers can be cited in International Publication No. 2019 / 181444. Examples of materials constituting the organic protective layer can be cited in International Publication No. 2021 / 200327, for example, as polysiloxane or amorphous fluoropolymer.

[0164] <Fluorescent layer>

[0165] The scintillator panel of the present invention has a phosphor layer within a unit divided by an isolation wall.

[0166] The phosphor layer absorbs the energy of incident X-rays and other radiation, and emits electromagnetic waves in the wavelength range of 300 nm to 800 nm, that is, light spanning from ultraviolet to infrared light with visible light as the core. The light emitted by 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 is preferably composed of a phosphor and an adhesive resin.

[0167] <Fluorescent>

[0168] Examples of phosphors can be cited in International Publication No. 2021 / 200327. In terms of high luminous efficiency, terbium-activated rare-earth sulfide-based phosphors are preferred.

[0169] <Adhesive Resin>

[0170] As an adhesive resin, examples can be cited, for instance, as an adhesive resin illustrated in International Publication No. 2021 / 200327.

[0171] The adhesive resin is preferably in contact with the protective layer. In this case, the adhesive resin only needs to be in contact with at least a portion of the protective layer. Therefore, in the scintillator panel, the phosphor is less likely to detach from the cell. Furthermore, as... Figure 1 As shown, the adhesive resin can be filled within the unit with almost no voids, or it can be filled with voids.

[0172] According to the scintillator panel of the present invention, a high-brightness image can be obtained.

[0173] <Manufacturing Method of Scintillator Panel>

[0174] The preferred method for manufacturing the scintillator panel of the present invention includes, for example: an isolation wall forming step, forming an isolation wall comprising the hardened material of the present invention on a substrate to divide the space into units; a reflective layer forming step, forming a metallic reflective layer or a protective layer on the surface of the isolation wall as needed; and a filling step, filling the units divided by the isolation wall with phosphor. Furthermore, in the following description, matters common to those described in the embodiments of the scintillator panel are suitably omitted.

[0175] <Isolation Wall Formation Process>

[0176] On the substrate, an isolation wall of the desired shape is formed in the same manner as in the described <method for manufacturing a hardened material>. In the method for manufacturing a scintillator panel of the present invention, the substrate in which the isolation wall is formed can be used as the substrate of the scintillator panel, or the isolation wall can be peeled off from the substrate and then placed on the substrate for use. The method for peeling the isolation wall off the substrate can use known methods such as a method of providing a peeling aid layer between the substrate and the isolation wall.

[0177] <Reflective layer formation process>

[0178] In cases where the surface of the isolation wall has a metallic reflective layer, as well as an inorganic protective layer and / or an organic protective layer, methods for forming these can be exemplified, for example, in International Publication No. 2019 / 181444 or International Publication No. 2021 / 200327 as the forming process of these.

[0179] <Filling Process>

[0180] As a method for filling phosphors, methods exemplified as filling steps in International Publication No. 2019 / 181444 or International Publication No. 2021 / 200327 can be cited, for example.

[0181] Semiconductor Devices

[0182] The semiconductor device of the present invention includes a semiconductor element and an insulating film comprising the cured material of the present invention. Examples of semiconductor devices include electro-optical devices or semiconductor circuit boards that connect semiconductor elements to a substrate, electronic devices comprising these, and electronic components such as multilayer wiring boards that connect semiconductor elements. Examples of insulating films include: interlayer insulating films for inductors, passivation films for semiconductors, surface protective films for semiconductor elements, interlayer insulating films between semiconductor elements / wiring layers or between multiple semiconductor elements or between wiring layers for high-density mounting of multilayer wiring, and insulating films for organic electroluminescent elements. By having an insulating film with a high aspect ratio comprising the cured material of the present invention, wiring density can be increased.

[0183] From the viewpoint of further increasing wiring density, the thickness of the insulating film is preferably 100 μm or more, and from the viewpoint of suppressing warping of the semiconductor device caused by film stress, the thickness of the insulating film is preferably 1,000 μm or less.

[0184] The aspect ratio of the insulating film can be calculated using the width L0 (μm) of the high-transmittance side surface, the width L100 (μm) of the low-transmittance side surface, and the height H (μm), and by H / {(L0+L100) / 2}. The aspect ratio of the insulating film is preferably 16 or more, more preferably greater than 16.0. The aspect ratio is preferably 30 or less, more preferably 30.0 or less.

