JP2003302497A - Manufacturing method of radiological image conversion panel - Google Patents
Manufacturing method of radiological image conversion panelInfo
- Publication number
- JP2003302497A JP2003302497A JP2002107054A JP2002107054A JP2003302497A JP 2003302497 A JP2003302497 A JP 2003302497A JP 2002107054 A JP2002107054 A JP 2002107054A JP 2002107054 A JP2002107054 A JP 2002107054A JP 2003302497 A JP2003302497 A JP 2003302497A
- Authority
- JP
- Japan
- Prior art keywords
- phosphor
- radiation image
- vapor deposition
- evaporation source
- image conversion
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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Links
Abstract
Description
【０００１】[0001]
【発明の属する技術分野】本発明は、蓄積性蛍光体を利
用する放射線画像記録再生方法に用いられる放射線像変
換パネルの製造方法に関するものである。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method of manufacturing a radiation image conversion panel used in a radiation image recording / reproducing method using a stimulable phosphor.
【０００２】[0002]
【従来の技術】Ｘ線などの放射線が照射されると、放射
線エネルギーの一部を吸収蓄積し、そののち可視光線や
赤外線などの電磁波（励起光）の照射を受けると、蓄積
した放射線エネルギーに応じて発光を示す性質を有する
蓄積性蛍光体（輝尽発光を示す輝尽性蛍光体等）を利用
して、この蓄積性蛍光体を含有するシート状の放射線像
変換パネルに、被検体を透過したあるいは被検体から発
せられた放射線を照射して被検体の放射線画像情報を一
旦蓄積記録した後、パネルにレーザ光などの励起光を走
査して順次発光光として放出させ、そしてこの発光光を
光電的に読み取って画像信号を得ることからなる、放射
線画像記録再生方法が広く実用に共されている。読み取
りを終えたパネルは、残存する放射線エネルギーの消去
が行われた後、次の撮影のために備えられて繰り返し使
用される。2. Description of the Related Art When radiation such as X-rays is irradiated, a part of the radiation energy is absorbed and accumulated, and then, when irradiated with electromagnetic waves (excitation light) such as visible light and infrared rays, the accumulated radiation energy is changed. A stimulable phosphor having a property of emitting light (such as a stimulable phosphor exhibiting stimulated luminescence) is used to apply a test object to a sheet-shaped radiation image conversion panel containing the stimulable phosphor. After the radiation image information of the subject is once stored and recorded by irradiating the transmitted or emitted radiation from the subject, the panel is scanned with excitation light such as laser light and sequentially emitted as emitted light, and the emitted light is emitted. A radiation image recording / reproducing method, which consists of photoelectrically reading an image signal to obtain an image signal, is widely used in practice. The panel that has finished reading is erased of the remaining radiation energy, and then prepared and used repeatedly for the next imaging.
【０００３】放射線画像記録再生方法に用いられる放射
線像変換パネル（蓄積性蛍光体シートともいう）は、基
本構造として、支持体とその上に設けられた蛍光体層と
からなるものである。ただし、蛍光体層が自己支持性で
ある場合には必ずしも支持体を必要としない。また、蛍
光体層の上面（支持体に面していない側の面）には通
常、保護層が設けられていて、蛍光体層を化学的な変質
あるいは物理的な衝撃から保護している。A radiation image conversion panel (also referred to as a stimulable phosphor sheet) used in the radiation image recording / reproducing method has a basic structure comprising a support and a phosphor layer provided thereon. However, when the phosphor layer is self-supporting, a support is not always necessary. In addition, a protective layer is usually provided on the upper surface of the phosphor layer (the surface not facing the support) to protect the phosphor layer from chemical alteration or physical impact.
【０００４】蛍光体層としては、蓄積性蛍光体とこれを
分散状態で含有支持する結合剤とからなるもの、蒸着法
や焼結法によって形成される結合剤を含まないで蓄積性
蛍光体の凝集体のみから構成されるもの、および蓄積性
蛍光体の凝集体の間隙に高分子物質が含浸されているも
のなどが知られている。The phosphor layer is composed of a stimulable phosphor and a binder which contains and supports the stimulable phosphor in a dispersed state. The phosphor layer does not include a binder formed by a vapor deposition method or a sintering method. Known are ones composed only of aggregates, ones in which polymer substances are impregnated in the gaps between the aggregates of stimulable phosphors, and the like.
【０００５】また、上記放射線画像記録再生方法の別法
として本出願人による特願平１１−３７２９７８号明細
書には、従来の蓄積性蛍光体における放射線吸収機能と
エネルギー蓄積機能とを分離して、少なくとも蓄積性蛍
光体（エネルギー蓄積用蛍光体）を含有する放射線像変
換パネルと、放射線を吸収して紫外乃至可視領域に発光
を示す蛍光体（放射線吸収用蛍光体）を含有する蛍光ス
クリーンとの組合せを用いる放射線画像形成方法が提案
されている。この方法は、被検体を透過などした放射線
をまず、該スクリーンまたはパネルの放射線吸収用蛍光
体により紫外乃至可視領域の光に変換した後、その光を
パネルのエネルギー蓄積用蛍光体にて放射線画像情報と
して蓄積記録する。次いで、このパネルに励起光を走査
して発光光を放出させ、この発光光を光電的に読み取っ
て画像信号を得るものである。このような放射線像変換
パネルおよび蛍光スクリーンも、本発明に包含される。As another method of the above-mentioned radiation image recording / reproducing method, Japanese Patent Application No. 11-372978 filed by the present applicant separates the radiation absorbing function and the energy storing function in the conventional stimulable phosphor. A radiation image conversion panel containing at least a stimulable phosphor (energy storage phosphor), and a phosphor screen containing a phosphor that absorbs radiation and emits light in the ultraviolet to visible region (radiation absorption phosphor). A radiation image forming method using a combination of the above has been proposed. In this method, radiation that has passed through a subject is first converted into light in the ultraviolet or visible region by the radiation-absorbing phosphor of the screen or panel, and the light is then converted into a radiation image by the energy-storing phosphor of the panel. Store and record as information. Next, the panel is scanned with excitation light to emit emitted light, and the emitted light is photoelectrically read to obtain an image signal. Such a radiation image conversion panel and a fluorescent screen are also included in the present invention.
