JP2006267013A - Stimulable phosphor panel, and manufacturing method for stimulable phosphor panel - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a stimulable phosphor panel of high quality capable of preventing a support body from being corroded by moisture absorption of a phosphor layer, and capable of preventing thereby deterioration of the phosphor layer from being promoted, and a manufacturing method for the stimulable phosphor panel. <P>SOLUTION: This stimulable phosphor panel is layered with a metal substrate 12, an inorganic oxide coating film 14, and a stimulable phosphor layer 16 in this order. The inorganic oxide coating film 14 is formed of anyone of an SiO<SB>2</SB>film, a ZrO<SB>2</SB>film and a TiO<SB>2</SB>film provided by drying an aqueous solution containing at least one out of one or more of metal alkoxides, and a hydrolysate obtained by hydrolyzing the one or more of metal alkoxides, or by drying an application liquid using an aqueous/alcoholic solution as a main agent, and containing at least one out of one or more of the metal alkoxides, and the hydrolysate obtained by hydrolyzing the one or more of metal alkoxides, or formed of a mixture of two kinds or more selected from a group of SiO<SB>2</SB>, ZrO<SB>2</SB>and TiO<SB>2</SB>. <P>COPYRIGHT: (C)2007,JPO&INPIT

Description

  The present invention belongs to the technical field of a photostimulable phosphor panel and a method for producing a photostimulable phosphor panel. Specifically, the present invention has a substrate having a characteristic deterioration due to moisture absorption and a photostimulable phosphor layer. The present invention relates to a photostimulable phosphor panel and a method for producing a photostimulable phosphor panel.

  When irradiated with radiation (X-rays, α-rays, β-rays, γ-rays, electron beams, ultraviolet rays, etc.), a part of this radiation energy is accumulated, and then irradiated with excitation light such as visible light, Phosphors that exhibit photostimulated luminescence according to the stored energy are known. This phosphor is called a stimulable phosphor (accumulating phosphor) and is used for various applications such as medical applications.

As an example, a photostimulable phosphor panel (hereinafter referred to as a phosphor panel (also referred to as a radiation image conversion sheet) having this photostimulable phosphor film (stimulable phosphor layer). The radiation image information recording / reproducing system using the above) is known, and has been put into practical use, for example, as FCR (Fuji Computed Radiography) manufactured by Fuji Photo Film Co., Ltd.
In this system, radiation image information of a subject is recorded on a phosphor panel (phosphor layer) by irradiating X-rays or the like through a subject such as a human body. After recording, the phosphor panel is scanned two-dimensionally with excitation light such as laser light to generate stimulated emission, and this stimulated emission light is read photoelectrically to obtain an image signal. Based on this image signal The reproduced image is output as a radiographic image of a subject to a display device such as a CRT or a recording material such as a photographic photosensitive material.

A phosphor panel is usually prepared by dispersing a stimulable phosphor powder in a solvent containing a binder or the like, and applying the paint to a panel-like support made of glass or resin, followed by drying. Is created.
On the other hand, a phosphor panel in which a phosphor layer is formed on a support by a vacuum film formation method (vapor phase film formation method) such as vacuum deposition or sputtering is also known. The phosphor layer formed by the vacuum film formation method is formed in a vacuum, so there are few impurities, and since there are almost no components such as binders other than the stimulable phosphor, there is little variation in performance, and the luminous efficiency Has excellent properties of being very good.

One factor that deteriorates the characteristics of the phosphor panel is moisture absorption of the phosphor layer.
A phosphor layer, particularly an alkali halide phosphor layer having good characteristics, has high hygroscopicity and easily absorbs moisture even in a normal (normal temperature / normal humidity) environment. This moisture absorption not only causes deterioration of the phosphor layer but also causes corrosion of the support of the phosphor layer. As a result, the mechanical strength and flatness of the phosphor panel are lowered, the phosphor layer is accelerated to deteriorate, and the sharpness of the reproduced image of the phosphor panel is lowered.

  An object of the present invention is to solve the problems of the prior art described above, preventing corrosion of the support due to moisture absorption of the phosphor layer, and further preventing the deterioration of the phosphor layer. It is an object to provide a quality photostimulable phosphor panel and a method for producing the photostimulable phosphor panel.

In order to achieve the above object, the present invention comprises depositing a metal substrate, an inorganic oxide film, and a stimulable phosphor layer in this order, and the inorganic oxide film is one or more kinds of metal alkoxides. And an aqueous solution containing at least one of a hydrolyzate obtained by hydrolyzing one or more metal alkoxides, or a hydrolyzate obtained by hydrolyzing one or more metal alkoxides and one or more metal alkoxides. Any of SiO ₂ film, ZrO ₂ film, TiO ₂ film, or SiO _2, ZrO _2, and TiO _{2 formed} by drying a coating solution mainly containing a water / alcohol solution containing at least one of decomposition products A stimulable phosphor panel characterized in that it is a film made of a mixture of any two or more of the above.

  In this invention, it is preferable that the film thickness of the said inorganic oxide film is 0.5 micrometer-10 micrometers.

  Moreover, in this invention, it is preferable that the surface roughness of the said metal substrate is 1 micrometer or less.

  In the present invention, the inorganic oxide film preferably has a surface roughness of 0.1 μm or less.

In the present invention, the inorganic oxide film is preferably a SiO ₂ film.

  In the metal substrate, Si is 0.38% to 0.42%, Fe is 0.48% to 0.52%, Cu is 1.2% to 2.0%, and Mn is 0.28% to 0.00. 32%, Mg 2.1% to 2.9%, Cr 0.18% to 0.28%, Zn 5.1% to 5.6%, and Zr 0.28% to 0.32 The photostimulable phosphor panel according to claim 1, wherein the stimulable phosphor panel is made of an aluminum alloy containing at least 1%.