[0185] The cured material of the present invention can be easily formed into patterns with a high aspect ratio, and is therefore preferably used for inductors in semiconductor devices that require a high aspect ratio insulating film.

[0186] Figure 3The diagram shows a cross-sectional view schematically illustrating the structure of an inductor, one embodiment of the semiconductor device of the present invention. The inductor 15 has coils 17 and insulating films 16 maintaining insulation between the coils 17 via resin layers 18 on both sides of a substrate 19. Furthermore, the inductor 15 has a magnetic agent 21 via an insulating film 20 and is sealed using molding resin 22.

[0187] By using the hardened material of the present invention as the insulating film of the inductor, an insulating film exhibiting sufficient insulation properties can be formed even with a small pattern width. Therefore, the cross-sectional area of ​​the coil wiring can be increased, thereby improving the inductance of the inductor.

[0188] Example

[0189] The present invention will be further described in detail below with reference to examples and comparative examples. The compounds used in the examples and comparative examples were synthesized using the following methods.

[0190] <Synthetic Example 1: Synthesis of Polyimide A-1>

[0191] 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 and Wako Pure Chemical Industries Co., Ltd.), and stirred at 120°C to dissolve. Next, 30.03 g (0.1 mol) of acid anhydride "Rikacid" (trademark registered) TDA-100 (hereinafter referred to as "TDA-100") (manufactured by Shin Nippon Rikka Co., Ltd.) was added together with 20 g of GBL, and stirred at 120°C for 1 hour, followed by stirring at 200°C for 4 hours to obtain a reaction solution. Next, the reaction solution was added to 3 L of water, causing a white precipitate to form. 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 polyimide A-1 with a weight average molecular weight of 4,000 and a basic functional group equivalent of more than 1,000 g / eq.

[0192] <Synthetic Example 2: Synthesis of Polyimide A-2>

[0193] Under a dry nitrogen stream, 32.96 g (0.09 mol) of BAHF was added to 80 g of GBL and dissolved by stirring 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, followed by stirring at 200 °C for 4 hours to obtain a reaction solution. The reaction solution was then added to 3 L of water, causing a white precipitate to form. 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 polyimide A-2 with a weight average molecular weight of 8,000 and a basic functional group equivalent of 1,000 g / eq or higher.

[0194] <Synthetic Example 3: Synthesis of Polyamide-Imide A-3>

[0195] 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 and Koimitsu Chemical Co., Ltd.), and the solution was cooled to -15°C. A solution prepared by dissolving 3-nitrobenzyl 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. After the addition was complete, the reaction mixture was stirred at -15°C for 4 hours, and then the reaction solution was brought back to room temperature. The precipitated white solid was separated by filtration and dried under vacuum at 50°C.

[0196] 30 g of the obtained white solid was placed in a 300 mL stainless steel autoclave and dispersed in 250 mL of methyl cellosolve (manufactured by Tokyo Chemical Industry Co., Ltd.). 2 g of 5% palladium-carbon was added. Hydrogen was introduced into the mixture using a balloon, and the mixture was stirred at room temperature to initiate a reduction reaction. After approximately 2 hours, stirring was stopped once the balloon was confirmed to be no longer shrinking. After stirring, the mixture was filtered to remove the palladium compound acting as a catalyst. The filtrate was concentrated using a rotary evaporator to obtain a hydroxyl-containing diamine compound (a).

[0197] 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 and Koko Pure Chemical Industries, Ltd.), and stirred at 120°C. Next, 0.0 g (0.1 mol) of TDA-100 (manufactured by Shin Nippon Rikka, Ltd.) was added along with 20 g of GBL, and the mixture was stirred at 120°C for 1 hour, followed by stirring at 200°C for 4 hours to obtain a reaction solution. The reaction solution was then added to 3 L of water, causing a white precipitate to form. 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 polyamide-imide A-3 with a weight average molecular weight of 5,000 and a basic functional group equivalent of 1,000 g / eq or higher.

[0198] In addition, the raw materials used in the embodiments and comparative examples are shown below.

[0199] (A) Resin

[0200] A-4: "Maruka Lyncur" (registered trademark) M (manufactured by Maruzen Petrochemical Co., Ltd.), poly(p-hydroxystyrene), resin with a weight average molecular weight of 4,000 and a basic functional group equivalent of 1,000 g / eq or higher.

