JP2009300213A - Scintillator panel and radiation flat panel detector - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a scintillator panel wherein the rates of sharpness degradation and singular faults are low in wetproof test with high luminance (light emission quantity) being maintained and there are less image non-uniformity and linear noise, and to provide a radiation flat panel detector using the same. <P>SOLUTION: In this scintillator panel which is a scintillator plate having a scintillator layer on a substrate, the scintillator layer includes a phosphor columnar crystal and a filling material as components, and the whole scintillator plate is covered with a protection layer. <P>COPYRIGHT: (C)2010,JPO&INPIT

Description

  The present invention relates to a scintillator panel used when forming a radiographic image of a subject and a radiation flat panel detector using the scintillator panel.

  Conventionally, radiographic images such as X-ray images have been widely used for diagnosis of medical conditions in the medical field. In particular, radiographic images using intensifying screen-film systems are still the world as an imaging system that combines high reliability and excellent cost performance as a result of high sensitivity and high image quality in the long history. Used in the medical field. However, these pieces of image information are so-called analog image information, and free image processing and instantaneous electric transmission cannot be performed like digital image information that has been developing in recent years.

  In recent years, digital radiographic image detection apparatuses represented by computed radiography (CR), flat panel type radiation detectors (FPD) and the like have appeared. In these, since a digital radiographic image is directly obtained and an image can be directly displayed on an image display device such as a cathode tube or a liquid crystal panel, image formation on a photographic film is not necessarily required. As a result, these digital X-ray image detection devices reduce the need for image formation by the silver halide photography method, and greatly improve the convenience of diagnosis work in hospitals and clinics.

  Computed radiography (CR) is currently accepted in the medical field as one of the digital technologies for X-ray images. However, the sharpness is insufficient and the spatial resolution is insufficient, and the image quality level of the screen / film system has not been reached. Further, as new digital X-ray imaging techniques, for example, the magazine Physics Today, November 1997, page 24, John Laurans's paper “Amorphous Semiconductor User in Digital X-ray Imaging”, magazine SPIE Vol. 32, 1997. A flat-plate X-ray detector using a thin film transistor (TFT) developed by El E. Antonuk's paper “Development of a High Resolution, Active Matrix, Flat-Panel Image with Enhanced Fill Factor”, etc. Has been.

  In order to convert radiation into visible light, a scintillator panel made of an X-ray phosphor having a characteristic of emitting light by radiation is used. In order to improve the S / N ratio in low-dose imaging, luminous efficiency is used. It is necessary to use a high scintillator panel. In general, the luminous efficiency of a scintillator panel is determined by the thickness of the scintillator layer (also referred to as “phosphor layer”) and the X-ray absorption coefficient of the phosphor, but the greater the thickness of the scintillator layer, Scattering of the emitted light occurs at, and sharpness decreases. Therefore, when the sharpness necessary for the image quality is determined, the film thickness is determined.

  In particular, cesium iodide (CsI) has a relatively high rate of change from X-rays to visible light, and phosphors can be easily formed into a columnar crystal structure by vapor deposition. Therefore, it was possible to increase the thickness of the scintillator layer.

  However, since CsI alone has low luminous efficiency, for example, a method in which CsI and sodium iodide (NaI) are mixed at an arbitrary molar ratio as described in Japanese Patent Publication No. 54-3560 is used by vapor deposition. Deposited on the substrate as sodium activated cesium iodide (CsI: Na), and recently mixed with any molar ratio of CsI and thallium iodide (TlI) on the substrate using vapor deposition. Visible conversion efficiency is improved by performing annealing (heat treatment) as a post-process on those deposited as cesium (CsI: Tl) and used as an X-ray phosphor.

  As another means for increasing the light output, a method of making the substrate on which the scintillator is formed reflective (for example, see Patent Document 1), a method of providing a reflective layer on the substrate (for example, see Patent Document 2), and on the substrate. A method of forming a scintillator on a reflective metal thin film provided on the substrate and a transparent organic film covering the metal thin film (see, for example, Patent Document 3) has been proposed. However, these methods increase the amount of light obtained. However, there is a drawback that sharpness is remarkably lowered.

  Further, for arranging the scintillator panel on the plane light receiving element surface, for example, there are methods described in JP-A-5-329661 and JP-A-6-331749. Deterioration of sharpness is unavoidable.

  Conventionally, as a scintillator manufacturing method by a gas layer method, it is common to form a scintillator layer on a rigid substrate such as aluminum or amorphous carbon, and to cover the entire surface of the scintillator with a protective film (for example, (See Patent Document 4). However, when a scintillator layer is formed on these substrates that cannot be bent freely, the flat panel detector is affected by the deformation of the substrate and the warpage during vapor deposition when the scintillator panel and the planar light receiving element surface are bonded together. There is a drawback that uniform image quality characteristics cannot be obtained within the light receiving surface.

  In addition, when the substrate is a metal, X absorption is large, which is a problem especially in terms of promoting low exposure. On the other hand, amorphous carbons that have begun to be used in recent years are useful in practical production because they have low X-ray absorption, but are not widely used for large-sized products and are very expensive. It was hard to say. Therefore, such a problem has become serious with the recent increase in the size of flat panel detectors.

  To avoid this problem, the scintillator panel can be replaced with a method of forming a scintillator by vapor deposition directly on the surface of the light receiving element (on the image sensor) or a medical intensifying screen with low sharpness but flexibility. It is generally used. In addition, an example in which a flexible protective layer such as polyparaxylylene is used as the protective layer is shown (for example, see Patent Document 5).

  However, although the scintillator material directly deposited on the light receiving element (direct vapor deposition type) has high image characteristics, the image characteristics of the scintillator material can be improved by heat treatment due to the cost disadvantage of wasting the expensive light receiving element when defective vapor deposition occurs. In spite of being removed, the light receiving element is vulnerable to heat, so that the temperature processing is restricted, or there is a disadvantage that an extra cost is imposed on the equipment. On the other hand, in the case of the indirect installation type in which the scintillator material vapor-deposited on the substrate is combined with the light receiving element, there is an advantage that the disadvantages of the direct vapor-deposited scintillator material (direct vapor deposition type) are improved.

However, a vapor-deposited layer made of a phosphor, which is an image forming layer of the vapor-deposited scintillator material, has deliquescence and is a material that is vulnerable to moisture (humidity). Then, although the sealing film was used as a protective layer with respect to a water | moisture content, there was a case where it was sometimes insufficient as moisture resistance (refer patent document 6).
Japanese Patent Publication No. 7-21560 Japanese Patent Publication No. 1-240887 JP 2000-356679 A Japanese Patent No. 3669926 JP 2002-116258 A JP 2007-139604 A

  The present invention has been made in view of the above problems, and the problem to be solved is that the deterioration rate of sharpness and the specific failure occurrence rate in the moisture resistance test are low while maintaining the luminance (light emission amount). To provide a scintillator panel with less image unevenness and linear noise and a radiation flat panel detector using the scintillator panel.

  The above-mentioned problem according to the present invention is solved by the following means.

  1. A scintillator plate having a scintillator layer on a substrate, the scintillator layer containing phosphor columnar crystals and a filler as its constituent elements, and the entire scintillator plate being covered with a protective layer A scintillator panel characterized by

  2. 2. The scintillator panel according to 1, wherein the filler has a refractive index (nD25) of 1.70 or less.

  3. The scintillator panel according to 1 or 2, wherein the filler is an organic substance.

  4). The scintillator panel according to any one of claims 1 to 3, wherein the filler is a liquid, and the solubility of the phosphor constituting the scintillator layer in the liquid is 0.1 or less. .

  5). The scintillator panel according to any one of claims 1 to 4, wherein the liquid as the filler is at least one of a fluorine-based water-repellent liquid and a silicone-based water-repellent liquid.