In order to achieve the above object, according to the present invention, at least one of the metal substrates has a viscosity of 3 mPa · s to 50 mPa · s, and hydrolyzes one or more metal alkoxides and one or more metal alkoxides. An aqueous solution containing at least one of the hydrolysates obtained by the above, or a water / alcohol solution containing at least one of the hydrolysates obtained by hydrolyzing the one or more metal alkoxides and one or more metal alkoxides Is applied to the substrate to a thickness of 5 μm to 100 μm, and the coating solution is dried on the substrate, and either an SiO ₂ film, a ZrO ₂ film, a TiO ₂ film, or SiO _2, ZrO _2, and the inorganic oxide film is formed consisting of a mixture of any two or more of TiO _2, wherein the inorganic acid There is provided a method of manufacturing a stimulable phosphor panel, which comprises forming a stimulable phosphor layer on the object film.

According to the present invention, using a coating solution that is industrially easy to handle, any of a SiO ₂ film, a ZrO ₂ film, a TiO ₂ film, or a SiO _2, ZrO ₂ film on a metal substrate by a sol-gel method in a simple process. _{In addition,} by providing an inorganic oxide film made of a mixture of any two or more of TiO ₂ , corrosion of the surface of the metal substrate 12 due to moisture absorption of the phosphor layer 16 is prevented, and the surface of the metal substrate 12 is always kept Therefore, it is possible to maintain a good quality, and thereby the high-quality photostimulable phosphor panel and photostimulability can be achieved without causing deterioration of the mechanical strength and flatness of the phosphor panel and the promotion of deterioration of the phosphor layer 16. A method for manufacturing a phosphor panel can be provided.

  Hereinafter, the photostimulable phosphor panel and the method for producing the photostimulable phosphor panel of the present invention will be described in detail with reference to the accompanying drawings.

FIG. 1 shows a schematic cross-sectional view of the photostimulable phosphor panel of the present invention manufactured by the manufacturing method of the present invention.
As shown in FIG. 1, a photostimulable phosphor panel (hereinafter referred to as phosphor panel) 10 of the present invention includes a metal substrate 12, an inorganic oxide film 14 formed on the metal substrate 12, and And at least a stimulable phosphor film (stimulable phosphor layer, hereinafter referred to as a phosphor layer) 16 formed on the inorganic oxide film 14, preferably covering the phosphor layer 16. A moisture-proof protective layer 18 for preventing the phosphor layer 16 from absorbing moisture is provided.
Further, the phosphor panel 10 of the present invention may have an adhesive layer 20 for sealing the phosphor layer 16 as long as the above configuration is satisfied.

In the phosphor panel 10 of the present invention, the metal substrate 12 is made of an aluminum alloy, Si is 0.38% to 0.42%, Fe is 0.48% to 0.52%, and Cu is 1.2. % To 2.0%, Mn from 0.28% to 0.32%, Mg from 2.1% to 2.9%, Cr from 0.18% to 0.28%, Zn from 5.1% to 5.6% and Zr containing 0.28% to 0.32% are preferable, but if it is a metal, there is no particular limitation such as an aluminum alloy, and various types used in the phosphor panel 10 may be used. Is available.
The surface roughness of the metal substrate 12 is preferably 1 μm or less, and particularly preferably 0.5 μm or less. By making the roughness of the surface of the metal substrate 12 1 μm or less, the surface roughness of the inorganic oxide film 14 formed thereon can be 0.1 μm or less.

  Here, the phosphor panel 10 of the present invention has an inorganic oxide film 14 on a metal substrate 12. The inorganic oxide film 14 covers the surface of the metal substrate 12 in order to prevent corrosion of the metal substrate 12 due to moisture absorption of the phosphor layer 16.

The inorganic oxide film 14 is an aqueous solution containing at least one of one or more kinds of metal alkoxides and one or more kinds of hydrolyzates obtained by hydrolyzing one or more kinds of metal alkoxides, or the one or more kinds of metal alkoxides and one kind. One of a SiO ₂ film, a ZrO ₂ film, and a TiO ₂ film formed by drying a coating solution mainly containing a water / alcohol solution containing at least one of hydrolysates obtained by hydrolyzing the above metal alkoxide, Alternatively _, it is a film made of a mixture of any two or more of SiO _2, ZrO _2, and TiO ₂ .

The inorganic oxide film 14 may be any one of the above-described SiO ₂ film, ZrO ₂ film, TiO ₂ film, or a film made of a mixture of any two or more of SiO _2, ZrO _2, and TiO _2. For example, there is no particular limitation, but a SiO ₂ film is particularly preferable.

The inorganic oxide film 14 preferably has a film thickness of 0.5 μm to 10 μm, particularly 1 μm to 6 μm. By setting the film thickness of the inorganic oxide film 14 to 0.5 μm or more, corrosion of the surface of the metal substrate 12 due to moisture absorption of the phosphor layer 16 can be well prevented, and by setting the film thickness to 10 μm or less, inorganic Breakage (crack) due to temperature change of the oxide film 14 can be prevented.
Further, the inorganic oxide film 14 preferably has a surface roughness of 0.1 μm or less, particularly 0.07 μm or less. By setting the surface roughness of the inorganic oxide film 14 to 0.1 μm or less, it is possible to improve the adhesion between the inorganic oxide film 14 and the phosphor layer 16 formed on the inorganic oxide film 14. . Moreover, the granularity of the radiation image by the fine structure of the fluorescent substance layer formed on the inorganic oxide film 14 can be made favorable.