【０００６】放射線画像記録再生方法（および放射線画
像形成方法）は上述したように数々の優れた利点を有す
る方法であるが、この方法に用いられる放射線像変換パ
ネルにあっても、できる限り高感度であってかつ画質
（鮮鋭度、粒状性など）の良好な画像を与えるものであ
ることが望まれている。The radiation image recording / reproducing method (and the radiation image forming method) has a number of excellent advantages as described above, and even the radiation image conversion panel used in this method has as high a sensitivity as possible. It is desired to provide an image having good image quality (sharpness, graininess, etc.).
【０００７】感度および画質を高めることを目的とし
て、例えば特公平６−７７０７９号公報に記載されてい
るように、蛍光体層を気相堆積法により形成することか
らなる放射線像変換パネルの製造方法が提案されてい
る。気相堆積法には蒸着法やスパッタ法などがあり、例
えば蒸着法は、蛍光体またはその原料からなる蒸発源を
抵抗加熱器や電子線の照射により加熱して蒸発源を蒸
発、飛散させ、金属シートなどの基板表面にその蒸発物
を堆積させることにより、蛍光体の柱状結晶からなる蛍
光体層を形成するものである。For the purpose of enhancing sensitivity and image quality, for example, as described in Japanese Patent Publication No. 6-77079, a method of manufacturing a radiation image conversion panel, which comprises forming a phosphor layer by a vapor deposition method. Is proposed. Vapor deposition methods include vapor deposition methods and sputtering methods. For example, the vapor deposition method heats an evaporation source made of a phosphor or its raw material by irradiation of a resistance heater or an electron beam to evaporate and scatter the evaporation source, By depositing the evaporation product on the surface of a substrate such as a metal sheet, a phosphor layer made of columnar crystals of the phosphor is formed.
【０００８】気相堆積法により形成された蛍光体層は、
結合剤を含有せず、蛍光体のみからなり、蛍光体の柱状
結晶と柱状結晶の間には空隙（クラック）が存在する。
このため、励起光の進入効率や発光光の取出し効率を上
げることができるので高感度であり、また励起光の平面
方向への散乱を防ぐことができるので高鮮鋭度の画像を
与えることができる。The phosphor layer formed by the vapor deposition method is
It does not contain a binder and is composed only of the phosphor, and there are voids (cracks) between the columnar crystals of the phosphor.
For this reason, it is possible to improve the entrance efficiency of the excitation light and the extraction efficiency of the emitted light, so that the sensitivity is high, and since it is possible to prevent the excitation light from being scattered in the plane direction, it is possible to provide an image with high sharpness. .
【０００９】ＰＣＴ特許出願第ＷＯ ０１／０３１５６
Ａ１号公報には、ユーロピウム付活ハロゲン化セシウム
（ＣｓＸ：Ｅｕ）輝尽性蛍光体を基板上に蒸着（一元蒸
着）させることからなる放射線像変換パネルの製造方法
が開示されている。しかしながら、この公報には、得ら
れた蒸着膜中に付活剤Ｅｕの濃度分布が生じることにつ
いても、更にはＥｕ濃度分布を解消するための手段につ
いても、全く記載されていない。PCT Patent Application No. WO 01/03156
A1 discloses a method for producing a radiation image conversion panel, which comprises depositing a europium-activated cesium halide (CsX: Eu) stimulable phosphor on a substrate (unitary vapor deposition). However, this publication does not describe the occurrence of the concentration distribution of the activator Eu in the obtained vapor-deposited film, nor the means for eliminating the Eu concentration distribution.
【００１０】[0010]
【発明が解決しようとする課題】本発明者は、ユーロピ
ウム付活アルカリ金属ハロゲン化物系輝尽性蛍光体から
なる蛍光体層を蒸着法により形成する方法について研究
した結果、母体成分と付活剤成分とで蒸気圧に大きな差
があるために、通常の一元蒸着では蒸気圧の高い母体成
分が先に蒸発しやすく、結果として蛍光体層中に付活剤
Ｅｕの濃度分布が生じて、蒸発源として仕込んだ蛍光体
の組成と形成された蛍光体層中の蛍光体の組成とが一致
しなかったり、蛍光体層の厚み方向に蛍光体の組成が均
一とならないなどの問題が生じることが分かった。この
ことは、蛍光体層からの輝尽発光量を減少させ、蛍光体
層の柱状結晶性を低下させ、更には蛍光体層に亀裂や剥
離突沸を発生させて放射線画像上に画像欠陥をもたらす
ものである。DISCLOSURE OF THE INVENTION The present inventors have studied a method of forming a phosphor layer composed of a europium-activated alkali metal halide stimulable phosphor by a vapor deposition method, and as a result, have found that a base component and an activator are used. Since there is a large difference in vapor pressure between the components, the base component having a high vapor pressure is likely to evaporate first in ordinary unitary vapor deposition, resulting in a concentration distribution of the activator Eu in the phosphor layer, which results in evaporation. Problems such as the composition of the phosphor charged as a source and the composition of the phosphor in the formed phosphor layer may not match, or the composition of the phosphor may not be uniform in the thickness direction of the phosphor layer may occur. Do you get it. This reduces the amount of stimulated luminescence from the phosphor layer, reduces the columnar crystallinity of the phosphor layer, and further causes cracks and peeling bumps in the phosphor layer to cause image defects on the radiation image. It is a thing.
【００１１】本発明は、高感度であって、高画質の放射
線画像を与える放射線像変換パネルの製造方法を提供す
ることにある。It is an object of the present invention to provide a method of manufacturing a radiation image conversion panel which is highly sensitive and gives a high quality radiation image.
【００１２】[0012]
【課題を解決するための手段】本発明は第一に、蒸着装
置内にて、蛍光体もしくは蛍光体原料を含む蒸発源を加
熱して発生する物質を基板上に蒸着させることにより蛍
光体層を形成する工程を含む放射線像変換パネルの製造
方法において、蒸着装置として蒸発源と該基板との間に
開閉可能なシャッタが備えられた蒸着装置を用い、蒸発
源として下記基本組成式（Ｉ）を有するユーロピウム付
活アルカリ金属ハロゲン化物系輝尽性蛍光体を含む蒸発
源を用いて、該シャッタを閉じた状態で蒸着を開始し、
一定時間経過後にシャッタを開いて基板上に該蛍光体を
蒸着させることを特徴とする放射線像変換パネルの製造
方法。SUMMARY OF THE INVENTION The first aspect of the present invention is to deposit a substance generated by heating an evaporation source containing a phosphor or a phosphor material in a vapor deposition apparatus on a substrate to deposit the phosphor layer. In a method of manufacturing a radiation image conversion panel including a step of forming an evaporation source, an evaporation apparatus having a shutter that can be opened and closed between the evaporation source and the substrate is used as the evaporation apparatus, and the following basic composition formula (I) is used as the evaporation source. Using an evaporation source containing a europium-activated alkali metal halide-based stimulable phosphor having, vapor deposition is started with the shutter closed.