  6). The scintillator panel according to any one of 1 to 3, wherein the filler is formed by a vapor phase growth method.

  7. The scintillator panel according to any one of 1 to 6, wherein the phosphor columnar crystal contains cesium iodide and is formed by a vapor phase growth method.

  8). The scintillator panel according to any one of 1 to 7, wherein the substrate is a heat resistant resin.

  9. The scintillator panel according to any one of 1 to 8, wherein a refractive index (nD25) of the filler is 1.40 or less.

  10. The scintillator panel according to any one of 1 to 9, further comprising at least one of a reflective layer and an undercoat layer between the substrate and the scintillator layer.

  11. A radiation flat panel detector comprising the scintillator panel according to any one of 1 to 10 and a planar light receiving element, wherein the scintillator panel is not physicochemically bonded to the planar light receiving element surface. Radiation flat panel detector.

  By the above means of the present invention, a scintillator panel having a low degradation rate of sharpness and a specific failure occurrence rate in a moisture resistance test with little light unevenness and linear noise in a state where light luminance is maintained, and radiation using the scintillator panel A flat panel detector can be provided.

  The scintillator panel of the present invention is a scintillator plate having a scintillator layer on a substrate, the scintillator layer contains phosphor columnar crystals and a filler as its constituent elements, and the scintillator plate as a whole is protected. It is characterized by being covered with a layer. This feature is a technical feature common to the inventions according to claims 1 to 11.

  As an embodiment of the present invention, it is preferable that the refractive index (nD25) of the filler is 1.70 or less. Here, “refractive index (nD25)” refers to the refractive index with respect to the sodium D line at 25 ° C.

  Moreover, it is preferable that the said filler is an organic substance. Furthermore, it is preferable that the filler is a liquid, and the solubility of the phosphor (fluorescent compound) constituting the scintillator layer in the liquid is 0.1 or less. Here, the “solubility” refers to the mass (g) of a solute (phosphor constituting the scintillator layer) dissolved in 100 g of a solvent (liquid) at 25 ° C.

  The liquid is preferably at least one of a fluorine-based water-repellent liquid and a silicone-based water-repellent liquid.

  In this invention, it is also preferable that the said filler is an aspect formed by the vapor phase growth method.

  In the present invention, it is preferable that the phosphor columnar crystal contains cesium iodide and is formed by a vapor phase growth method. Furthermore, the substrate is preferably a heat resistant resin.

  As an embodiment of the present invention, it is preferable that a refractive index (nD25) of the filler is 1.40 or less. Moreover, it is preferable that it is an aspect which has at least one of a reflective layer and an undercoat layer between the said board | substrate and a scintillator layer.

  When the scintillator panel of the present invention is used for a radiation flat panel detector equipped with a planar light receiving element, it is preferable that the scintillator panel is a radiation flat panel detector in an aspect that is not physicochemically bonded to the surface of the planar light receiving element. .

  Hereinafter, the present invention, its components, and the best mode and mode for carrying out the present invention will be described in detail.

(Configuration of scintillator plate and panel)
The scintillator panel of the present invention is a scintillator plate having a scintillator layer on a substrate, the scintillator layer contains phosphor columnar crystals and a filler as its constituent elements, and the scintillator plate as a whole is protected. It is characterized by being covered with a layer.

  The scintillator plate according to the present invention is preferably an embodiment in which a reflective layer, an undercoat layer, and a scintillator layer are provided in this order on a substrate.

(Scintillator layer)
The scintillator layer according to the present invention is characterized by containing at least a phosphor columnar crystal and a filler as its constituent elements. The term “phosphor” as used in the present application refers to a substance that exhibits a phenomenon (referred to as “scintillation”) that emits fluorescence by absorbing radiation energy when radiation is incident.

  As a material for forming the phosphor constituting the scintillator layer (also referred to as “phosphor layer”), various known phosphor materials can be used, but the change rate from X-ray to visible light is compared. Since the phosphor can be easily formed into a columnar crystal structure by vapor deposition, it is possible to suppress the scattering of the emitted light in the crystal by the light guide effect, and to increase the thickness of the scintillator layer. Cesium iodide (CsI) is preferred.

  However, since only CsI has low luminous efficiency, various activators are added. For example, as shown in Japanese Patent Publication No. 54-35060, a mixture of CsI and sodium iodide (NaI) at an arbitrary molar ratio can be mentioned. Further, for example, CsI as disclosed in Japanese Patent Application Laid-Open No. 2001-59899 is deposited, and thallium (Tl), europium (Eu), indium (In), lithium (Li), potassium (K), rubidium (Rb) ), CsI containing an activating substance such as sodium (Na) is preferred. In the present invention, thallium (Tl) and europium (Eu) are particularly preferable. Furthermore, thallium (Tl) is preferred.

  In the present invention, it is particularly preferable to use an additive containing one or more types of thallium compounds and cesium iodide as raw materials. That is, thallium activated cesium iodide (CsI: Tl) is preferable because it has a wide emission wavelength from 400 nm to 750 nm.

  As the thallium compound as an additive containing one or more types of thallium compounds according to the present invention, various thallium compounds (compounds having oxidation numbers of + I and + III) can be used.

In the present invention, a preferred thallium compound is thallium bromide (TlBr), thallium chloride (TlCl), thallium fluoride (TlF, TlF ₃ ), or the like.

  The melting point of the thallium compound according to the present invention is preferably in the range of 400 to 700 ° C. If the temperature exceeds 700 ° C., the additives in the columnar crystals exist non-uniformly, resulting in a decrease in luminous efficiency. In the present invention, the melting point is a melting point at normal temperature and pressure.

  Moreover, it is preferable that the molecular weight of a thallium compound exists in the range of 206-300.

  In the scintillator layer of the present invention, the content of the additive is desirably an optimum amount according to the target performance and the like, but is 0.001 to 50 mol% with respect to the content of cesium iodide. It is preferable that it is 1-10.0 mol%.

  Here, when the additive is less than 0.001 mol% with respect to cesium iodide, the target light emission luminance cannot be obtained without much difference from the light emission luminance obtained by using cesium iodide alone. Moreover, when it exceeds 50 mol%, the property and function of cesium iodide cannot be maintained.

  In the present invention, after a scintillator layer is formed on the polymer film by vapor deposition of the raw material of the scintillator, it is one hour in an atmosphere in a temperature range of −50 ° C. to + 20 ° C. based on the glass transition temperature of the polymer film. The above heat treatment is required. Thereby, the deformation | transformation of a film and generation | occurrence | production of peeling of a fluorescent substance do not occur, and a scintillator panel with high luminous efficiency is realizable.

  As can be seen from the above description, the scintillator layer according to the present invention is preferably a columnar phosphor layer containing cesium iodide, and is preferably formed by a vapor phase growth method. As the vapor phase growth method, a conventionally known vacuum deposition method, sputtering method, CVD method or the like can be used.

  In addition, it is preferable that the thickness of a fluorescent substance layer is 100-800 micrometers, and it is more preferable that it is 120-700 micrometers from the point from which the characteristic of a brightness | luminance and sharpness is acquired with sufficient balance.

(filler)
In the present invention, as described above, the scintillator layer is characterized by containing phosphor columnar crystals and a filler as its constituent elements. Various forms can be adopted as the form of the contained state, but a form in which a filler is contained between the columnar crystals of the phosphor constituting the scintillator layer is preferable.

  The filler preferably has a refractive index (nD25) of 1.70 or less. Furthermore, it is preferable that it is 1.40 or less. The refractive index is preferably as small as possible, but more preferably 1.20 or more.

  In the present invention, the filler can be used regardless of whether it is organic or inorganic, or liquid or solid, and is preferably organic. However, when the filler is a liquid, the solubility of the phosphor (fluorescent compound) constituting the scintillator layer in the liquid is preferably 0.1 or less.