The formation method of the inorganic oxide film 14 is not particularly limited, and various methods can be used as long as the inorganic oxide film 14 is obtained by drying a coating solution made of the above materials.
Especially, the manufacturing method of the phosphor panel of the present invention, that is, the inorganic oxide film 14 has a viscosity of 3 mPa · s to 50 mPa · s, particularly 5 mPa · s to 20 mPa · s. It is preferable that at least one is applied so that the thickness of the coating solution at the time of coating is 5 μm to 100 μm, particularly 10 μm to 70 μm, and dried.
By applying the coating liquid on the metal substrate 12 so that the viscosity of the coating liquid is 3 mPa · s to 50 mPa · s and the thickness of the coating liquid at the time of coating is 5 μm to 100 μm, the fineness of the metal substrate 12 is achieved. The holes can be satisfactorily filled with the coating liquid, the coating liquid is not unevenly coated, and the uniformity of the inorganic oxide film 14 is improved. Furthermore, the formation of cells and the occurrence of cracks during drying of the coating liquid can be reduced, and the inorganic oxide film 14 having no defects can be formed. Moreover, the roughness of the surface of the inorganic oxide film 14 described above can be satisfactorily reduced to 1 μm or less.
There is no particular limitation on the method for drying the coating solution, and it may be heated or dried at room temperature. The primary drying is performed at a temperature of 15 ° C to 40 ° C, and the drying is performed at a temperature of 150 ° C to 350 ° C. It is preferable to dry separately from the secondary drying.

Here, in the present invention, as described above, an aqueous solution containing at least one of one or more kinds of metal alkoxides and one or more kinds of hydrolyzates obtained by hydrolyzing one or more kinds of metal alkoxides, or the one or more kinds of metals. SiO ₂ film, ZrO ₂ film, TiO ₂ film formed by drying a coating solution mainly containing a water / alcohol solution containing at least one of an alkoxide and one or more kinds of hydrolyzates obtained by hydrolyzing one or more metal alkoxides Or an inorganic oxide film 14 made of a mixture of any two or more of SiO _2, ZrO _2, and TiO ₂ on the metal substrate 12 so that the phosphor layer 16 absorbs moisture. Even if the surface of the metal substrate 12 is not corroded, the surface of the metal substrate 12 can always be kept good, and the quality is high. A photostimulable phosphor panel and a method for producing the photostimulable phosphor panel can be provided.
JP-A-2004-61159 discloses a radiation image conversion panel having excellent uniformity of the activator in the phosphor layer and high brightness and high sharpness, and a method for manufacturing the radiation image conversion panel. Further, a phosphor layer having a film thickness of 50 μm to 20 mm is formed on the support by an air layer method, and the support is formed of an aluminum substrate on which an oxide film is formed, and a radiation image conversion panel and a radiation image A method for manufacturing a conversion panel is disclosed. Furthermore, a method is disclosed in which an Al alkoxide compound is applied as an oxide film on an aluminum substrate by applying the Al alkoxide compound onto the aluminum substrate with a spin coater and drying. However, since the Al alkoxide solution is very unstable and solidifies immediately, it cannot be used as a coating solution for forming the inorganic oxide film 14.
On the other hand, the material used for forming the inorganic oxide film 14 in the present invention includes at least one of one or more metal alkoxides and a hydrolyzate obtained by hydrolyzing one or more metal alkoxides. A coating solution mainly comprising an aqueous solution or a water / alcohol solution containing at least one of the hydrolyzate obtained by hydrolyzing the one or more metal alkoxides and the one or more metal alkoxides, Since the material is stable and industrially easy to handle, the photostimulable phosphor panel and the method for producing the photostimulable phosphor panel of the present invention are easily realized.

In the phosphor panel 10 of the present invention, various types of stimulable phosphors that form the phosphor layer 16 can be used. As an example, the following stimulable phosphors are preferably exemplified.
“SrS: Ce, Sm”, “SrS: Eu, Sm”, “ThO ₂ : Er”, and “SrS: Ce, Sm”, which are described in US Pat. No. 3,859,527, _{La 2 O 2 S: Eu,} Sm ".

As disclosed in JP-A-55-12142, “ZnS: Cu, Pb”, “BaO.xAl ₂ O ₃ : Eu (provided that 0.8 ≦ x ≦ 10)”, and the general formula “M ^II ” Stimulable phosphor represented by “O.xSiO ₂ : A”.
(In the above formula, M ^II is at least one selected from the group consisting of Mg, Ca, Sr, Zn, Cd and Ba, and A is Ce, Tb, Eu, Tm, Pb, Tl, Bi and Mn. And at least one selected from the group consisting of 0.5 ≦ x ≦ 2.5.)

A stimulable phosphor represented by the general formula “LnOX: xA” disclosed in JP-A No. 55-12144.
(In the above formula, Ln is at least one selected from the group consisting of La, Y, Gd and Lu, X is at least one of Cl and Br, and A is at least one of Ce and Tb. Also, 0 ≦ x ≦ 0.1.)

A photostimulable phosphor represented by the general formula “(Ba _1-x , M ²⁺ _x ) FX: yA” disclosed in JP-A No. 55-12145.
(In the above formula, M ²⁺ is at least one selected from the group consisting of Mg, Ca, Sr, Zn and Cd, and X is at least one selected from the group consisting of Cl, Br and I. , A is at least one selected from the group consisting of Eu, Tb, Ce, Tm, Dy, Pr, Ho, Nd, Yb, and Er, 0 ≦ x ≦ 0.6, and 0 ≦ y. ≦ 0.2.)