A method for manufacturing a radiation image conversion panel, comprising: opening a shutter after a lapse of a predetermined time to deposit the phosphor on a substrate.
【００１３】
基本組成式（Ｉ）：
ＭIＸ・ａＭIIＸ’2・ｂＭIIIＸ”3：ｚＥｕ ‥‥（Ｉ）
［ただし、ＭIはＬｉ、Ｎａ、Ｋ、Ｒｂ及びＣｓからな
る群より選ばれる少なくとも一種のアルカリ金属を表
し；ＭIIはＢｅ、Ｍｇ、Ｃａ、Ｓｒ、Ｂａ、Ｎｉ、Ｃ
ｕ、Ｚｎ及びＣｄからなる群より選ばれる少なくとも一
種のアルカリ土類金属又は二価金属を表し；ＭIIIはＳ
ｃ、Ｙ、Ｌａ、Ｃｅ、Ｐｒ、Ｎｄ、Ｐｍ、Ｓｍ、Ｅｕ、
Ｇｄ、Ｔｂ、Ｄｙ、Ｈｏ、Ｅｒ、Ｔｍ、Ｙｂ、Ｌｕ、Ａ
ｌ、Ｇａ及びＩｎからなる群より選ばれる少なくとも一
種の希土類元素又は三価金属を表し；Ｘ、Ｘ’及びＸ”
はそれぞれ、Ｆ、Ｃｌ、Ｂｒ及びＩからなる群より選ば
れる少なくとも一種のハロゲンを表し；そしてａ、ｂ及
びｚはそれぞれ、０≦ａ＜０．５、０≦ｂ＜０．５、０
＜ｚ＜１．０の範囲内の数値を表す］[0013] The basic formula (I): M I X · aM II X '2 · bM III X "3: zEu ‥‥ (I) [ However, M I is the group consisting of Li, Na, K, Rb and Cs Represents at least one alkali metal selected from the group; M II is Be, Mg, Ca, Sr, Ba, Ni, C
represents at least one alkaline earth metal or divalent metal selected from the group consisting of u, Zn and Cd; M III is S
c, Y, La, Ce, Pr, Nd, Pm, Sm, Eu,
Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu, A
represents at least one rare earth element or trivalent metal selected from the group consisting of 1, Ga and In; X, X ′ and X ″
Each represent at least one halogen selected from the group consisting of F, Cl, Br and I; and a, b and z represent 0 ≦ a <0.5, 0 ≦ b <0.5, 0, respectively.
<Represents a numerical value within the range of z <1.0]
【００１４】本発明は第二に、蛍光体もしくはその原料
を含む蒸発源を加熱することによって発生する物質を基
板上に蒸着させることにより蛍光体層を形成する工程を
含む放射線像変換パネルの製造方法において、該蒸発源
として上記基本組成式（Ｉ）を有するユーロピウム付活
アルカリ金属ハロゲン化物系輝尽性蛍光体を含む蒸発源
を用い、そして蒸発源に少なくとも該蛍光体の母体成分
を補給しながら、基板上に蛍光体を蒸着させることを特
徴とする放射線像変換パネルの製造方法にもある。Second, the present invention manufactures a radiation image conversion panel including a step of forming a phosphor layer by depositing a substance generated by heating an evaporation source containing the phosphor or its raw material on a substrate. In the method, an evaporation source containing a europium-activated alkali metal halide stimulable phosphor having the above basic composition formula (I) is used as the evaporation source, and the evaporation source is replenished with at least a matrix component of the phosphor. However, there is also a method of manufacturing a radiation image conversion panel, which is characterized in that a phosphor is vapor-deposited on a substrate.
【００１５】[0015]
【発明の実施の形態】本発明の第一の製造方法におい
て、蒸発源が全て蒸発するのに要する時間をＴとすると
き、蒸着開始後１／１０Ｔ乃至１／２Ｔ経過時にシャッ
タを開くことが好ましく、そして蒸着開始後１／５Ｔ乃
至１／２Ｔ経過時にシャッタを開くことがより好まし
い。BEST MODE FOR CARRYING OUT THE INVENTION In the first manufacturing method of the present invention, when the time required for the evaporation source to completely evaporate is T, the shutter can be opened 1 / 10T to 1 / 2T after the start of vapor deposition. It is more preferable that the shutter is opened 1 / 5T to 1 / 2T after the start of vapor deposition.
【００１６】更に一定時間経過後に再びシャッタを閉じ
て基板上への蛍光体の蒸着を中止することが好ましい。
その場合に、蒸着開始後１／２Ｔ乃至９／１０Ｔ経過時
にシャッタを閉じることが好ましく、そして蒸着開始後
１／２Ｔ乃至２／３Ｔ経過時にシャッタを閉じることが
好ましい（ただし、１／２Ｔ経過時にシャッタを開くと
き、１／２Ｔは含まない）。Further, it is preferable to close the shutter again after a lapse of a certain time to stop the vapor deposition of the phosphor on the substrate.
In that case, it is preferable to close the shutter when 1 / 2T to 9 / 10T has elapsed after the start of vapor deposition, and it is preferable to close the shutter when 1 / 2T to 2 / 3T has elapsed after the vapor deposition has started (however, when 1 / 2T has elapsed). (When opening the shutter, 1 / 2T is not included).
【００１７】蒸発源に少なくとも蛍光体の母体成分を補
給しながら、蒸着を行うことが好ましい。It is preferable to perform vapor deposition while supplying at least the matrix component of the phosphor to the evaporation source.
【００１８】本発明の第二の製造方法において、蒸発源
から蒸発するユーロピウムの蒸発量に応じて、少なくと
も蛍光体母体成分の補給速度を制御することが好まし
い。また、蒸発源に、蒸発源中の蛍光体のユーロピウム
含量よりも低いユーロピウム含量の該蛍光体を補給する
ことが好ましい。In the second production method of the present invention, it is preferable to control at least the replenishment rate of the phosphor matrix component in accordance with the amount of europium evaporated from the evaporation source. Further, it is preferable to supplement the evaporation source with the phosphor having a lower europium content than that of the phosphor in the evaporation source.