[0201] (B) Epoxides or oxetanes

[0202] B-1: OXT-191 (manufactured by Dong-A Synthetic (Stock) Co.), having an average of twelve oxocyclic butyl groups, having the structure represented by the general formula (1), R 1 For polysilicate, R 2 It is an ethyl, non-water-soluble compound without a polyalkylene glycol chain.

[0203] B-2: OXT-121 (manufactured by Dong-A Synthetic Co., Ltd.), a difunctional oxobutane compound without a polyalkylene glycol chain: a non-water-soluble compound.

[0204] B-3: "DENACOL" (registered trademark) EX-861 (manufactured by Nagase ChemteX Co., Ltd.), a difunctional epoxy compound with a polyethylene glycol chain: water-soluble compound

[0205] B-4: "TEPIC" (registered trademark) - VL (manufactured by Nissan Chemical Co., Ltd.), trifunctional epoxy compounds without polyalkylene glycol chains: non-water-soluble compounds

[0206] (C) Photocationic polymerization initiator

[0207] C-1: CPI-410S (manufactured by San-Apro (stock)), aromatic sulfonium = phosphate.

[0208] C-2: CPI-410B (manufactured by San-Apro (stock)), aromatic sulfonium = borate.

[0209] Next, the evaluation methods in each embodiment and comparative example will be described.

[0210] <Transmission Rate>

[0211] Three randomly selected locations were cut from the photosensitive polyimide varnish coating films prepared in the various embodiments and comparative examples, with a width of 20 μm perpendicular to the surface, to obtain samples with a thickness of 20 μm. For each sample, the transmittance in the thickness direction was measured using a microspectrophotometer at positions 10 μm from one surface and 10 μm from the other surface, and the average value of the three locations was calculated. The value with the higher transmittance was designated Tα, and the value with the lower transmittance was designated Tβ.

[0212] For three randomly selected locations from the lattice-shaped isolation walls formed in each embodiment and comparative example, the transmittance was measured and the average value was calculated. The location with the higher transmittance value was designated as T'α, and the location with the lower transmittance value was designated as T'β.

[0213] <(C) Content of photocationic polymerization initiator>

[0214] For the photosensitive polyimide varnish coatings prepared in the various examples and comparative examples, 100 mg portions of each sample were collected from the high-transmittance side surface and the low-transmittance side surface, respectively, at approximately 10% depth and 90% depth from the high-transmittance side surface, as test samples. After adding 0.5 mL of acetonitrile to 10 mg of each test sample, the sample was subjected to ultrasonic treatment for 60 minutes and centrifuged at 20,000 g for 15 minutes. A portion of the supernatant after centrifugation was transferred to a brown glass vial for analysis. The peak of the anionic component originating from the (C) photocationic polymerization initiator was quantitatively analyzed by HPLC to calculate the content of the (C) photocationic polymerization initiator. The content of the (C) photocationic polymerization initiator at a depth of 10% from the surface on the side where the transmittance is Tα (%) was calculated, and the content of the (C) photocationic polymerization initiator at a depth of 90% from the surface was calculated, C10 (mass%).

[0215] <Height H' of the partition wall, top width L'0, bottom width L'100, L'n, L'0 / L'100, maximum rate of change of width, aspect ratio>

[0216] Regarding three randomly selected locations from the lattice-shaped isolation walls formed in the various embodiments and comparative examples, the cross-sections exposed by cutting along a direction perpendicular to the substrate and perpendicular to the long side, or by using a polishing device such as a cross-section polisher, were observed using a scanning electron microscope. The width of the top of the isolation wall, the width of the isolation wall at the contact point between the isolation wall and the substrate, and the height of the isolation wall were measured, and their average values ​​were calculated and denoted as L'0, L'100, and H', respectively. Based on these measured values, the ratio of L'0 / L'100 to the longitudinal dimension (H' / ((L'0+L'100) / 2)) was calculated. In addition, the width Ln of the isolation wall was measured at a depth of n% from the top of the isolation wall relative to the height H' of the isolation wall, in 1% depth increments, and the maximum rate of change of width (the maximum value of {L'(n+1)-L'n} / (L'100-L'0)) was calculated. The width L'n of the isolation wall was set as the average of the measured values ​​of the three locations.