One of the following photostimulable phosphors disclosed in JP-A-57-148285.
That is, the photostimulable phosphor represented by the general formula “xM ₃ (PO ₄ ) ₂ .NX ₂ : yA” or “M ₃ (PO ₄ ) ₂ .yA”;
(In the above formula, M and N are at least one selected from the group consisting of Mg, Ca, Sr, Ba, Zn and Cd, respectively, and X is selected from the group consisting of F, Cl, Br and I. A is at least one selected from the group consisting of Eu, Tb, Ce, Tm, Dy, Pr, Ho, Nd, Yb, Er, Sb, Tl, Mn, and Sn. 0 ≦ x ≦ 6 and 0 ≦ y ≦ 1.)

A photostimulable phosphor represented by the general formula “nReX ₃ · mAX ′ ₂ : xEu” or “nReX ₃ · mAX ′ ₂ : xEu, ySm”;
(In the above formula, Re is at least one selected from the group consisting of La, Gd, Y and Lu, A is at least one selected from the group consisting of Ba, Sr and Ca, and X and X 'Is at least one selected from the group consisting of F, Cl, and Br. Also, 1 × 10 ⁻⁴ <x <3 × 10 ⁻¹ and 1 × 10 ⁻⁴ <y <1 × 10 ⁻¹ , and further 1 × 10 ⁻³ <n / m <7 × 10 ⁻¹ .)

And an alkali halide photostimulable phosphor represented by the general formula “M ^I X · aM ^II X ′ ₂ .bM ^III X ″ ₃ : cA”.
(In the above formula, M ^I is at least one selected from the group consisting of Li, Na, K, Rb and Cs, and M ^II is Be, Mg, Ca, Sr, Ba, Zn, Cd, Cu and at least one trivalent metal selected from the group consisting of Ni, M ^III is, Sc, Y, La, Ce , Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, At least one trivalent metal selected from the group consisting of Tm, Yb, Lu, Al, Ga and In, and X, X ′ and X ″ are selected from the group consisting of F, Cl, Br and I A is from Eu, Tb, Ce, Tm, Dy, Pr, Ho, Nd, Yb, Er, Gd, Lu, Sm, Y, Tl, Na, Ag, Cu, Bi, and Mg. At least one selected from the group consisting of . Also, a 0 ≦ a <0.5, a 0 ≦ b <0.5, a 0 ≦ c <0.2.)

A photostimulable phosphor represented by the general formula “(Ba _1-X , M ^II X) F ₂ .aBaX ₂ : yEu, zA” disclosed in JP-A-56-116777.
(In the above formula, M ^II is at least one selected from the group consisting of Be, Mg, Ca, Sr, Zn and Cd, and X is at least one selected from the group consisting of Cl, Br and I. A is at least one of Zr and Sc, 0.5 ≦ a ≦ 1.25, 0 ≦ x ≦ 1, and 1 × 10 ⁻⁶ ≦ y ≦ 2 × 10 ⁻¹ . Yes, 0 <z ≦ 1 × 10 ⁻²

A stimulable phosphor represented by the general formula “M ^III OX: xCe”, disclosed in JP-A-58-69281.
(In the above formula, M ^III is at least one trivalent metal selected from the group consisting of Pr, Nd, Pm, Sm, Eu, Tb, Dy, Ho, Er, Tm, Yb, and Bi; Is at least one of Cl and Br, and 0 ≦ x ≦ 0.1.)

A stimulable phosphor represented by the general formula “Ba _1-x Ma La FX: yEu ²⁺ ” disclosed in JP _-A- 58-206678.
(In the above formula, M is at least one selected from the group consisting of Li, Na, K, Rb and Cs, and L is Sc, Y, La, Ce, Pr, Nd, Pm, Sm, Gd, It is at least one trivalent metal selected from the group consisting of Tb, Tb, Dy, Ho, Er, Tm, Yb, Lu, Al, Ga, In and Tl, and X is composed of Cl, Br and I. And at least one selected from the group, 1 × 10 ⁻² ≦ x ≦ 0.5, 0 ≦ y ≦ 0.1, and a is x / 2.)

Stimulated fluorescence represented by the general formula “M ^II FX · aM ^I X ′ · bM ′ ^II X ″ ₂ · cM ^III X ₃ · xA: yEu ²⁺ ” disclosed in JP-A-59-75200 body. (In the above formula, M ^II is at least one selected from the group consisting of Ba, Sr and Ca, and M ^I is at least one selected from the group consisting of Li, Na, K, Rb and Cs. M ′ ^II is at least one divalent metal of Be and Mg, and M ^III is at least one trivalent metal selected from the group consisting of Al, Ga, In, and Tl, A is a metal oxide, and X, X ′, and X ″ are at least one selected from the group consisting of F, Cl, Br, and I. Also, 0 ≦ a ≦ 2. 0 ≦ b ≦ 1 × 10 ⁻² , 0 ≦ c ≦ 1 × 10 ⁻² , a + b + c ≧ 10 ⁻⁶ , 0 <x ≦ 0.5, and 0 <y ≦ 0.2.)

In particular, the alkali halide photostimulable phosphor disclosed in Japanese Patent Application Laid-Open No. 57-148285 is preferable in that it has excellent photostimulated luminescence properties and the effects of the present invention can be obtained satisfactorily. In particular, alkali halide photostimulable phosphors in which M ^I contains at least Cs, X contains at least Br, and A is Eu or Bi are preferable. A photostimulable phosphor represented by “CsBr: Eu” is preferable.