【００１９】本発明の第一及び第二の製造方法におい
て、基本組成式（Ｉ）におけるＭIＸがＣｓＢｒであ
り、そしてｚが０．００１≦ｚ≦０．１の範囲内の数値
であることが好ましい。[0019] In the first and second production process of the present invention, an M I X in the basic formula (I) is CsBr, and z is a number in the range of 0.001 ≦ z ≦ 0.1 It is preferable.
【００２０】以下に、本発明の放射線像変換パネルの第
一の製造方法について、電子線蒸着法により蛍光体層を
形成する場合を例にとって図面を参照しながら詳細に説
明する。The first method of manufacturing the radiation image storage panel of the present invention will be described in detail below with reference to the drawings, taking the case of forming a phosphor layer by an electron beam evaporation method as an example.
【００２１】蛍光体層形成のための基板は、通常は放射
線像変換パネルの支持体を兼ねるものであり、従来の放
射線像変換パネルの支持体として公知の材料から任意に
選ぶことができるが、特に好ましい基板は、石英ガラス
シート、サファイアガラスシート；アルミニウム、鉄、
スズ、クロムなどからなる金属シート；アラミドなどか
らなる樹脂シートである。公知の放射線像変換パネルに
おいて、パネルとしての感度もしくは画質（鮮鋭度、粒
状性）を向上させるために、二酸化チタンなどの光反射
性物質からなる光反射層、もしくはカーボンブラックな
どの光吸収性物質からなる光吸収層などを設けることが
知られている。本発明で用いられる基板についても、こ
れらの各種の層を設けることができ、それらの構成は所
望の放射線像変換パネルの目的、用途などに応じて任意
に選択することができる。さらに、放射線画像の鮮鋭度
を向上させる目的で、基板の蛍光体層側の表面（支持体
の蛍光体層側の表面に下塗層（接着性付与層）、光反射
層あるいは光吸収層などの補助層が設けられている場合
には、それらの補助層の表面であってもよい）には微小
な凹凸が形成されていてもよい。The substrate for forming the phosphor layer usually doubles as a support for the radiation image conversion panel, and can be arbitrarily selected from materials known as a support for conventional radiation image conversion panels. Particularly preferred substrates are quartz glass sheets, sapphire glass sheets; aluminum, iron,
A metal sheet made of tin, chromium, etc .; a resin sheet made of aramid, etc. In a known radiation image conversion panel, in order to improve sensitivity or image quality (sharpness, graininess) as a panel, a light reflecting layer made of a light reflecting material such as titanium dioxide, or a light absorbing material such as carbon black. It is known to provide a light absorption layer and the like. The substrate used in the present invention can also be provided with these various layers, and their configuration can be arbitrarily selected according to the desired purpose and application of the radiation image conversion panel. Further, for the purpose of improving the sharpness of the radiation image, the surface of the substrate on the side of the phosphor layer (a subbing layer (adhesion-imparting layer) on the surface of the support on the side of the phosphor layer, a light reflection layer or a light absorption layer, etc.) When the auxiliary layers are provided, they may be the surfaces of these auxiliary layers), and fine irregularities may be formed.
【００２２】本発明に用いられるユーロピウム付活アル
カリ金属ハロゲン化物系輝尽性蛍光体は、前記の基本組
成式（Ｉ）で示される。基本組成式（Ｉ）において、蛍
光体母体を表すＭIＸはＣｓＢｒであることが好まし
く、付活剤Ｅｕの量を表すｚは０．００１≦ｚ≦０．１
の範囲内の数値であることが好ましい。さらに、基本組
成式（Ｉ）には必要に応じて、酸化アルミニウム、二酸
化珪素、酸化ジルコニウムなどの金属酸化物を添加物と
して、ＭIＸ１モルに対して０．５モル以下の量で加え
てもよい。The europium-activated alkali metal halide stimulable phosphor used in the present invention is represented by the above basic composition formula (I). Basic composition formula (I), it is preferred that the M I X representing a phosphor matrix is CsBr, z is 0.001 ≦ z ≦ representing the amount of the activator Eu 0.1
It is preferably a numerical value within the range. Furthermore, if necessary, a metal oxide such as aluminum oxide, silicon dioxide, or zirconium oxide may be added to the basic composition formula (I) as an additive in an amount of 0.5 mol or less relative to 1 mol of M I X. Good.
【００２３】まず、上記の輝尽性蛍光体を含む蒸発源を
用意する。蒸発源は、一般には輝尽性蛍光体のみから構
成されるが、例えば輝尽性蛍光体と付活剤成分や添加物
成分との混合物であってもよい。蒸発源は、突沸防止な
どの点からその含水量が０．５重量％以下であることが
好ましい。蛍光体がＣｓＢｒ：Ｅｕのように吸湿性であ
る場合には特に、含水量をこのような低い値に抑えるこ
とは突沸防止などの点から重要である。蒸発源の脱水
は、蛍光体を減圧下で１００〜３００℃の温度範囲で加
熱処理したり、あるいは窒素雰囲気などの水分を含まな
い雰囲気中で、蛍光体の融点以上の温度で数十分乃至数
時間加熱溶融することにより行うことができる。First, an evaporation source containing the above stimulable phosphor is prepared. The evaporation source is generally composed of only the stimulable phosphor, but may be, for example, a mixture of the stimulable phosphor and an activator component or an additive component. The evaporation source preferably has a water content of 0.5 wt% or less from the viewpoint of preventing bumping. Especially when the phosphor is hygroscopic like CsBr: Eu, it is important to suppress the water content to such a low value from the viewpoint of bumping prevention. The evaporation source is dehydrated by heating the phosphor under reduced pressure in the temperature range of 100 to 300 ° C., or in a moisture-free atmosphere such as a nitrogen atmosphere at a temperature equal to or higher than the melting point of the phosphor for several tens of minutes. It can be performed by heating and melting for several hours.
【００２４】また、蒸発源の相対密度は、８０％以上９
８％以下であることが好ましく、より好ましくは９０％
以上９６％以下である。蒸発源が相対密度の低い粉体状
態であると、蒸着の際に粉体が飛散するなどの不都合が
生じたり、蒸発源の表面から均一に蒸発しないで蒸着膜
の膜厚が不均一となったりする。よって、安定した蒸着
を実現するためには蒸発源の密度がある程度高いことが
望ましい。上記相対密度とするには一般に、粉体を２０
ＭＰａ以上の圧力で加圧成形したり、あるいは融点以上
の温度で加熱溶融して、タブレット（錠剤）の形状にす
る。ただし、蒸発源は必ずしもタブレットの形状である
必要はない。The relative density of the evaporation source is 80% or more and 9
It is preferably 8% or less, more preferably 90%
It is above 96%. If the evaporation source is in a powder state with a low relative density, it may cause inconveniences such as powder scattering during vapor deposition, or the film thickness of the vapor deposition film may not be uniform because it does not evaporate uniformly from the surface of the evaporation source. Or Therefore, in order to realize stable vapor deposition, it is desirable that the density of the evaporation source is high to some extent. To obtain the above-mentioned relative density, 20
It is pressed under a pressure of MPa or higher, or is heated and melted at a temperature of a melting point or higher to form a tablet. However, the evaporation source does not necessarily have to be tablet-shaped.