[0217] <Example 1>

[0218] <Preparation of photosensitive polyimide varnish>

[0219] 10 g of polyimide A-1 obtained from Synthesis Example 1, which is (A) resin, 10 g of B-1, 1.0 g of B-2, 1.0 g of B-3, which are (B) epoxy compounds and / or oxetane compounds, and 0.066 g of C-1, which is (C) photocationic polymerization initiator, were weighed and dissolved in GBL. The amount of GBL added was adjusted such that the components other than GBL were set as solid components and the concentration of solid components was 60% by mass. Then, the solution was pressure filtered using a filter that retains a particle size of 30 μm to obtain photosensitive polyimide varnish 1 for high transmittance.

[0220] 10 g of polyimide A-1 obtained from Synthesis Example 1, which is (A) resin, 10 g of B-1, 1.0 g of B-2, 1.0 g of B-3, which are (B) epoxy compounds and / or oxetane compounds, and 0.22 g of C-1, which is (C) photocationic polymerization initiator, were weighed and dissolved in GBL. The amount of GBL added was adjusted such that the components other than GBL were set as solid components and the concentration of solid components was 70% by mass. Then, the solution was pressure filtered using a filter that retains a particle size of 30 μm to obtain photosensitive polyimide varnish 2 for the low transmittance side.

[0221] <Creating a Scintillator Panel>

[0222] <The Formation of the Insulation Wall>

[0223] As the substrate, a PET film measuring 125 mm in length, 125 mm in width, and 0.25 mm in thickness was used. The photosensitive polyimide varnish 2 was coated onto the substrate surface using a die coater to achieve a thickness of 70 μm after thermal cross-linking and curing. The coated film was then dried in a 110°C hot air oven for 1 hour to form a coating film of photosensitive polyimide varnish 2. Next, the photosensitive polyimide varnish 1 was coated onto the photosensitive polyimide varnish 2 coating film using a die coater to achieve a thickness of 280 μm after thermal cross-linking and curing. The coated film was then dried in a 110°C hot air oven for 3 hours to form a coating film of photosensitive polyimide varnish 1.

[0224] Next, using a chromium mask with lattice-shaped openings spaced 200 μm apart and linewidths of 12 μm, 15 μm, and 20 μm, and employing an ultra-high pressure mercury lamp and a bandpass filter with a cutoff wavelength of 405 nm, at 5000 mJ / cm², a light source was obtained. 2 The laminate of the photosensitive polyimide varnish coating was exposed to a specific exposure level. After exposure, it was heated in a hot air oven at 100°C for 90 minutes. The exposed / heated coating was then developed in a 0.5% (w / w) potassium hydroxide aqueous solution at 30°C until the unexposed areas were removed, resulting in a lattice pattern. The obtained lattice pattern was then heated in air at 200°C for 60 minutes to thermally crosslink and harden, forming a lattice-shaped insulating wall.

[0225] <Formation of Metallic Reflective Layer and Inorganic Protective Layer>

[0226] For the formed lattice-shaped isolation wall, a commercially available sputtering apparatus was used to sputter a silver alloy containing palladium and copper, namely APC (manufactured by Furuya Metal Co., Ltd.), as the sputtering target to form a metallic reflective layer. Sputtering was performed with a glass plate placed near the substrate where the isolation wall was formed, and the thickness of the metallic layer formed on the glass plate was 300 nm. After forming the metallic reflective layer, SiN was sputtered as an inorganic protective layer in the same vacuum batch to form an inorganic protective layer. At this time, the thickness of the inorganic protective layer formed on the glass substrate was 100 nm.

[0227] <Formation of Organic Protective Layer>

[0228] A resin solution is prepared by mixing 1 part by weight of the amorphous fluorinated resin "CYTOP" (registered trademark) CTL-809M with 1 part by weight of the fluorinated solvent CT-SOLV180 (manufactured by AGC).

[0229] The obtained resin solution was vacuum printed onto the isolation wall after the formation of the metal reflective layer and the inorganic protective layer. It was then dried at 90°C for 1 hour, followed by heating at 190°C for 1 hour to form the organic protective layer. The isolation wall profile was exposed using a triple ion polishing apparatus EMTIC3X (manufactured by Leica). The profile was then imaged using a field emission scanning electron microscope (FE-SEM) with a Merlin (manufactured by Zeiss). The thickness of the organic protective layer was measured, and the thickness of the organic protective layer on the central side of the isolation wall in the height direction was determined to be 1 μm.