The phosphor layer 16 is made of such a photostimulable phosphor, and the formation method is not particularly limited, and can be obtained by various vacuum film formation methods such as vacuum deposition, sputtering, and CVD (Chemical Vapor Deposition). Is available.
Among them, the phosphor layer 16 formed by vacuum deposition is preferable in terms of productivity and the like, and in particular, the material of the phosphor component and the material of the activator (activator) component are separately heated and evaporated. The phosphor layer 16 formed by multi-source vacuum deposition is preferable. For example, in the case of the phosphor layer 16 of the “CsBr: Eu”, cesium bromide (CsBr) is used as the material of the phosphor component, and europium bromide (EuBr _x (x is typically 2) to 3)) are preferably used, each being heated and evaporated separately, and preferably formed by multi-source vacuum deposition.
There is no particular limitation on the heating method in vacuum vapor deposition, and for example, it may be formed by electron beam heating using an electron gun or the like, or resistance heating. Further, when formed by multi-source vacuum deposition, all materials may be heated and evaporated by the same heating means (for example, electron beam heating), or the phosphor component material may be heated by electron beam heating. The material of the activator component that is a trace amount may be formed by resistance heating and heating and evaporation.

The phosphor layer 16 is not limited to any particular film formation conditions, and is obtained by appropriately forming the phosphor layer obtained according to the film formation method and the composition of the phosphor layer 16 to be formed. 16 may be sufficient. As an example, in the case of vacuum deposition, a phosphor layer obtained by forming a film at a film formation rate of 0.05 μm / min to 300 μm / min at a vacuum degree of 1 × 10 ⁻⁵ Pa to 1 × 10 ⁻² Pa. 16 is preferred. In addition, when formed by multi-source vacuum evaporation, the evaporation rate of both materials is controlled so that the amount ratio of the base component and the activator component falls within the target range.
Further, according to the examination by the present applicant, when the above-mentioned various storage phosphors, particularly alkali halide storage phosphors, particularly CsBr: Eu, are formed by vacuum deposition, the inside of the system is once temporarily used. After evacuating to a high degree of vacuum, argon gas or nitrogen gas is introduced into the system to obtain a medium vacuum degree of about 0.01 Pa to 3 Pa, particularly about 0.5 Pa to 1.5 Pa. It is preferable to form the phosphor layer 16 by performing vacuum deposition by heating or the like. The alkali halide phosphor layer 16 such as CsBr: Eu has a columnar crystal structure, and the phosphor layer 16 obtained by forming a film under such a medium vacuum has a particularly good columnar crystal structure. It is preferable in terms of the sharpness of the photostimulated luminescence characteristic image.
Further, the phosphor layer 16 formed may be heated at 300 ° C. or lower, preferably 200 ° C. or lower during film formation by heating the metal substrate 12 or the like.
Furthermore, although there is no limitation also in thickness, the fluorescent substance layer 16 of 50 micrometers or more, especially 200 micrometers or more is preferable.

The phosphor layer 16 formed in this way is subjected to heat treatment (annealing) in order to exhibit the stimulated light emission characteristics well and improve the stimulated light emission characteristics.
The heat treatment conditions of the phosphor layer 16 are not particularly limited, but as an example, under an inert atmosphere such as a nitrogen atmosphere, 50 ° C. to 600 ° C., particularly 100 ° C. to 300 ° C., 10 minutes to 10 hours, In particular, it is preferably performed for 30 minutes to 3 hours.
The heat treatment of the phosphor layer 16 may be performed by a known method such as a method using a firing furnace, and if it is a vacuum deposition apparatus having a heating means for the metal substrate 12, the heat treatment is performed using this. You may implement.

  The phosphor layer 16 by vapor deposition has high hygroscopicity, and its characteristics are easily deteriorated by moisture absorption. Therefore, in the method for manufacturing the phosphor panel 10 of the present invention, in addition to the above configuration, in order to prevent moisture absorption of the phosphor layer 16, the phosphor layer 16 is covered with a moisture-proof protective layer 18 described in detail below. The phosphor layer 16 is preferably sealed to prevent moisture absorption.

As long as the moisture-proof protective layer 18 has sufficient moisture-proof properties, various types can be used, and there is no particular limitation. As an example, a moisture-proof protective layer 18 formed by forming three layers of a SiO ₂ film, a hybrid layer of SiO ₂ and PVA (polyvinyl alcohol), and a SiO ₂ film on a PET (polyethylene terephthalate) film is exemplified. In addition to this, a glass plate (film), a resin film such as polyethylene terephthalate or polycarbonate, a film in which an inorganic substance such as SiO ₂ , Al ₂ O ₃ , or SiC is deposited on the resin film are also preferably exemplified. Note that the on the PET film, the SiO ₂ film / SiO ₂ and the moisture-proof protective layer 18 formed of three layers of hybrid layer / SiO ₂ film of PVA, for example, SiO ₂ film, by a sputtering method, SiO The hybrid layer of ₂ and PVA may be formed using a sol-gel method so that the ratio of PVA and SiO ₂ is 1: 1.

The method for sealing the phosphor layer 16 with the moisture-proof protective layer 18 is not particularly limited. As an example, a method of adhering the moisture-proof protective layer 18 to the surface of the metal substrate 12 by the adhesive layer 20 is illustrated. In the present invention, the moisture-proof protective layer 18 and only the surface of the metal substrate 12 may be bonded. However, in order to obtain the phosphor panel 10 having higher durability, the moisture-proof protective layer is used as shown in the example of the drawing. 18 is preferably bonded not only to the surface of the metal substrate 12 but also to the surface of the phosphor layer 16.
The adhesive layer 20 is not particularly limited as long as it is formed of an adhesive having excellent moisture resistance. As an example, a polyester-based adhesive is preferably exemplified. Further, when the surface of the phosphor layer 16 is also bonded to the moisture-proof protective layer 18, it is preferable that the phosphor layer 16 has an optical characteristic that does not hinder the incidence of radiation and the emission of stimulated emission light.
There is no particular limitation on the formation method and the formation conditions. As an example, coating formation is illustrated.
After providing the adhesive layer 20, the moisture-proof protective layer 18 is placed on the phosphor layer 16, and the moisture-proof protective layer 18 and the metal substrate 12 or further the phosphor layer 16 are sealed and bonded. Although there is no limitation in particular in this sealing adhesion method, Thermal lamination is illustrated, for example.
Further, the phosphor layer 16 is sealed by the moisture-proof protective layer 18 so that the adhesion strength when the moisture-proof protective layer 18 and the surface of the metal substrate 12 are bonded by the adhesive layer 20 is improved and good adhesive strength is obtained. Prior to heating, the sealing portion (adhered portion between the moisture-proof protective layer 18 and the surface of the metal substrate 12) and the phosphor layer 16 may be heated by, for example, heating the metal substrate 12 or the like.