  As the liquid that can be used as the filler, various water repellent liquids can be used as long as the above requirements are satisfied. Preferred examples include fluorine-based water-repellent liquids (for example, Novec HFE7100, 7600 (hydrofluoroether; manufactured by Sumitomo 3M)), and silicone-based water-repellent liquids (for example, TSF451-0.65 (dimethylsilicone oil-based; Momentive Performance Materials Japan GK).

As a method for containing the filler according to the present invention, (1) a scintillator layer of a scintillator plate at a low pressure of at least 1.0 × 10 ⁵ Pa (normal pressure 1 atm), preferably under conditions closer to vacuum When only a certain surface is immersed in a liquid as a filler, the space between the columnar crystals can be filled with the liquid. The scintillator plate in this state is packaged (sealed) under reduced pressure with a protective layer. Alternatively, (2) after packing the scintillator plate with a protective layer under reduced pressure (sealing), a filler between the columnar crystals of the scintillator layer using a micro syringe or the like for the innermost layer (thermal welding layer) of the sealing ear (For example, lipophilic liquid) is introduced, and then only the microsyringe introduction portion is sealed (heat fusion) again. In addition, the process of introducing the filler using a microsyringe or the like is 1.0 × 10 ⁵ Pa (normal pressure 1 atm) or less, and the sealing pressure condition during decompression packaging is preferable. However, it is not limited to these methods.

  In the present invention, the filler may be formed between the columnar crystals of the phosphor and on the surface of the columnar crystals by a vapor phase growth method. As a material that can be used for this purpose, a paraxylylene-based resin (for example, Parylene C, Parylene N; manufactured by Japan Parylene Co., Ltd.) can be used. Note that as the vapor deposition method, a vacuum deposition method, a sputtering method, a CVD method, or the like can be used.

(Reflective layer)
The reflective layer according to the present invention is for reflecting light emitted from the scintillator to enhance light extraction efficiency. The reflective layer is preferably formed of a material containing any element selected from the element group consisting of Al, Ag, Cr, Cu, Ni, Ti, Mg, Rh, Pt, and Au. In particular, it is preferable to use a metal thin film made of the above elements, for example, an Ag film, an Al film, or the like. Two or more such metal thin films may be formed.

  In addition, it is preferable from a viewpoint of the emitted light extraction efficiency that the thickness of a reflection layer is 0.01-0.3 micrometer.

(Undercoat layer)
The undercoat layer according to the present invention needs to be provided between the reflective layer and the scintillator layer from the viewpoint of protecting the reflective layer.

  The undercoat layer preferably contains a polymer binder (binder), a dispersant and the like.

  The thickness of the undercoat layer is preferably 0.1 to 3 μm. If the thickness is 3 μm or less, light scattering in the undercoat layer is small and sharpness is good. Further, when the thickness of the undercoat layer is 2 μm or less, columnar crystallinity is not disturbed even if heat treatment is performed.

  Hereinafter, components of the undercoat layer will be described.

<Polymer binder>
The undercoat layer according to the present invention is preferably formed by applying and drying a polymer binder (hereinafter also referred to as “binder”) dissolved or dispersed in a solvent. Specific examples of the polymer binder include polyimide or polyimide-containing resin, polyurethane, vinyl chloride copolymer, vinyl chloride-vinyl acetate copolymer, vinyl chloride-vinylidene chloride copolymer, vinyl chloride-acrylonitrile copolymer. Polymer, butadiene-acrylonitrile copolymer, polyamide resin, polyvinyl butyral, polyester, cellulose derivative (nitrocellulose, etc.), styrene-butadiene copolymer, various synthetic rubber resins, phenol resin, epoxy resin, urea resin, melamine resin , Phenoxy resin, silicon resin, acrylic resin, urea formamide resin, and the like. Of these, polyurethane, polyester, vinyl chloride copolymer, polyvinyl butyral, and nitrocellulose are preferably used.

  As the polymer binder according to the present invention, polyimide or a polyimide-containing resin, polyurethane, polyester, vinyl chloride copolymer, polyvinyl butyral, nitrocellulose and the like are particularly preferable in terms of close contact with the scintillator layer. Moreover, it is preferable that the glass transition temperature (Tg) is a polymer having a temperature of 30 to 100 ° C. in terms of attaching a film between the deposited crystal and the substrate. From this viewpoint, a polyester resin is particularly preferable. However, if the heat treatment temperature is improved to improve image characteristics such as luminance, a polymer having a Tg of 30 to 100 ° C. may not be able to ensure sufficient heat resistance. In this case, polyimide or a polyimide-containing resin is used.

  Solvents that can be used to prepare the undercoat layer include N, N-dimethylacetamide, N-methyl-2-pyrrolidone, lower alcohols such as methanol, ethanol, n-propanol, and n-butanol, methylene chloride, and ethylene chloride. Chlorine atom containing hydrocarbons such as, ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, aromatic compounds such as toluene, benzene, cyclohexane, cyclohexanone, xylene, lower fatty acids such as methyl acetate, ethyl acetate, butyl acetate and lower alcohol And ethers such as dioxane, ethylene glycol monoethyl ester, ethylene glycol monomethyl ester, and mixtures thereof.

  The undercoat layer according to the present invention may contain a pigment or a dye in order to prevent scattering of light emitted by the scintillator and improve sharpness and the like.

(Protective layer)
The protective layer according to the present invention focuses on protecting the scintillator layer. That is, cesium iodide (CsI) absorbs water vapor in the air and deliquesces when exposed to a high hygroscopic property, and therefore the main purpose is to prevent this. The protective layer can be formed using various materials.

  In the scintillator panel according to the present invention, as the protective layer, first, a protective film can be provided on the scintillator layer of the scintillator plate.

  Further, the scintillator panel is sealed by a first protective film disposed on the scintillator layer side and a second protective film disposed on the outside of the substrate, and the first protective film is physicochemically bonded to the scintillator layer. It is preferable to set it as the aspect which is not adhere | attached on.

  Here, “not physically bonded” means that it is not bonded by physical interaction or chemical reaction using an adhesive as described above. This non-bonded state is a state in which the scintillator layer surface and the protective film can be treated as a discontinuous optically and mechanically even though the scintillator layer surface and the protective film are point contacted microscopically. It can be said.

  Next, the protective film used in the present invention will be described in detail.

(Protective film)
As a structural example of the protective film used for this invention, the multilayer laminated material which has the structure of outermost layer (protective function layer) / intermediate layer (moisture-proof layer) / innermost layer (thermal welding layer) is mentioned. Furthermore, each layer can be a multilayer as required.

<Innermost layer (thermal welding layer)>
As the innermost thermoplastic resin film, it is preferable to use EVA, PP, LDPE, LLDPE and LDPE, LLDPE produced by using a metallocene catalyst, or a film using a mixture of these films and HDPE films.

<Intermediate layer (moisture-proof layer)>
As the intermediate layer (moisture-proof layer), a layer having at least one inorganic film as described in JP-A-6-95302 and the vacuum handbook revised editions p132 to p134 (ULVAC Japan Vacuum Technology KK) is used. Can be mentioned. Examples of the inorganic film include a metal vapor-deposited film and an inorganic oxide vapor-deposited film.

The metal deposited film, for example _{ZrN, SiC, TiC, Si 3} N 4, a single crystal Si, ZrN, PSG, amorphous Si, W, aluminum and the like, and particularly preferred metal vapor deposition film include, for example, aluminum .