[0230] <Formation of the fluorophore>

[0231] A phosphor paste was prepared by mixing 10 parts by mass of the phosphor GOS:Tb (Tb-doped gadolinium sulfide) with 5 parts by mass of a 10% by mass binder resin solution made by dissolving 7cp of the binder resin "ethocel" (registered trademark) (manufactured by Dow Chemical Co., Ltd.) in benzyl alcohol (manufactured by Fujifilm and Koden Pharmaceutical Co., Ltd.). Furthermore, the average particle size D50 of the phosphor, measured using an MT3300 particle size distribution measuring device (manufactured by Nikkiso Co., Ltd.), was 11 μm.

[0232] As described above, within the unit divided by the isolation wall after forming the metal reflective layer, the inorganic protective layer and the organic protective layer, the obtained phosphor paste is vacuum printed with a phosphor volume fraction of 65%, and dried at 150°C for 15 minutes to form a phosphor layer, thereby obtaining a scintillator panel.

[0233] <Examples 2-9, Comparative Examples 1-2>

[0234] The isolation wall and scintillator panel were prepared in the same manner as in Example 1, except that the types and amounts (parts by weight) of (A) resin, (B) oxobutane compound and / or epoxy compound, and (C) photocationic polymerization initiator were changed as described in Table 1.

[0235] <Example 10>

[0236] The drying time of photosensitive polyimide varnish 1 was changed to 2 hours, and the isolation wall and scintillator panel were made in the same manner as in Example 1.

[0237] <Example 11>

[0238] The drying time of photosensitive polyimide varnish 1 was changed to 1 hour, and the isolation wall and scintillator panel were made in the same manner as in Example 1.

[0239] <Example 12>

[0240] Photosensitive polyimide varnish 1 was coated onto a 50 μm thick PET film using a die coater, achieving a thickness of 280 μm after thermal cross-linking and curing. The film was then dried at 110°C for 3 hours to form a coated film of photosensitive polyimide varnish 1. Separately, photosensitive polyimide varnish 2 was coated onto the surface of a glass substrate using a die coater, achieving a thickness of 70 μm after thermal cross-linking and curing. The film was then dried in a hot air oven at 110°C for 1 hour to form a coated film of photosensitive polyimide varnish 2. For two substrates with a photosensitive polyimide varnish coating, the coating films were placed facing each other and laminated using a vacuum film laminator (manufactured by Meiki Seisakusho Co., Ltd., MVLP-500 / 600). The lamination was performed under the following conditions: upper and lower hot plate temperature 80°C, vacuum time 20 seconds, vacuum pressing time 30 seconds, and bonding pressure 0.5 MPa. Only the PET film was peeled off, forming a resin composition film with a thickness of 350 μm on the glass substrate. The obtained resin composition film was used as a laminate of the photosensitive polyimide varnish coating film. Otherwise, the isolation wall and scintillator panel were fabricated in the same manner as in Example 1.

[0241] The results obtained by evaluating each embodiment and comparative example using the described method are shown in Tables 3 and 4.

[0242] [Table 1]

[0243]

[0244] [Table 2]

[0245]

[0246] [Table 3]

[0247]

[0248] [Table 4]

[0249]