【００２５】さらに、蒸発源は、アルカリ金属不純物
（蛍光体の構成元素以外のアルカリ金属）の含有量が１
０ｐｐｍ以下であり、そしてアルカリ土類金属不純物
（蛍光体の構成元素以外のアルカリ土類金属）の含有量
が１ｐｐｍ以下であることが望ましい。このような蒸発
源は、アルカリ金属やアルカリ土類金属など不純物の含
有量の少ない原料を使用することにより調製することが
できる。これによって、不純物の混入が少ない蒸着膜を
形成することができるとともに、そのような蒸着膜は発
光量が増加する。Further, the evaporation source has a content of alkali metal impurities (alkali metals other than the constituent elements of the phosphor) of 1
It is preferably 0 ppm or less, and the content of alkaline earth metal impurities (alkaline earth metal other than the constituent elements of the phosphor) is 1 ppm or less. Such an evaporation source can be prepared by using a raw material having a low content of impurities such as an alkali metal or an alkaline earth metal. This makes it possible to form a vapor-deposited film with less impurities mixed therein, and such a vapor-deposited film increases the amount of light emission.
【００２６】次に、図１に示すような蒸着装置を用いて
基板上に蒸着膜を形成する。図１は、本発明に用いられ
る一元蒸着用蒸着装置の構成の例を概略的に示す断面図
である。図１において、蒸着装置は、蒸着チャンバ１、
基板加熱用ヒータ２、基板保持部材３、シャッタ５、蒸
着速度モニタ６、電子銃７、電子銃用るつぼ９、排気ポ
ンプ１１、および吸入ポンプ１２から構成される。Next, a vapor deposition film is formed on the substrate by using the vapor deposition apparatus as shown in FIG. FIG. 1 is a cross-sectional view schematically showing an example of the configuration of a vapor deposition device for unitary vapor deposition used in the present invention. In FIG. 1, the vapor deposition apparatus includes a vapor deposition chamber 1,
The substrate heating heater 2, the substrate holding member 3, the shutter 5, the vapor deposition rate monitor 6, the electron gun 7, the electron gun crucible 9, the exhaust pump 11, and the suction pump 12 are included.
【００２７】図２は、図１のシャッタ５を概略的に示す
斜視図である。シャッタ５は、基板保持部材３に保持固
定される基板４と電子銃用るつぼ９に装填される蒸発源
１０（後述）との間に位置するように設置されていて、
蒸着チャンバ１の外部からの制御信号により、水平方向
（矢印の方向）に回転して開閉する。シャッタ５と蒸発
源１０との距離は、蒸発流が回り込まず、かつ蒸発流と
干渉しない距離に保たれている。また、シャッタ５は、
通常はステンレス鋼などからなる円盤状であり、その直
径は基板への蒸着を防ぐのに十分な大きさを有し、そし
て閉じた状態（図１及び図２に示した状態）で蒸発源１
０からの前処理蒸発流を遮断する機能を果たす。FIG. 2 is a perspective view schematically showing the shutter 5 of FIG. The shutter 5 is installed so as to be located between the substrate 4 held and fixed to the substrate holding member 3 and an evaporation source 10 (described later) loaded in the crucible 9 for an electron gun,
By a control signal from the outside of the vapor deposition chamber 1, it is opened and closed by rotating in the horizontal direction (the direction of the arrow). The distance between the shutter 5 and the evaporation source 10 is kept such that the evaporation flow does not go around and does not interfere with the evaporation flow. Further, the shutter 5 is
Usually, it is a disk shape made of stainless steel or the like, the diameter of which is large enough to prevent vapor deposition on the substrate, and the evaporation source 1 in the closed state (the state shown in FIGS. 1 and 2).
It serves to block the pretreatment vapor stream from zero.
【００２８】上述した蒸発源１０を図１の装置の電子銃
用るつぼ９に装填する。また、基板４、４’を基板保持
部材３に保持させて固定する。装置内を排気ポンプ１１
により排気して１×１０-5〜１×１０-2Ｐａ程度の真空
度とする。このとき、真空度をこの程度に保持しなが
ら、吸入ポンプ１２によりＡｒガス、Ｎｅガスなどの不
活性ガスを導入してもよい。また、装置内の雰囲気中の
水分圧を、排気ポンプ１１としてディフュージョンポン
プとコールドトラップの組合せなどを用いることによ
り、７．０×１０-3Ｐａ以下にすることが好ましい。蒸
着の際に必要に応じて基板４、４’を、基板加熱ヒータ
２により裏面から加熱してもよい。あるいは基板４、
４’を冷却してもよい。The evaporation source 10 described above is loaded into the crucible 9 for the electron gun of the apparatus shown in FIG. Further, the substrates 4 and 4'are held and fixed by the substrate holding member 3. Exhaust pump 11 inside the device
To evacuate to obtain a vacuum degree of about 1 × 10 −5 to 1 × 10 −2 Pa. At this time, an inert gas such as Ar gas or Ne gas may be introduced by the suction pump 12 while maintaining the degree of vacuum at this level. Further, the water pressure in the atmosphere in the apparatus is preferably set to 7.0 × 10 −3 Pa or less by using a combination of a diffusion pump and a cold trap as the exhaust pump 11. At the time of vapor deposition, the substrates 4 and 4 ′ may be heated from the back surface by the substrate heater 2 if necessary. Or substrate 4,
4'may be cooled.
【００２９】シャッタ５を閉じた状態で、電子銃７から
電子ビーム８を発生させて蒸発源１０に照射する。この
とき、電子線の加速電圧を１．５ｋＶ以上で、５．０ｋ
Ｖ以下に設定することが望ましい。電子線の照射によ
り、蒸発源である輝尽性蛍光体は加熱されて蒸発、飛散
するが、閉状態にあるシャッタ５により蒸発流は遮断さ
れて基板表面には到達しない。With the shutter 5 closed, an electron beam 8 is generated from the electron gun 7 and irradiated on the evaporation source 10. At this time, if the acceleration voltage of the electron beam is 1.5 kV or more, 5.0 kV
It is desirable to set it to V or less. Upon irradiation with an electron beam, the stimulable phosphor, which is the evaporation source, is heated and evaporated and scattered, but the evaporation flow is blocked by the shutter 5 in the closed state and does not reach the substrate surface.