Thin film handbooks p879-p901 (Japan Society for the Promotion of Science), vacuum technology handbooks p502-p509, p612, p810 (Nikkan Kogyo Shimbun), vacuum handbook revised editions p132-p134 (ULVAC Japan Vacuum Technology KK) Inorganic vapor-deposited films as described in (1). As these inorganic vapor deposition films, for example, Cr ₂ O ₃ , Si _x O _y (x = 1, y = 1.5 to 2.0), Ta ₂ O ₃ , ZrN, SiC, TiC, PSG, Si ₃ N ₄ , single crystal Si, amorphous Si, W, AI ₂ O ₃ or the like is used.

  The thermoplastic resin film used as the base material of the intermediate layer (moisture-proof layer) is ethylene tetrafluoroethyl copolymer (ETFE), high-density polyethylene (HDPE), expanded polypropylene (OPP), polystyrene (PS), polymethyl Film materials used for general packaging films such as methacrylate (PMMA), biaxially stretched nylon 6, polyethylene terephthalate (PET), polycarbonate (PC), polyimide, and polyether styrene (PES) can be used.

  As a method for forming a deposited film, vacuum technology handbook and packaging technology Vol 29-No. 8, for example, by resistance or high frequency induction heating method, electrobeam (EB) method, plasma (PCVD) or the like. The thickness of the deposited film is preferably in the range of 40 to 200 nm, more preferably in the range of 50 to 180 nm.

<Outermost layer: protective functional layer>
Low density, which is a polymer film (for example, a polymer film described in Toray Research Center, Inc., a new development of functional packaging materials) used as a general packaging material as a thermoplastic resin film used via a vapor-deposited film sheet Polyethylene (LDPE), HDPE, linear low density polyethylene (LLDPE), medium density polyethylene, unstretched polypropylene (CPP), OPP, stretched nylon (ONy), PET, cellophane, polyvinyl alcohol (PVA), stretched vinylon (OV) , Ethylene-vinyl acetate copolymer (EVOH), vinylidene chloride (PVDC), a polymer of fluorine-containing olefin (fluoroolefin), a fluorine-containing olefin copolymer, or the like can be used.

  Of these thermoplastic resin films, a multilayer film made by coextrusion with a different film, a multilayer film made by laminating at different stretching angles, etc. can be used as required. Furthermore, it is naturally possible to combine the density and molecular weight distribution of the film used to obtain the required physical properties of the packaging material. As the innermost thermoplastic resin film, LDPE, LLDPE produced using LDPE, LLDPE and a metallocene catalyst, or a film using a mixture of these films and HDPE films are used.

  When the inorganic vapor deposition layer is not used, the protective layer needs to have a function as an intermediate layer. In this case, the thermoplastic resin film used for the protective layer may be a simple substance or may be used by laminating two or more kinds of films as required. For example, CPP / OPP, PET / OPP / LDPE, Ny / OPP / LDPE, CPP / OPP / EVOH, Saran UB / LLDPE A biaxially stretched film is used as a raw material.) K-OP / PP, K-PET / LLDPE, K-Ny / EVA (where K is a film coated with vinylidene chloride resin) and the like are used. .

  As a method for producing these protective films, various generally known methods are used. For example, a wet laminate method, a dry laminate method, a hot melt laminate method, an extrusion laminate method, and a thermal laminate method are used. Is possible. Of course, the same method can be used in the case where a film on which an inorganic material is deposited is not used, but in addition to these, depending on the material used, it can be formed by a multilayer inflation method or a coextrusion method.

  As the adhesive used for laminating, generally known adhesives can be used. For example, polyethylene thermoplastic resins such as various polyethylene resins, various polypropylene resins, hot melt adhesives, ethylene-propylene copolymer resins, ethylene-vinyl acetate copolymer resins, ethylene-ethyl acrylate copolymer resins, etc. There are thermoplastic resin hot-melt adhesives such as coalescence resins, ethylene-acrylic acid copolymer resins, ionomer resins, and other hot-melt rubber adhesives. Typical examples of emulsion-type adhesives that are emulsion and latex adhesives are polyvinyl acetate resin, vinyl acetate-ethylene copolymer resin, vinyl acetate and acrylate copolymer resin, vinyl acetate and maleate ester. There are emulsions such as copolymer resins, acrylic acid copolymers, and ethylene-acrylic acid copolymers. Typical examples of latex adhesives include rubber latexes such as natural rubber, styrene butadiene rubber (SBR), acrylonitrile butadiene rubber (NBR), and chloroprene rubber (CR). Dry laminate adhesives include isocyanate adhesives, urethane adhesives, polyester adhesives, and others, as well as paraffin wax, microcrystalline wax, ethylene-vinyl acetate copolymer resin, and ethylene-ethyl acrylate. Known adhesives such as hot melt laminate adhesives, pressure sensitive adhesives, heat sensitive adhesives and the like blended with polymer resins can also be used. More specifically, the polyolefin-based resin adhesive for extrusion laminating includes, in addition to polymers and ethylene copolymer (EVA, EEA, etc.) resins made of polyolefin resins such as various polyethylene resins, polypropylene resins and polybutylene resins, Ionomer resin (ionic copolymer resin) such as L-LDPE resin copolymerized with ethylene and other monomers (α-olefin), DuPont Surlyn, Mitsui Polychemical Co., Ltd., and Mitsui Petrochemical Admer (adhesive polymer), etc. Other UV curable adhesives have recently begun to be used. In particular, LDPE resin and L-LDPE resin are preferable because they are inexpensive and have excellent laminating properties. A mixed resin in which two or more of the above-described resins are blended to cover the defects of each resin is particularly preferable. For example, when L-LDPE resin and LDPE resin are blended, spreadability is improved and neck-in is reduced, so that the lamination speed is improved and pinholes are reduced.

  The thickness of the protective film is preferably 12 μm or more and 200 μm or less, more preferably 50 μm or more, taking into consideration the formability of the voids, the scintillator layer (phosphor layer) protection, sharpness, moisture resistance, workability, etc. 150 μm or less is preferable. The haze ratio is preferably 3% or more and 40% or less, more preferably 3% or more and 10% or less in consideration of sharpness, radiation image unevenness, manufacturing stability, workability, and the like. A haze rate shows the value measured by Nippon Denshoku Industries Co., Ltd. NDH 5000W. The required haze ratio is appropriately selected from commercially available polymer films and can be easily obtained.

(substrate)
As the substrate according to the present invention, various metals, carbon, α-carbon, a heat-resistant resin substrate, and the like can be used, but a heat-resistant resin substrate is particularly preferable in view of image characteristics and cost.

  Conventionally known resins can be used as the heat resistant resin, but so-called engineering plastics are preferably used. Here, “engineering plastics” are high-performance plastics used in industrial applications (industrial applications), and generally have high strength, heat-resistant temperature, excellent chemical resistance, etc. Have advantages.

  The engineering plastics according to the present invention is not particularly limited. For example, polysulfone resin, polyethersulfone resin, polyimide resin, polyetherimide resin, polyamide resin, polyacetal resin, polycarbonate resin, polyethylene terephthalate resin Polybutylene terephthalate resin, aromatic polyester resin, modified polyphenylene oxide resin, polyphenylene sulfide resin, polyether ketone resin and the like are preferably used. These engineering plastics may be used independently and 2 or more types may be used together.

  Furthermore, depending on the curing temperature, it is also preferable to use a super engineering plastic represented by polyether ether ketone (PEEK), polytetrafluoroethylene (PTFE), or the like.

  In this invention, it is preferable to form a board | substrate with resin containing polyimide like the polyimide resin or polyetherimide resin excellent in heat resistance, workability, mechanical strength, and cost.

  Note that, when the scintillator panel and the planar light receiving element surface are bonded, the image quality is not uniform within the light receiving surface of the flat panel detector due to the influence of deformation of the substrate and warpage during vapor deposition. By making the substrate a resin substrate having a thickness of 50 μm or more and 500 μm or less, the scintillator panel is deformed into a shape that matches the planar light receiving element surface shape, and uniform sharpness is obtained over the entire light receiving surface of the flat panel detector.