  In the method for manufacturing the phosphor panel 10 of the present invention, the process after sealing the phosphor layer 16 is not particularly limited.

An example of the manufacturing method of the phosphor panel 10 of the present invention will be described.
First, at least one of a hydrolyzate obtained by hydrolyzing one or more metal alkoxides and one or more metal alkoxides having a viscosity of 3 mPa · s to 50 mPa · s, particularly 5 mPa · s to 20 mPa · s. Or an aqueous / alcoholic solution containing at least one of hydrolyzate obtained by hydrolyzing one or more metal alkoxides and one or more metal alkoxides. This coating solution is applied to at least one of the surfaces of the metal substrate 12 so that the coating solution has a thickness of 5 μm to 100 μm, particularly 10 μm to 70 μm. Next, the coating liquid is heated or dried at room temperature, and either SiO ₂ film, ZrO ₂ film, TiO ₂ film, or a mixture of any two or more of SiO _2, ZrO _2, and TiO ₂ is used. An inorganic oxide film 14 is formed.
After forming the inorganic oxide film 14 on the surface of the metal substrate 12, the phosphor layer 16 is formed on the inorganic oxide film 14. On the other hand, the adhesive layer 20 is formed on the entire surface of the moisture-proof protective layer 18 with an appropriately selected adhesive so as to have a predetermined thickness.
The adhesive layer 20 bonds the moisture-proof protective layer 18 and the phosphor layer 16, and further bonds the moisture-proof protective layer 18 and the metal substrate 12. Such an adhesive layer 20 is formed by integrating the layer for adhering the moisture-proof protective layer 18 and the phosphor layer 16 and the layer for adhering the phosphor layer 16 and the metal substrate 12 together. It is possible to form. Further, as described above, it is more preferable in terms of durability and the like.
A moisture-proof protective layer 18 having an adhesive layer 20 is placed on the inorganic oxide film 14, and the phosphor layer 16, the moisture-proof protective layer 18, and the moisture-proof protective layer 18 and the metal substrate 12 are thermally laminated at a predetermined temperature and linear velocity. Adhering by carrying out
Prior to sealing of the phosphor layer 16 by the moisture-proof protective layer 18, the metal substrate 12 may be heated.

  As mentioned above, although the manufacturing method of the photostimulable phosphor panel and the photostimulable phosphor panel of the present invention have been described, the present invention is not limited to the above-mentioned examples, Of course, improvements and changes may be made.

  Hereinafter, specific examples of the present invention will be given, and the present invention will be described in more detail with reference to the accompanying drawings. Needless to say, the present invention is not limited to the following examples.

[Example 1]
As a film forming material for the inorganic oxide film 14, a Si alkoxide solution-based coating solution (Nikko Co., Ltd .: GS-600-1, solid concentration: 36%, viscosity: 8 mPa · sec) is used as the metal substrate 12. A metal substrate 12 made of an aluminum alloy having an area of 450 mm × 450 mm and a surface roughness of 0.03 μm (product name: YH75, manufactured by Nippon Steel Corporation, JIS name: 7075) was prepared.
A coating solution is applied to the surface of the metal substrate 12 by a doctor knife method so that the thickness of the coating solution becomes 30 μm, and then the metal substrate 12 coated with the coating solution is 30 ° C. in an atmosphere of 25 ° C. and a humidity of 40% RH. The film was naturally dried for 5 minutes, and further dried for 1 hour under a temperature condition of 200 ° C. to form an inorganic oxide film 14 which is a SiO ₂ film.
The film thickness of the inorganic oxide film 14 at this time was about 4 μm.

CsBr: is formed on the surface of the inorganic oxide film 14 formed as described above by binary vacuum deposition using europium bromide as an activator film forming material and cesium bromide as a phosphor film forming material. A phosphor layer 16 made of Eu was formed.
Both film forming materials were heated by a resistance heating apparatus using a tantalum crucible and a DC power source with an output of 6 kW.
An aluminum alloy metal substrate 12 having an area of 450 mm × 450 mm is set in a substrate holder of a vacuum deposition apparatus (vacuum chamber), and after depositing each film forming material at each predetermined position, the vacuum chamber is closed and exhausted. Started. For the exhaust, a diffusion pump and a cryocoil were used.
When the degree of vacuum reaches 8 × 10 ⁻⁴ Pa, argon gas is introduced into the vacuum chamber to set the degree of vacuum to 0.5 Pa, and then the crucible filled with the film forming material is energized using a DC power source. Then, the phosphor layer 16 was formed on the surface of the metal substrate 12 by resistance heating.
The outputs of the DC power sources of both crucibles were adjusted so that the Eu / Cs molar concentration ratio in the phosphor layer 16 was 0.003: 1 and the film formation rate was 8 μm / min.
During film formation, the surface of the metal substrate 12 was directly heated using a halogen lamp.
When the thickness of the phosphor layer 16 reached about 700 μm, the film formation was completed, and the metal substrate 12 was taken out from the vacuum chamber. The film thickness was controlled by an experiment conducted in advance.
Next, the metal substrate 12 that had been formed was subjected to an annealing process at a temperature of 200 ° C. for 2 hours in a nitrogen atmosphere.