[0250] Explanation of icon numbers

[0251] 1: Components for radiation detectors

[0252] 2: Scintillator Panel

[0253] 3: Output board

[0254] 4: Substrate

[0255] 5: Isolation wall

[0256] 6: Fluorescent layer

[0257] 7: Diaphragm layer

[0258] 8: Photoelectric conversion layer

[0259] 9: Output Layer

[0260] 10: Substrate

[0261] 11: Metal Reflective Layer

[0262] 12: Organic protective layer

[0263] 13: Fluorescent material

[0264] 14: Adhesive resin

[0265] 15: Inductor

[0266] 16: Insulating film

[0267] 17: Coil

[0268] 18: Resin layer

[0269] 19: Substrate

[0270] 20: Insulating film

[0271] 21: Magnetic Materials

[0272] 22: Molding resin

[0273] H': Height of the isolation wall

[0274] L'0: Top width of the isolation wall

[0275] L'100: Bottom width of the isolation wall

[0276] P: Spacing between adjacent isolation walls

Claims

1. A photosensitive resin composition film comprising (A) a resin, (B) an epoxy compound and / or an oxetane compound, and (C) a photocationic polymerization initiator, wherein the transmittance Tα (%) of one surface at a wavelength of 405 nm and the transmittance Tβ (%) of the other surface at a wavelength of 405 nm satisfy the following formula (1). Tα>Tβ(1) The content of the (C) photocationic polymerization initiator at a depth of 10% from the surface of the side where the transmittance per unit film thickness at wavelength 405 nm is Tα (%), relative to the thickness of the photosensitive resin composition film, C10 (mass%), and the content of the (C) photocationic polymerization initiator at a depth of 90% from the surface, satisfy the following formula (2). 0.050≦C10 / C90≦0.85(2).

2. The photosensitive resin composition film according to claim 1, comprising a first film and a second film, the first film comprising a first photosensitive resin composition containing (A) resin, (B) epoxy compound and / or oxetane compound, and (C) photocationic polymerization initiator, the second film comprising a second photosensitive resin composition containing (A) resin, (B) epoxy compound and / or oxetane compound, and (C) photocationic polymerization initiator, wherein the content of (C) photocationic polymerization initiator in the first photosensitive resin composition is different from the content of (C) photocationic polymerization initiator in the second photosensitive resin composition.

3. The photosensitive resin composition film according to claim 1 or 2, wherein the resin (A) contains polyimide, polyamide, polyamide-imide and / or polybenzoxazole.

4. A curable material formed by curing a photosensitive resin composition containing (A) a resin, (B) an epoxy compound and / or an oxetane compound, and (C) a photocationic polymerization initiator, wherein the transmittance T'α (%) of one surface at a wavelength of 405 nm and the transmittance T'β (%) of the other surface at a wavelength of 405 nm satisfy the following formula (3). T'α>T'β(3) The height H (μm) is 100 μm or more.

5. The hardened material according to claim 4, wherein the width L0 (μm) of the surface of the hardened material on the side where the transmittance per unit thickness at wavelength 405 nm is T'α (%) and the width L100 (μm) of the surface of the hardened material on the side where the transmittance per unit thickness at wavelength 405 nm is T'β (%) satisfy the following formula (4). L0 / L100≦0.90(4).

6. The hardened material according to claim 4 or 5, wherein when the width of the surface of the side from which the transmittance per unit thickness at wavelength 405 nm of the hardened material is T'α (%) is defined as n% at a depth relative to the height H (μm) of the hardened material is set as Ln, the following equation (5) is satisfied in the range of n being 0% to 99%. {L(n+1)-Ln} / (L100-L0)<0.10(5).

7. The hardened material according to any one of claims 4 to 6, wherein the width L0 (μm) of the surface of the hardened material on the side where the transmittance per unit thickness at wavelength 405 nm is T'α (%), the width L00 (μm) of the side where the transmittance per unit thickness at wavelength 405 nm is T'β (%), and the height H (μm) satisfy the following formula (7). H / {(L0+L100) / 2}>16.0 (7).

8. The hardened compound according to any one of claims 4 to 7, wherein the resin (A) contains polyimide, polyamide, polyamide-imide and / or polybenzoxazole.

9. A method for manufacturing a photosensitive resin composition film, comprising the steps of: forming a first film using a first photosensitive resin composition containing (A) resin, (B) epoxy compound and / or oxetane compound, and (C) photocationic polymerization initiator; and forming a second film on the first film using a second photosensitive resin composition containing (A) resin, (B) epoxy compound and / or oxetane compound, and (C) photocationic polymerization initiator, wherein the content of (C) photocationic polymerization initiator in the first photosensitive resin composition is different from the content of (C) photocationic polymerization initiator in the second photosensitive resin composition.

10. A method for manufacturing a cured material, comprising: an exposure step of exposing a photosensitive resin composition film as described in any one of claims 4 to 8 in an image-like manner; and a development step of removing unexposed portions using a developing solution.

11. A scintillator panel comprising: a substrate; an isolation wall formed on the substrate; and a phosphor layer filled into cells defined by the isolation wall, wherein the isolation wall comprises a hardened material as described in any one of claims 4 to 8.

12. A semiconductor device having a semiconductor element and an insulating film, wherein the insulating film comprises a hardened material as described in any one of claims 4 to 8.

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