【００３０】本発明において、前記基本組成式（Ｉ）を
有するユーロピウム付活アルカリ金属ハロゲン化物系輝
尽性蛍光体は、その母体成分ＭIＸよりも付活剤成分Ｅ
ｕの方が蒸気圧が顕著に高いために、蒸着開始直後の蒸
発流は殆ど母体成分であり、逆に蒸着終了直前には付活
剤成分Ｅｕの濃度が当初の蛍光体組成比よりも高くなる
傾向にある。よって、シャッタ５を一定時間閉じて蒸着
開始直後の蒸発流を使用しないことにより、得られる蒸
着膜中の付活剤Ｅｕ濃度の分布（ムラ）を低減すること
ができる。[0030] In the present invention, europium activated alkali metal halide stimulable phosphor having the basic composition formula (I), activator component E than its parent component M I X
Since u has a remarkably higher vapor pressure, the evaporating flow immediately after the start of vapor deposition is almost the matrix component, and conversely immediately before the end of vapor deposition, the concentration of the activator component Eu is higher than the initial phosphor composition ratio. Tends to become. Therefore, the distribution (unevenness) of the activator Eu concentration in the obtained vapor deposition film can be reduced by closing the shutter 5 for a certain period of time and not using the evaporation flow immediately after the start of vapor deposition.
【００３１】蒸発源が全て蒸発するのに要する時間をＴ
とするとき（すなわち蒸着開始時刻０、蒸着終了時刻Ｔ
であるとき）、閉状態にあるシャッタ５を蒸着開始後１
／１０Ｔ乃至１／２Ｔ経過した時点で開いて、基板上に
輝尽性蛍光体を蒸着させることが好ましい。より好まし
くは、蒸着開始後１／５Ｔ乃至１／２Ｔ経過時にシャッ
タを開き、そして特に好ましくは、蒸着開始後１／３Ｔ
乃至１／２Ｔ経過時にシャッタを開く。The time required for the evaporation source to completely evaporate is T
(That is, vapor deposition start time 0, vapor deposition end time T
1) after starting the deposition of the shutter 5 in the closed state.
It is preferable to open after a time of / 10T to 1 / 2T to deposit a stimulable phosphor on the substrate. More preferably, the shutter is opened 1 / 5T to 1 / 2T after the start of vapor deposition, and particularly preferably 1 / 3T after the vapor deposition is started.
The shutter is opened when ˜1 / 2T has passed.
【００３２】また、開いたシャッタ５を一定時間経過後
に再度閉じて、基板上への蛍光体の蒸着を中止すること
が好ましい。これにより、蒸着膜中のＥｕ濃度分布（ム
ラ）をより一層低減することができる。蒸着開始後１／
２Ｔ乃至９／１０Ｔ経過時にシャッタ５を閉じることが
好ましい。より好ましくは、蒸着開始後１／２Ｔ乃至４
／５Ｔ経過時にシャッタを閉じ、そして特に好ましく
は、蒸着開始後１／２Ｔ乃至２／３Ｔ経過時にシャッタ
を閉じる。ただし、シャッタ開が１／２Ｔ経過時である
ときには、シャッタ閉は１／２Ｔ経過時より遅い時点と
する。あるいは、シャッタ５を閉じる代わりに、電子銃
の出力を下げることにより蒸着それ自体を強制的に終了
させることもできる。Further, it is preferable to close the opened shutter 5 again after a lapse of a certain period of time to stop the vapor deposition of the phosphor on the substrate. As a result, the Eu concentration distribution (unevenness) in the deposited film can be further reduced. 1 / after starting vapor deposition
It is preferable to close the shutter 5 after 2T to 9 / 10T. More preferably, 1 / 2T to 4 after the start of vapor deposition
The shutter is closed after elapse of / 5T, and particularly preferably, the shutter is closed after elapse of 1 / 2T to 2 / 3T after the start of vapor deposition. However, when the shutter is opened for 1 / 2T, the shutter is closed later than for 1 / 2T. Alternatively, instead of closing the shutter 5, the vapor deposition itself can be forcibly terminated by lowering the output of the electron gun.
【００３３】従って、基板上に輝尽性蛍光体を蒸着堆積
させる時間は、一般には９／１０Ｔ以下であり、好まし
くは１／６Ｔ乃至４／５Ｔの範囲にあり、特に好ましく
は１／６Ｔ乃至１／２Ｔの範囲にある。Therefore, the time for depositing the stimulable phosphor on the substrate by vapor deposition is generally 9/10 T or less, preferably 1/6 T to 4/5 T, and particularly preferably 1/6 T to It is in the range of 1 / 2T.
【００３４】シャッタ５が開状態にあるとき、基板表面
には輝尽性蛍光体が堆積する。蒸着速度は、一般には
０．１〜１０００μｍ／分の範囲にあり、好ましくは１
〜１００μｍ／分の範囲にある。また、基板４、４’を
基板保持部材３により水平方向に回転させて、各基板上
に蛍光体が均一に堆積するようにしてもよい。When the shutter 5 is open, the stimulable phosphor is deposited on the surface of the substrate. The vapor deposition rate is generally in the range of 0.1 to 1000 μm / min, preferably 1
˜100 μm / min. Alternatively, the substrates 4 and 4 ′ may be rotated in the horizontal direction by the substrate holding member 3 so that the phosphor is uniformly deposited on each substrate.
【００３５】このようにして、輝尽性蛍光体からなる柱
状結晶がほぼ厚み方向に成長した層が得られる。蛍光体
層の層厚は、通常は５０〜１０００μｍの範囲にあり、
好ましくは２００μｍ〜７００ｍｍの範囲にある。In this way, a layer is obtained in which the columnar crystals of the stimulable phosphor are grown substantially in the thickness direction. The layer thickness of the phosphor layer is usually in the range of 50 to 1000 μm,
It is preferably in the range of 200 μm to 700 mm.