On the other hand, an SiO ₂ film having a thickness of 100 nm is formed on a PET film having a thickness of 6 μm by sputtering, and a PVA and SiO ₂ film is formed on the SiO ₂ film so that the ratio of PVA to SiO ₂ is 1: 1. A SiO ₂ hybrid layer was formed to 600 nm, and a SiO ₂ film was formed to a thickness of 100 nm on the hybrid layer using a sputtering method to form a moisture-proof protective layer 18.

Using a dispenser, an epoxy resin (Cemedine: EP001) to be the adhesive layer 20 was applied to the peripheral edge on the metal substrate 12. The epoxy resin was applied so that the adhesive layer 20 after bonding had a width of 5 mm and a thickness of 7 μm.
Next, the above-described moisture-proof protective layer 18 cut to a size of 420 mm × 420 mm is placed on the phosphor layer 16 so that the SiO ₂ film side faces the phosphor layer 16, and a press mold having a shape corresponding to the above-described adhesive layer 20 is applied. (Press surface is rubber) Pressed and kept pressed, phosphor layer 16 was sealed, and a phosphor panel having the same configuration as panel 10 shown in FIG. 1 was created.

[Comparative Example 1]
The surface roughness of the metal substrate 12 was not specified, and the phosphor panel 10 was obtained in the same manner as in Example 1 except that the inorganic oxide film 14 was not provided on the metal substrate 12.

[Comparative Example 2]
The surface roughness of the metal substrate 12 is not defined, and the phosphor panel 10 is exactly the same as in Example 1 except that the Al alkoxide solution is used as the coating liquid and the Al ₂ O ₃ film is used as the inorganic oxide film 14. Got.
The Al alkoxide solution was very difficult to manage, and an Al ₂ O ₃ film as the inorganic oxide film 14 could not be applied and formed on the metal substrate 12.

[Comparative Example 3]
A phosphor panel 10 was obtained in exactly the same manner as in Example 1 except that the Al ₂ O ₃ film formed by alumite treatment was changed to the inorganic oxide film 14.

[Example 2]
A phosphor panel 10 was obtained in exactly the same manner as in Example 1 except that the type of the metal substrate 12 was pure aluminum.

[Example 3]
Except that the coating solution used in Example 1 was diluted with isopropyl alcohol so that the viscosity of the coating solution was 4 mPa · s and the thickness of the coating solution during coating was about 10 μm. Thus, the phosphor panel 10 was obtained.

[Example 4]
The coating liquid used in Example 1 was stirred in an open container, and the organic solvent component in the coating liquid was evaporated to make the coating liquid have a viscosity of 40 mPa · s, exactly as in Example 1. The phosphor panel 10 was obtained.

[Example 5]
A phosphor panel 10 was obtained in exactly the same manner as in Example 1 except that the metal substrate 12 having a surface roughness of 2 μm was used.

[Example 6]
Except that the coating solution used in Example 1 was diluted with isopropyl alcohol so that the viscosity of the coating solution was 2 mPa · s and the thickness of the coating solution at the time of coating was about 150 μm. Thus, the phosphor panel 10 was obtained.

[Example 7]
The coating liquid used in Example 1 was stirred in an open container, and the organic solvent component in the coating liquid was evaporated, whereby the viscosity of the coating liquid was 57 mPa · s and the thickness of the coating liquid at the time of coating was about A phosphor panel 10 was obtained in the same manner as in Example 1 except that the thickness was 12 μm.

  The film thickness a of the inorganic oxide film 14 of the obtained phosphor panel, the surface roughness, the presence or absence of cracks, the level of corrosion of the phosphor layer 16, and the uniformity of the obtained radiation image are as follows: It was measured.

[Film thickness of inorganic oxide film]
After depositing the inorganic oxide film 14 on the metal substrate 12, the sample is cut out with a size of 10 mm × 10 mm using an appropriate jig, the cross section of the sample is polished, and a scanning electron microscope (manufactured by JEOL: JSM- 6360), the cross section of the sample was observed, and the film thickness of the inorganic oxide film 14 formed on the surface of the metal substrate 12 was measured.

[Surface roughness of inorganic oxide film]
After depositing the inorganic oxide film 14 on the metal substrate 12, the inorganic oxide film 14 was measured according to JIS B 0651.
The surface roughness of the metal substrate 12 was also measured by the same method.

[Presence or absence of cracks in inorganic oxide film]
After forming the inorganic oxide film 14 on the metal substrate 12, the metal substrate 12 was heated at 200 ° C. to visually evaluate whether the inorganic oxide film 14 was cracked. The case where “a crack was confirmed in the inorganic oxide film 14” was indicated as “X”, and the case where “there was no crack in the inorganic oxide film 14” was indicated as “◯”.

[Corrosion level of phosphor layer]
The phosphor panel obtained as described above is allowed to stand for 3 days in an environment of 30 ° C. and humidity 60% RH, and then mounted on a reader (Fujifilm: Velocity-U) to uniformly distribute 80 kvp X-rays. Radiation images were obtained by irradiating 1 mR and performing a reading operation.
The corroded portion of the phosphor layer 16 is observed as low emission light on the radiographic image. The level at which “no corrosion corrosion is observed” is marked as “◯”, “the level at which corrosion corrosion is observed, but there is no practical problem”, and “the level at which corrosion corrosion is observed and impractical” is marked as “X”. This is also shown in Table 1.