(Scintillator plate and panel manufacturing method, etc.)
Next, an embodiment of the present invention will be described with reference to FIGS. 1 to 5, but the present invention is not limited to this.

  FIG. 1 is a schematic plan view of a scintillator panel. FIG. 1A is a schematic plan view of a scintillator panel in which a scintillator plate is sealed with a protective film with a four-way seal. FIG. 1B is a schematic plan view of a scintillator panel in which a scintillator plate is sealed with a protective film with a two-way seal. FIG. 1C is a schematic plan view of a scintillator panel in which a scintillator plate is sealed with a protective film with a three-way seal.

  The scintillator panel in FIG. In the figure, reference numeral 1a denotes a scintillator panel. The scintillator panel 1a includes a scintillator plate 101, a first protective film 102a disposed on the scintillator layer 101b (see FIG. 3) side of the scintillator plate 101, and a second protection disposed on the substrate 101a side of the scintillator plate 101. And a film 102b (see FIG. 3). Reference numerals 103 a to 103 d denote four sealing portions of the protective film 102 a and the second protective film 102 b (see FIG. 3), and the sealing portions 103 a to 103 d are formed outside the peripheral edge portion of the scintillator plate 101. Has been. The four-way seal means a state having sealing portions in four directions as shown in the figure. The four-sided seal shown in this figure has a scintillator plate sandwiched between two plate-like protective films of a first protective film 102a and a second protective film 102b (see FIG. 3). It can be manufactured by sealing. In this case, the 1st protective film 102a and the 2nd protective film 102b (refer FIG. 3) may differ or may be the same, and can be suitably selected as needed.

  The scintillator panel in FIG. In the figure, 1b represents a scintillator panel. The scintillator panel 1b includes a scintillator plate 101, a first protective film 104 disposed on the scintillator layer 101b (see FIG. 3) side of the scintillator plate 101, and a second protection disposed on the substrate 101a side of the scintillator plate 101. And a film (not shown). Reference numerals 105 a and 105 b denote two sealing portions of the protective film 104 and a second protective film (not shown) arranged on the substrate side, and the sealing portions 105 a and 105 b are both outside the peripheral portion of the scintillator plate 101. Is formed. The two-side seal means a state having a sealing portion in two directions as shown in the figure. The two-way seal shown in this figure can be manufactured by sandwiching a scintillator plate between protective films formed into a cylindrical shape by the inflation method and sealing the two sides. In this case, the protective films used for the first protective film 104 and the second protective film (not shown) are the same.

  The scintillator panel in FIG. In the figure, 1c shows a scintillator panel. The scintillator panel 1c includes a scintillator plate 101, a first protective film 106 disposed on the scintillator layer 101b (see FIG. 3) side of the scintillator plate 101, and a second protective film disposed on the substrate 101a side of the scintillator plate 101. (Not shown). Reference numerals 107 a to 107 c denote three sealing portions of the first protective film 106 and a second protective film (not shown) disposed on the substrate side. The sealing portions 107 a to 107 c are arranged from the peripheral portion of the scintillator plate 101. Is also formed on the outside. The three-way seal means a state having a sealing portion in three directions as shown in the figure. The three-sided seal shown in this figure can be manufactured by folding a single protective film around the center and sandwiching the scintillator plate between the two protective films that have been molded. . In this case, the protective films used for the first protective film 106 and the second protective film (not shown) are the same. As shown in FIGS. 1 (a) to 1 (c), since the sealing portion of the two protective films of the first protective film and the second protective film is outside the peripheral edge of the scintillator plate, It is possible to prevent moisture from entering. The scintillator layer of the scintillator plate shown in FIGS. 1A to 1C is preferably formed on the substrate by the above-described vapor deposition method. As the vapor deposition method, an evaporation method, a sputtering method, a CVD method, an ion plating method, or the like can be used.

  The form of the scintillator panel shown in FIGS. 1A to 1C can be selected depending on the type of scintillator layer of the scintillator plate, the manufacturing apparatus, and the like.

  FIG. 2 is a schematic diagram showing an example of the configuration of the scintillator panel and the configuration of the ears of the protective layer. In the present application, the sealing of the protective film means that the heat-welded layer, which is the innermost layer of the protective film, is sealed by heating (heat-sealing). Called stop ear). The moisture-proof property (water vapor barrier property) of the protective layer is due to the moisture-proof property (water vapor barrier property) of the intermediate layer (moisture-proof layer). It has an extremely high moisture resistance (water vapor barrier property). Therefore, it is conceivable that if the length of the sealing ear is short, that portion causes deterioration of the scintillator layer due to intrusion of water vapor. Therefore, it can be seen that the length of the protective layer ear has an important meaning on the moisture-proof performance of the protective layer formed by sealing.

One of the typical indicators of moisture resistance (water vapor barrier property) is moisture permeability. This moisture permeability is defined in JIS Z 0208 and is expressed in g / (m ² · 24h) as a unit. When discussing the water vapor transmission rate of a certain material, for example, if the resin film is composed of a single component, the unit does not include the dimension of the film thickness, so if the film thickness is not specified, the relative water vapor transmission rate is determined. It will not be.

  Conversely, even in the case of a composite material composed of a plurality of layers such as a commercially available barrier film material, it is not necessary to worry about the thickness. In general, it may be considered that the moisture permeability of the barrier film material is determined by the moisture-proof layer which is the most moisture-proof (water vapor barrier) layer. That is, the moisture permeability of the barrier film material may be considered to be the moisture permeability of the moisture-proof layer. This is because the moisture permeability of the moisture-proof layer is usually 1 to 3 digits lower than the other layers (= the moisture resistance is 1 to 3 digits higher).

As described above, when the sealed configuration is adopted, the ear portion of the protective layer becomes a rate-limiting portion of the scintillator layer deterioration due to intrusion of water vapor through the protective film, and the length is ideally expressed by the following formula (A-2). I understand that I should take However, in reality, the ear portion of the protective layer is a portion that does not contribute to image formation, so there is also a demand to make it shorter and more practical. In addition, the thickness of the heat-welded layer in the protective layer ear configuration (A) is At, and the total thickness Bt of the heat-welded layer and intermediate layer support in the protective layer ear configuration (B) is as thin as μm. . Therefore, when considering the ratio of At and Bt in the cross section of the ear of the protective layer in the area of the protective film, it is usually as low as about 1%. Specifically, when a protective film of 10 cm × 10 cm is sealed and the thickness At of the heat-welded layer is 20 μm (= 0.02 cm) in the case of the protective layer ear configuration (A), the protective film The total area of the surface is 100 × 2 (upper and lower surfaces) = 200 cm ² . Further, in the case of the four-side sealing, the total area of the heat-welding layer at the ear of the protective layer is 10 × 0.02 × 2 (upper and lower surfaces) × 4 (four directions) = 1.6 cm ² (1.6 / 200) × 100% = 0.8% (about 1%). Therefore, the formula (A-1) is devised from the viewpoint of making the ears of the protective layer short and practical and the contribution of area.

Formula (A-1): Ear length of protective layer = highest moisture permeability among layers existing between each of the moisture-proof layers of the first protective film and the second protective film forming the ear of the protective layer The length in which the layer is equivalent to at least twice the moisture permeability in the thickness direction of the moisture-proof layer of the first protective film in the length direction of the ear Formula (A-2): Length of the ear of the protective layer = The layer having the highest moisture permeability among the layers of the moisture-proof layers of the first protective film and the second protective film forming the ears of the protective layer is the first protection in the length direction of the ears. Length equivalent to the moisture permeability in the thickness direction of the moisture-proof layer of the film Note that it is difficult to actually measure the moisture permeability in the length direction of the ear of the protective layer. It is possible to calculate based on the measurement result. Specifically, if the moisture permeability of a thickness of 1 μm is 300 g / (m ² · 24 h), the moisture permeability of a thickness of 100 μm (= 1 mm) is 0.3 g / (m ² · 24 h).