【００３６】なお、上記本発明の方法において蒸着装置
は、図１に示した装置に限定されるものではなく、基板
上への蒸着を遮断しうるシャッタを備えた一元蒸着用の
装置であればよい。蒸発源の加熱手段も、電子銃に限定
されるものではなく、抵抗加熱などのような他の加熱方
法も利用することができる。In the above method of the present invention, the vapor deposition apparatus is not limited to the apparatus shown in FIG. 1, but any vapor deposition apparatus provided with a shutter capable of blocking vapor deposition on the substrate may be used. Good. The heating means of the evaporation source is not limited to the electron gun, and other heating methods such as resistance heating can be used.
【００３７】次に、本発明の第二の製造方法について詳
細に説明する。図３は、本発明に用いられる蒸発源補給
装置の構成の例を概略的に示す斜視図である。図３にお
いて、蒸発源補給装置は、蒸着チャンバ１内に設置され
た蒸発源補給系２１と、蒸着チャンバ１の外部に設けら
れた補給速度制御系２５とから構成される。蒸発源補給
系２１は、補給材料タンク２２、補給材料送りガイド２
３、および補給調整部材２４からなる。補給材料を蓄え
るための補給材料タンク２２には、筒状の補給材料送り
ガイド２３が接続され、送りガイド２３の途中には上下
移動可能な補給調整部材２４が設けられ、そして補給調
整部材２４は補給速度制御系２５に接続されている。Next, the second manufacturing method of the present invention will be described in detail. FIG. 3 is a perspective view schematically showing an example of the configuration of the evaporation source replenishing device used in the present invention. In FIG. 3, the evaporation source replenishing device is composed of an evaporation source replenishing system 21 installed in the vapor deposition chamber 1 and a replenishment rate control system 25 provided outside the vapor deposition chamber 1. The evaporation source replenishment system 21 includes a replenishment material tank 22 and a replenishment material feeding guide 2.
3 and a supply adjusting member 24. A cylindrical replenishment material feed guide 23 is connected to the replenishment material tank 22 for storing the replenishment material, a vertically movable replenishment adjustment member 24 is provided in the middle of the feed guide 23, and the replenishment adjustment member 24 is It is connected to the replenishment speed control system 25.
【００３８】補給材料としては、上記輝尽性蛍光体の母
体成分ＭIＸもしくは輝尽性蛍光体を用いる。この場合
に輝尽性蛍光体としては、蒸発源中の蛍光体のＥｕ含量
よりも低いＥｕ含量の蛍光体を用いる。この補給材料の
形態に特に制限はないが、粉体または顆粒状であること
が好ましい。その場合に、粒径は輸送性や蒸発しやすさ
などに依って決まるが、一般には１乃至１０μｍの範囲
にある。[0038] As the supply material, using a matrix material M I X or the stimulable phosphor of the stimulable phosphor. In this case, a phosphor having an Eu content lower than the Eu content of the phosphor in the evaporation source is used as the stimulable phosphor. The form of the supplementary material is not particularly limited, but it is preferably powder or granules. In this case, the particle size is determined depending on the transportability and the easiness of evaporation, but it is generally in the range of 1 to 10 μm.
【００３９】補給材料送りガイド２３は、図３に示した
ように、補給材料が飛散しにくい筒状であって、かつ蒸
発源１０への供給を容易にするために傾斜していること
が好ましい。なお、送りガイド２３は、溝状または板状
であってもよいし、あるいは蒸発源１０表面に均一に供
給できるようにガイド先端部を所望の形状に細工しても
よい。As shown in FIG. 3, the replenishment material feed guide 23 preferably has a cylindrical shape in which the replenishment material is less likely to scatter, and is inclined to facilitate the supply to the evaporation source 10. . The feed guide 23 may have a groove shape or a plate shape, or the guide tip may be formed into a desired shape so that it can be uniformly supplied to the surface of the evaporation source 10.
【００４０】補給調整部材２４は、補給速度制御系２５
からの制御信号により上下方向に移動することができ、
それによって蒸発源１０に供給される補給材料の供給速
度が調整される。The replenishment adjusting member 24 includes a replenishment speed control system 25.
Can be moved up and down by the control signal from
Thereby, the supply rate of the supplementary material supplied to the evaporation source 10 is adjusted.
【００４１】補給速度制御系２５において、補給速度
は、例えば予め、蒸発源である輝尽性蛍光体のみを蒸発
させて得られた蒸着膜中の付活剤Ｅｕの濃度分布を厚み
方向に沿って測定し、その測定結果に基づいて補給材料
の補給速度をシミュレートすることにより決定すること
ができ、この補給速度に基づいて制御信号が補給調整部
材２４に送られる。あるいは、蒸着装置内にプラズマ発
光分光器等の測定機器を設置しておき、蒸着の際に付活
剤Ｅｕの蒸発量を測定し、そのデータをリアルタイムで
制御系２５に送って補給速度を決定してもよい。補給調
整部材２４には、この補給速度に基づく制御信号がリア
ルタイムで送られる（フィードバックされる）。In the replenishment rate control system 25, the replenishment rate is, for example, the concentration distribution of the activator Eu in the vapor deposition film obtained in advance by evaporating only the stimulable phosphor as the evaporation source, along the thickness direction. Can be determined by simulating the replenishment rate of the replenishment material based on the measurement result, and a control signal is sent to the replenishment adjustment member 24 based on this replenishment rate. Alternatively, a measuring device such as a plasma emission spectroscope is installed in the vapor deposition apparatus, the evaporation amount of the activator Eu is measured during vapor deposition, and the data is sent to the control system 25 in real time to determine the replenishment rate. You may. A control signal based on this replenishment speed is sent (feedback) to the replenishment adjustment member 24 in real time.
【００４２】まず、蒸着に先立って上記の補給材料を補
給材料タンク２２に装填する。次いで、前述と同様にし
て電子銃７から電子線８を発生させて蒸発源１０に照射
すると、蒸発源１０からは輝尽性蛍光体が蒸発し、飛散
して基板表面に堆積する。このとき同時にタンク２２か
らは、補給材料が送りガイド２３を通って蒸発源１０に
供給される。そして、補給調整部材２４は補給速度制御
系２５からの制御により上下に移動して、補給材料が所
望の補給速度で蒸発源１０に供給されることになる。First, the above-mentioned replenishment material is loaded into the replenishment material tank 22 prior to vapor deposition. Next, when the electron beam 8 is generated from the electron gun 7 and is applied to the evaporation source 10 in the same manner as described above, the stimulable phosphor is evaporated from the evaporation source 10 and scattered to be deposited on the substrate surface. At this time, at the same time, the replenishment material is supplied from the tank 22 to the evaporation source 10 through the feed guide 23. Then, the replenishment adjustment member 24 moves up and down under the control of the replenishment rate control system 25, and the replenishment material is supplied to the evaporation source 10 at a desired replenishment rate.