[Uniformity of radiation image]
The phosphor panel obtained as described above was treated in the same manner as in the [corrosion level of phosphor layer] measurement to obtain a radiation image.
The uniformity of the obtained radiographic image was visually evaluated. “Level that image is uniform and has no problem” is indicated by “Good”, “Level that image is slightly rough but has no practical problem” is indicated by “ The result is shown in Table 1 with “x” indicating “the level that is rough and impractical”.

  [Inorganic oxide film thickness], [Surface roughness of inorganic oxide film], [Presence of cracks in inorganic oxide film] [Corrosion level of phosphor layer], and [Uniformity of radiation image] Based on this, the phosphor panels obtained as described above were comprehensively evaluated. In this comprehensive evaluation, ◯ is “no image quality problem”, Δ is “slightly inferior image quality but no practical problem”, and x is “image quality is inferior and impractical”. The overall evaluation is also shown in Table 1.

As can be seen from Table 1, Example 1 is an excellent phosphor panel in which cracks and corrosion are not observed in the inorganic oxide film 14 and the image is uniform, that is, practical. is there.
In Example 2, since the rigidity of the metal substrate is low, the flatness is low, and the image has a slight roughness, but at a level that does not cause a problem in practical use. In Example 3, there is a pinhole in the inorganic oxide film 14, corrosion is observed in a part of the phosphor layer 16, and the image has a slight roughness, but at a level that does not cause a problem in practical use. . In Example 4, fine cracks are observed in a part of the inorganic oxide film 14 and the image has a slight roughness, but at a level that does not cause a problem in practical use. In Example 5, cracks occurred in the inorganic oxide film 14, corrosion was observed in a part of the phosphor layer 16, and the image was slightly rough, but at a level that does not cause a problem in practice. In Example 6, since the surface roughness of the inorganic oxide film 14 was set to 0.15 μm, the image has a slight roughness, but is at a level causing no practical problem. In Example 7, streaks and unevenness of the coating liquid occur on the surface of the metal substrate 12 during coating, and the image has a slight roughness, but at a level that is not problematic in practice.
On the other hand, in Comparative Example 1, since the inorganic oxide film is not provided on the metal substrate 12, corrosion is observed in the phosphor layer 16, the image is rough, and the level is not practical. . In Comparative Example 2, an attempt was made to apply and form an Al ₂ O ₃ film, which is an inorganic oxide film 14, using an alkoxide solution as a coating solution. However, since it is difficult to manage the coating solution, a film is formed on the metal substrate 12. It could not be formed, and a phosphor panel could not be obtained. As for Comparative Example 3, an Al ₂ O ₃ film was formed on the surface of the metal substrate 12 by alumite treatment, but cracks were observed in the inorganic oxide film 14, corrosion in the phosphor layer 16 was observed, and the image was rough. Therefore, it is a level that is not practical in general.

It is sectional drawing which shows schematic structure of one Embodiment of the fluorescent panel manufactured with the manufacturing method of this invention.

Explanation of symbols

10 photostimulable phosphor panel 12 metal substrate 14 inorganic oxide film 16 photostimulable phosphor layer 18 moisture-proof protective layer 20 adhesive layer

Claims (7)

A metal substrate, an inorganic oxide film, and a stimulable phosphor layer are deposited in this order,
An aqueous solution containing at least one of the hydrolyzate obtained by hydrolyzing one or more kinds of metal alkoxides and one or more kinds of metal alkoxides, or the one or more kinds of metal alkoxides and one kind. One of a SiO ₂ film, a ZrO ₂ film, and a TiO ₂ film formed by drying a coating solution mainly containing a water / alcohol solution containing at least one of hydrolysates obtained by hydrolyzing the above metal alkoxide, Alternatively, the photostimulable phosphor panel is a film made of a mixture of any two or more of SiO _2, ZrO _2, and TiO ₂ .   The photostimulable phosphor panel according to claim 1, wherein the inorganic oxide film has a thickness of 0.5 μm to 10 μm.   The photostimulable phosphor panel according to claim 1 or 2, wherein the surface roughness of the metal substrate is 1 µm or less.   The photostimulable phosphor panel according to claim 1, wherein the inorganic oxide film has a surface roughness of 0.1 μm or less. Stimulable phosphor panel according to claim 1 wherein the inorganic oxide coating is a SiO ₂ film.   In the metal substrate, Si is 0.38% to 0.42%, Fe is 0.48% to 0.52%, Cu is 1.2% to 2.0%, and Mn is 0.28% to 0.00. 32%, Mg 2.1% to 2.9%, Cr 0.18% to 0.28%, Zn 5.1% to 5.6%, and Zr 0.28% to 0.32 The photostimulable phosphor panel according to any one of claims 1 to 5, wherein the photostimulable phosphor panel is made of an aluminum alloy containing 1%. An aqueous solution containing at least one of a hydrolyzate obtained by hydrolyzing at least one metal alkoxide and at least one metal alkoxide having a viscosity of 3 mPa · s to 50 mPa · s on at least one of the metal substrates. Alternatively, a coating solution mainly composed of a water / alcohol solution containing at least one of the one or more metal alkoxides and a hydrolyzate obtained by hydrolyzing the one or more metal alkoxides has a thickness of 5 μm to 100 μm. And apply as
The coating liquid is dried on the substrate, and the SiO ₂ film, ZrO ₂ film, TiO ₂ film, or a mixture of any two or more of SiO _2, ZrO _2, and TiO ₂ is used. Forming an inorganic oxide film,
A method for producing a photostimulable phosphor panel, comprising forming a photostimulable phosphor layer on the inorganic oxide film.

Images