  FIG. 3 is a diagram showing a schematic cross section along AA ′ of FIG. 1A and a contact state with the planar light receiving element. FIG. 3A is a diagram showing a schematic enlarged cross-section along AA ′ in FIG. 1A and a contact state with the planar light receiving element. FIG. 3B is a schematic enlarged view of a portion indicated by P in FIG.

  The scintillator plate 101 has a substrate 101a and a scintillator layer 101b formed on the substrate 101a. Reference numeral 102b denotes a second protective film disposed on the substrate 101a side of the scintillator plate 101. Reference numeral 108 denotes a gap (air layer) formed between the point contact portions E to I that are in partial contact between the first protective film 102a and the scintillator layer 101b. The void portion (air layer) 108 is an air layer, and the relationship between the refractive index of the void portion (air layer) 108 and the refractive index of the first protective film 102a is the refractive index of the protective film 102a >> Air layer) 108 has a refractive index.

  Reference numeral 109 denotes a gap (air layer) formed between the point contact portions J to O that are in partial contact between the first protective film 102a and the planar light receiving element 201. The void portion (air layer) 109 is an air layer, and the relationship between the refractive index of the void portion (air layer) 109 and the refractive index of the first protective film 102a is the refractive index of the protective film 102a >> Air layer) 109 has a refractive index.

  In the case of the scintillator panels shown in FIGS. 1B and 1C, the relationship between the refractive index of the gaps (air layers) 108 and 109 and the refractive index of the first protective film 102a is shown in FIG. Same as the case.

That is, the first protective film 102a arranged on the scintillator layer 101b side is not in a state of close contact with the scintillator layer 101b but is in partial contact with the point contact portions E to I. When the entire surface of the scintillator layer 101b is covered with the first protective film 102a disposed on the scintillator layer 101b side, the point contact portions E to H are 0.1 sites / mm ² or more with respect to the surface area of the scintillator layer 101b. It is preferable to be 25 locations / mm ² or less. In the present invention, such a state is referred to as a state in which the first protective film disposed on the scintillator layer side is not substantially adhered. In the case of the scintillator panels shown in FIGS. 1B and 1C, the relationship between the number of point contact portions and the surface area of the scintillator layer is the same as that in this figure.

Further, the first protective film 102a is not in a state of close contact with the planar light receiving element 201 but is in partial contact with the point contact portions J to O. The locations of the point contact portions J to O are preferably 0.1 locations / mm ² or more and 25 locations / mm ² or less with respect to the surface area of the planar light receiving element 201.

Sharpness deteriorates when the number of point contact portions between the first protective film 102a and the scintillator layer 101b and the number of point contact portions between the first protective film 102a and the planar light receiving element 201 exceed 25 locations / mm ² , respectively. It is one of the causes. Even when the number of point contact portions is less than 0.1 / mm ² , this is one of the causes of deterioration in luminance and sharpness.

  The number of point contact portions can be measured by the following method.

  The scintillator panel is irradiated with X-rays and the emitted light is read by a planar light receiving element using a CMOS or CCD to obtain signal value data. Power spectrum data for each spatial frequency is obtained by Fourier transforming this data. The number of point contact portions can be known from the position of the peak of the power spectrum. That is, a minute luminance difference occurs between the point portion where the protective layer is in contact and the non-contact portion, and the number of contact points can be known by measuring this period.

  However, in this method, the total number of point contact portions between the first protective film 102a and the scintillator layer 101b and the number of point contact portions between the first protective film 102a and the planar light receiving element 201 is detected. For example, there is a method in which the first protective film 102a and the scintillator layer 101b are completely adhered by an adhesive, and only the number of contact points of the point contact portion between the first protective film 102a and the planar light receiving element 201 is measured. .

  As shown in the figure, the scintillator panel 1a includes a substrate 101a and a scintillator layer 101b, which are a first protective film 102a disposed on the scintillator layer 101b side of the scintillator plate 101 and a second protective film 102b disposed on the substrate 101a side. Is covered with the first protective film 102a in a substantially non-adhered state, and each end of the four sides of the first protective film 102a and the second protective film 102b is sealed.

  As a method of covering the entire surface of the scintillator layer 101b with the first protective film 102a being not substantially adhered, the following method is exemplified.

  1) The surface roughness of the surface of the first protective film that contacts the scintillator layer is 0.05 μm to 0 in terms of Ra, taking into consideration the adhesiveness to the first protective film, the sharpness, the adhesiveness to the planar light receiving element, and the like. .8 μm. The surface shape of the first protective film can be easily adjusted by selecting a resin film to be used or coating a coating film containing an inorganic substance on the surface of the resin film. In addition, surface roughness Ra shows the value measured by Tokyo Seimitsu Co., Ltd. Surfcom 1400D.

  2) When the scintillator plate is sealed with the first protective film and the second protective film, it is performed under a reduced pressure condition of 5 Pa to 8000 Pa. In this case, the number of point contact portions between the protective film and the scintillator layer increases when sealed on the high vacuum side, whereas the number of point contact portions decreases when sealed on the low vacuum side. On the other hand, when the pressure is 8000 Pa or more, wrinkles are easily generated on the surface of the protective film, which is not realistic.

  By combining the above methods 1) to 2) singly or in combination, the entire surface of the scintillator layer 101b can be covered with the first protective film 102a substantially not adhered.

  As a method for making the first protective film 102a and the planar light receiving element 201 not substantially bonded, the following method may be mentioned.

1) A method in which the scintillator panel 1a and the planar light receiving element are arranged so as to overlap each other and then pressed from the second protective film side with an appropriate pressure using the elasticity of a foam material such as a sponge. The planar light receiving element 201 can be substantially not adhered.

  The thickness of the protective film is preferably 12 μm or more and 200 μm or less, more preferably 20 μm or more and 40 μm or less, taking into consideration the formability of the voids, the scintillator layer protection, sharpness, moisture resistance, workability and the like. Thickness shows the value which measured and averaged ten places by the stylus type | mold stylus-type film thickness meter (PG-01).

  The haze ratio is preferably 3% or more and 40% or less, and more preferably 3% or more and 10% or less in consideration of sharpness, radiation image unevenness, manufacturing stability, workability, and the like. A haze rate shows the value measured by Nippon Denshoku Industries Co., Ltd. NDH 5000W.

  The light transmittance of the protective film is preferably 70% or more at 550 nm in consideration of photoelectric conversion efficiency, scintillator emission wavelength, etc., but a film having a light transmittance of 99% or more is difficult to obtain industrially. Substantially 99% to 70% is preferable. The light transmittance indicates a value measured with a spectrophotometer (U-1800) manufactured by Hitachi High-Technologies Corporation.

The moisture permeability of the protective film is preferably 50 g / (m ² · 24 h) (40 ° C./90% RH) (measured according to JIS Z0208) or less, more preferably 10 g in consideration of the protection of the scintillator layer, deliquescence and the like. / (M ² · 24 h) (40 ° C., 90% RH) (measured according to JIS Z0208) is preferable.

  As shown in the figure, the scintillator plate 101 may be sealed with the first protective film 102a and the second protective film 102b by any known method. For example, the scintillator plate 101 can be efficiently sealed by thermal welding using an impulse sealer. For this reason, it is preferable that the innermost layer in contact between the protective film 102a and the protective film 102b is a resin film having heat-fusibility.

  FIG. 4 is a schematic diagram showing a light refraction state in the gap 108 shown in FIG. 3 and a light refraction state in a state where the conventional protective film and the scintillator layer are in close contact with each other. FIG. 4A is a schematic diagram showing a state of light refraction in the gap 108 shown in FIG. FIG. 4B is a schematic view showing a state of light refraction in a state where the conventional protective film and the scintillator layer are in close contact with each other.

  This will be described with reference to FIG.

  In the case shown in this figure, since there is a gap (air layer) 108 between the protective film and the scintillator layer, the refractive index of the first protective film 102a and the refraction of the gap (air layer) 108 are present. The relationship with the refractive index is the refractive index of the first protective film >> the refractive index of the air gap (air layer). For this reason, the light R to T emitted from the scintillator layer is incident on the protective film without being reflected at the interface between the first protective film 102a and the gap (air layer) 108 (in a state having no critical angle). The incident light is emitted to the outside without being re-reflected at the interface between the protective film and the air layer by the optical control structure of air layer (low refractive index layer) / protective film / air layer. Can be prevented.

  This will be described in the case of FIG.

  In the case shown in the figure, since the protective film and the scintillator layer are in close contact with each other, the light Z having an angle exceeding the critical angle θ among the light X to Z emitted from the phosphor surface is the protective layer-air layer. This increases the proportion of total reflection at the interface. For this reason, it becomes one of the causes that sharpness deteriorates.

  In the present invention, when the scintillator plate is sealed with the first protective film and the second protective film, the scintillator layer and the first protective film are not substantially adhered as shown in FIG. It becomes possible to manufacture a scintillator panel that does not deteriorate sharpness by making the protective film and the surface of the planar light receiving element substantially unbonded.

  In addition, by making the substrate a polymer film having a thickness of 50 μm or more and 500 μm or less and making the total thickness of the scintillator panel 1 mm or less, the scintillator panel is transformed into a shape that matches the planar light receiving element surface shape, and a flat panel detector It has been found that uniform sharpness can be obtained over the entire light receiving surface, and the present invention has been achieved.

  In the present invention, as shown in FIGS. 1 to 3, when the scintillator plate is sealed with the first protective film and the second protective film, the first protective film covering the scintillator layer is not substantially adhered. The following effects were obtained (providing a point contact location between the scintillator layer and the first protective film and providing a gap (air layer) between the point contact locations).

  1) Polypropylene film and polyethylene terephthalate film which were difficult to use because of their high refractive index and low sharpness while having excellent physical properties as a protective film in terms of strength The use of polyethylene naphthalate film and the like has become easier, and it has become possible to produce scintillator panels that are of high quality and prevent long-term performance degradation.

  2) Since a highly scratch-resistant protective film can be used without degrading the image quality, a scintillator panel having excellent durability over a long period of time can be realized.

  3) A protective layer having excellent durability can be realized without inhibiting the light guide effect of the phosphor crystal.

  FIG. 5 is a schematic view of a vapor deposition apparatus for forming a scintillator layer on a substrate by a vapor deposition method.

  In the figure, 2 indicates a vapor deposition apparatus. The vapor deposition apparatus 2 includes a vacuum vessel 201, an evaporation source 202 that is provided in the vacuum vessel 201 and deposits vapor on the substrate 3, a substrate holder 203 that holds the substrate 3, and the substrate holder 203 with respect to the evaporation source 202. A substrate rotating mechanism 204 that deposits vapor from the evaporation source 202 by rotating, a vacuum pump 205 that exhausts the vacuum container 201 and introduces the atmosphere, and the like are provided.

  Since the evaporation source 202 contains the scintillator layer forming material and is heated by a resistance heating method, the evaporation source 202 may be composed of an alumina crucible wound with a heater, or a boat or a heater made of a refractory metal. Also good. Further, the method of heating the scintillator layer forming material may be a method such as heating by an electron beam or heating by high frequency induction other than the resistance heating method, but in the present invention, it is easy to handle with a relatively simple configuration, inexpensive, In addition, the resistance heating method is preferable because it can be applied to a large number of substances. The evaporation source 202 may be a molecular beam source by a molecular source epitaxial method.

  The support rotating mechanism 204 includes, for example, a rotating shaft 204a that supports the substrate holder 203 and rotates the substrate holder 204, and a motor (not shown) that is disposed outside the vacuum vessel 201 and serves as a driving source for the rotating shaft 204a. It is configured.

  The substrate holder 203 is preferably provided with a heater (not shown) for heating the substrate 3. By heating the substrate 3, the adsorbed material on the surface of the substrate 3 is separated and removed, and the generation of an impurity layer between the surface of the substrate 3 and the scintillator layer forming material is prevented. The film quality can be adjusted.

  Further, a shutter (not shown) that blocks a space from the evaporation source 202 to the substrate 3 may be provided between the substrate 3 and the evaporation source 202. It is possible to prevent substances other than the object attached to the surface of the scintillator layer forming material from evaporating at the initial stage of vapor deposition and adhering to the substrate 3 by the shutter.

  In order to form a scintillator layer on the substrate 3 using the vapor deposition apparatus 2 configured in this way, first, the support 3 is attached to the substrate holder 203. Next, the vacuum vessel 201 is evacuated. Thereafter, the substrate holder 203 is rotated with respect to the evaporation source 202 by the support rotating mechanism 204, and when the vacuum container 201 reaches a vacuum degree capable of vapor deposition, the scintillator layer forming material is evaporated from the heated evaporation source 202, A phosphor is grown on the surface of the substrate 3 to a desired thickness. The degree of vacuum during vapor deposition is preferably 5 Pa or less, more preferably 0.001 to 1.0 Pa or less in a vacuum atmosphere by introducing an inert gas such as argon into the inside of the vacuum vessel. In this case, the distance between the substrate 3 and the evaporation source 202 is preferably set to 100 mm to 1500 mm. The scintillator layer forming material used as the evaporation source may be processed into a tablet shape by pressure compression or may be in a powder state. Further, instead of the scintillator layer forming material, a raw material or a raw material mixture may be used.

(Radiation flat panel detector)
In the radiation flat panel detector according to the present invention, an image can be converted into digital data by converting the light emitted from the scintillator panel into electric charges on the plane light receiving element surface.

  In the direct vapor deposition type (integrated type), the vapor deposition is directly performed on the surface of the planar light receiving element, and the planar light receiving element and the scintillator layer become an integrated scintillator. The panel is placed. In this case, the scintillator panel is characterized in that it is not physicochemically bonded to the plane light receiving element surface.

  EXAMPLES Hereinafter, although an Example is given and this invention is demonstrated in detail, this invention is not limited to these.

Example 1
(Preparation of scintillator plate)
(Preparation of substrate)
A polyimide film (90 mm × 90 mm) having a thickness of 0.125 mm was prepared as a substrate.

(Formation of reflective layer)
For the polyimide (PI) film substrate, silver was sputtered on one side to a thickness of 0.2 μm (2000 mm).

(Formation of undercoat layer)
Resin undercoat layer A:
Byron 630 (manufactured by Toyobo Co., Ltd .: polymer polyester resin) 100 parts by weight Methyl ethyl ketone (MEK) 100 parts by weight Toluene 100 parts by weight The above formulation is mixed and dispersed in a bead mill for 15 hours to obtain a coating solution for undercoat coating. It was. The coating solution was applied to the substrate surface with a bar coater so that the dry film thickness was 1.0 μm, and then dried at 100 ° C. for 8 hours to prepare an undercoat layer.

(Formation of scintillator layer)
Using the vapor deposition apparatus shown in FIG. 5, a phosphor (CsI: 0.003Tl) was vapor-deposited on the prepared substrate to form a scintillator layer, and a scintillator plate was produced.

  A phosphor material (CsI: 0.003 Tl) was filled in a resistance heating crucible, a substrate was placed on the support holder, and the distance between the resistance heating crucible and the substrate was adjusted to 400 mm. Subsequently, the inside of the vapor deposition apparatus was once evacuated, Ar gas was introduced and the degree of vacuum was adjusted to 0.5 Pa, and then the substrate temperature was maintained at 140 ° C. while rotating the substrate at a speed of 10 rpm. Next, the resistance heating crucible was heated to deposit a phosphor, and when the scintillator layer had a film thickness of 600 μm, the deposition was terminated to obtain a scintillator plate.

(Annealing of scintillator plates)
The scintillator plate was annealed at 150 ° C. for 3 hours in an inert oven under a nitrogen atmosphere.

  Next, the corners of the annealed scintillator plate were processed as shown in FIG. 5 to prepare a scintillator plate.

(Preparation of protective film)
A first protective film and a second protective film were prepared as shown in Table 1.

  This adhesive layer was made of a polyol-isocyanate (= urethane) adhesive and was laminated by a dry laminating method.

(Production of scintillator panel)
The prepared scintillator plate was sealed in the form shown in FIG.1 (c) using the prepared protective film, and the scintillator panel was produced.

  In addition, the sealing was carried out under a reduced pressure of 1000 Pa so that the length of the ear of the protective layer serving as the fused portion was 3.5 mm. The impulse sealer heater used for the fusion was a 5 mm width heater.

(Measurement of emission luminance)
The radiation image conversion panel is set on a 10 cm × 10 cm CMOS flat panel (Radicon X-ray CMOS camera system Shadow_Box 4KEV), and X-rays with a tube voltage of 80 kVp are applied to the back surface of each sample (with a scintillator phosphor layer). Irradiation was performed from the surface not formed), and the measured count value was defined as emission luminance (sensitivity). However, it represents with the relative value which sets the light emission luminance of the scintillator panel of the comparative example 1 to 1.0.

(Moisture resistance test)
20 ° C. 5.5 hours → temperature rise 0.5 hour → 30 ° C. 80% RH 5 hours → temperature drop 1 hour → 20 ° C. humidification cycle thermo 7 days, the deterioration rate of the sharpness of this sample was measured (sharpness The evaluation method will be described later).

Sharpness degradation rate = {1- (sharpness after test / initial sharpness)} × 100%
The sharpness deterioration rate was evaluated as follows.

◎ Less than 0 to 5% ○ Less than 5 to 20% △ Less than 20 to 30% x 30% or more (Specific failure occurrence rate in moisture resistance test)
A specific failure occurrence rate when 1000 samples of the above moisture resistance test were performed was calculated as follows.

  The specific failure occurrence means an evaluation sample that is lowered by two ranks from the average value, with the above-mentioned ◎, ◯, Δ, and × being four ranks.

  The occurrence rate of specific failure occurrence samples is defined as a specific failure occurrence rate (Equation 1).

Specific failure rate = (number of specific failure occurrence samples / 1000 evaluation samples) × 100% (Equation 1)
From the above-mentioned specific failure rate, the following evaluation was made.

◎ 0%
○ More than 0 to less than 5% △ Less than 5 to 20% × 20% or more (Sharpness evaluation)
Each sample is set on a 10 cm long × 10 cm wide CMOS flat panel (X-ray CMOS camera system Shad-o-Box 4KEV manufactured by Radicon), and MTF is measured and calculated for each sample from 12-bit output data.

  Specifically, X-rays with a tube voltage of 80 kVp are irradiated from the back of each sample (surface on which no phosphor layer is formed) through a lead MTF chart, and image data is detected by a CMOS flat panel and recorded on a hard disk. did. Thereafter, the recording on the hard disk was analyzed by a computer to calculate the modulation transfer function (MTF (Modulation Transfer Function)) of the X-ray image recorded on the hard disk. The calculation result (MTF value (%) at a spatial frequency of 1 cycle / mm) was obtained. The higher the MTF value, the better the sharpness.

(Evaluation of image unevenness and linear noise)
Each sample was set on a 10 cm × 10 cm CMOS flat panel (Radicon X-ray CMOS camera system Shad-o-Box 4KEV), and X-rays with a tube voltage of 80 kVp were applied to the back of each sample (scintillator phosphor). A solid image was taken by irradiating from a surface on which no layer was formed. This was reproduced as an image by an image reproducing device, enlarged twice as much as the output device and printed out, and the obtained printed image was visually observed to evaluate the appearance of image unevenness and linear noise. Each of image unevenness and linear noise was evaluated as shown below and shown in Table 1.

◎: No image unevenness or linear noise ○: Light image unevenness or linear noise is observed in less than 1 to 2 locations in the plane △: Light image unevenness or linear noise is observed in less than 2 to 4 locations in the plane X: Image unevenness and linear noise are observed at 4 or more locations in the plane, but the dark portions are less than 5 locations and the evaluation results are summarized in Tables 1 to 3.

  As is apparent from the results shown in Table 3, in the examples according to the present invention, the sharpness deterioration rate and the specific failure occurrence rate in the moisture resistance test are low and the image unevenness is maintained in a state where the light emission luminance is maintained. It can also be seen that there is significantly less linear noise.

Schematic plan view of scintillator panel Schematic diagram showing examples of scintillator panel configuration and protective layer ear configuration Schematic cross-sectional view along AA 'in FIG. FIG. 3 is a schematic diagram showing the state of light refraction in the gap shown in FIG. 3 and the state of light refraction in a state where the conventional protective film and the scintillator layer (phosphor layer) are in close contact with each other. Schematic diagram of a vapor deposition device that forms a scintillator layer on a substrate by vapor deposition.

Explanation of symbols

1a to 1c scintillator panel 101 scintillator plate 101a, 3 substrate 101b scintillator layer (phosphor layer)
101c Reflective layer 101d Resin undercoat layer 102a, 104 First protective film 102b Second protective film 103a-103d, 105a, 105b, 107a-107c Sealing part 108 Air gap part (air layer)
E to H Point contact portion R to T, X to Z Light 2 Vapor deposition apparatus 201 Vacuum container 202 Evaporation source 203 Substrate holder 204 Substrate rotation mechanism 205 Vacuum pump

Claims (11)

A scintillator plate having a scintillator layer on a substrate, the scintillator layer containing phosphor columnar crystals and a filler as its constituent elements, and the entire scintillator plate being covered with a protective layer A scintillator panel characterized by The scintillator panel according to claim 1, wherein a refractive index (nD25) of the filler is 1.70 or less. The scintillator panel according to claim 1, wherein the filler is an organic substance. The scintillator according to any one of claims 1 to 3, wherein the filler is a liquid, and the solubility of the phosphor constituting the scintillator layer in the liquid is 0.1 or less. panel. The scintillator panel according to any one of claims 1 to 4, wherein the liquid as the filler is at least one of a fluorine-based water-repellent liquid and a silicone-based water-repellent liquid. The scintillator panel according to any one of claims 1 to 3, wherein the filler is formed by a vapor deposition method. The scintillator panel according to any one of claims 1 to 6, wherein the phosphor columnar crystal contains cesium iodide and is formed by a vapor phase growth method. The scintillator panel according to claim 1, wherein the substrate is a heat resistant resin. The scintillator panel according to any one of claims 1 to 8, wherein a refractive index (nD25) of the filler is 1.40 or less. The scintillator panel according to any one of claims 1 to 9, further comprising at least one of a reflective layer and an undercoat layer between the substrate and the scintillator layer. It is a radiation flat panel detector provided with the scintillator panel as described in any one of Claims 1-10, and a planar light receiving element, Comprising: The said scintillator panel is not physicochemically adhere | attached on the planar light receiving element surface. Characteristic radiation flat panel detector.

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