【００４３】このように蒸発源に補給材料を供給しなが
ら蒸着を行うことによって、輝尽性蛍光体の母体成分Ｍ
IＸと付活剤成分Ｅｕとの蒸気圧差のために母体成分が
優先的に蒸発して蒸発源中のＥｕ濃度が次第に高くなる
のを抑制することができる。すなわち、蒸発流中のＥｕ
濃度が常に一定になるように制御しながら蒸着を実施す
ることができる。By performing vapor deposition while supplying the replenishment material to the evaporation source in this manner, the matrix component M of the stimulable phosphor is obtained.
It is possible to prevent the parent component from evaporating preferentially due to the vapor pressure difference between IX and the activator component Eu, and the Eu concentration in the evaporation source from gradually increasing. That is, Eu in the evaporating flow
The vapor deposition can be carried out while controlling the concentration to be always constant.
【００４４】このようにして、輝尽性蛍光体からなる柱
状結晶がほぼ厚み方向に成長した層が得られる。蛍光体
層の層厚は、通常は５０〜１０００μｍの範囲にあり、
好ましくは２００μｍ〜７００ｍｍの範囲にある。In this way, a layer is obtained in which columnar crystals of stimulable phosphor are grown substantially in the thickness direction. The layer thickness of the phosphor layer is usually in the range of 50 to 1000 μm,
It is preferably in the range of 200 μm to 700 mm.
【００４５】なお、本発明において蒸発源補給装置は、
図３に示した装置に限定されるものではなく、例えば上
記したようにプラズマ発光分光器等のＥｕ蒸発量の測定
が可能な機器を備えていてもよい。あるいは、蒸発源補
給系２１を二系統以上有していてもよく、その場合には
母体成分ＭIＸと付活剤成分Ｅｕとを別々に補給するこ
とができる。さらに、各蒸発源補給系に対応して補給速
度制御系も二系統以上有していてもよい。In the present invention, the evaporation source replenishing device is
The device is not limited to the device shown in FIG. 3, and may be equipped with a device capable of measuring the amount of Eu evaporation such as a plasma emission spectroscope as described above. Alternatively, it may have a vapor source supply system 21 dual or higher, in which case it can be replenished separately and maternal component M I X and activator component Eu. Further, two or more replenishment rate control systems may be provided corresponding to each evaporation source replenishment system.
【００４６】本発明の第一及び第二いずれの方法におい
ても、電子線の照射を複数回に分けて行って二層以上の
蛍光体層を形成することができる。また、蒸着終了後に
蛍光体層を加熱処理（アニール処理）してもよい。In both the first and second methods of the present invention, it is possible to form the phosphor layer of two or more layers by performing the electron beam irradiation in plural times. Further, the phosphor layer may be subjected to a heat treatment (annealing treatment) after completion of the vapor deposition.
【００４７】あるいは、上記輝尽性蛍光体からなる蒸着
膜を形成するに先立って、蛍光体母体成分のみからなる
蒸着膜を形成してもよい。これによって、柱状結晶性の
良好な蒸着膜を得ることができる。なお、蛍光体からな
る蒸着膜中の付活剤など微量成分は、特に蒸着時の加熱
および／または蒸着後の加熱処理によって、蛍光体母体
からなる蒸着膜中に拡散するために、両者の境界は必ず
しも明確ではない。Alternatively, prior to the formation of the vapor-deposited film containing the stimulable phosphor, a vapor-deposited film containing only the phosphor matrix component may be formed. This makes it possible to obtain a vapor deposition film having good columnar crystallinity. In addition, since trace components such as an activator in the vapor-deposited film made of the phosphor are diffused into the vapor-deposited film made of the phosphor matrix by heating at the time of vapor deposition and / or heat treatment after the vapor deposition, the boundary between the two Is not always clear.
【００４８】蒸着法としては、上述した電子線蒸着法以
外にも、抵抗加熱器を用いる抵抗加熱法など公知の任意
の方法を採ることができる。また、上記第一の方法に係
るシャッタの開閉と、第二の方法に係る補給材料の補給
とを組み合わせて実施することもできる。As the vapor deposition method, in addition to the electron beam vapor deposition method described above, any known method such as a resistance heating method using a resistance heater can be adopted. Further, the opening and closing of the shutter according to the first method and the replenishment of the replenishment material according to the second method can be performed in combination.
【００４９】なお、基板は必ずしも放射線像変換パネル
の支持体を兼ねる必要はなく、蛍光体層形成後、蛍光体
層を基板から引き剥がし、別に用意した支持体上に接着
剤を用いるなどして接合して、支持体上に蛍光体層を設
ける方法を利用してもよい。あるいは、蛍光体層に支持
体（基板）が付設されていなくてもよい。The substrate does not necessarily have to serve also as a support for the radiation image conversion panel. After the phosphor layer is formed, the phosphor layer is peeled off from the substrate and an adhesive is used on a separately prepared support. You may utilize the method of joining and providing a fluorescent substance layer on a support body. Alternatively, the support (substrate) may not be attached to the phosphor layer.
【００５０】この蛍光体層の表面には、放射線像変換パ
ネルの搬送および取扱い上の便宜や特性変化の回避のた
めに、保護層を設けることが望ましい。保護層は、励起
光の入射や発光光の出射に殆ど影響を与えないように、
透明であることが望ましく、また外部から与えられる物
理的衝撃や化学的影響から放射線像変換パネルを充分に
保護することができるように、化学的に安定で防湿性が
高く、かつ高い物理的強度を持つことが望ましい。It is desirable to provide a protective layer on the surface of the phosphor layer for the convenience of transportation and handling of the radiation image conversion panel and for avoiding a change in characteristics. The protective layer has almost no effect on the incidence of excitation light or the emission of emitted light,
It is desirable to be transparent, and it is chemically stable, highly moisture-proof, and has high physical strength so that the radiation image conversion panel can be sufficiently protected from external physical impact and chemical influences. It is desirable to have.
【００５１】保護層としては、セルロース誘導体、ポリ
メチルメタクリレート、有機溶媒可溶性フッ素系樹脂な
どのような透明な有機高分子物質を適当な溶媒に溶解し
て調製した溶液を蛍光体層の上に塗布することで形成さ
れたもの、あるいはポリエチレンテレフタレートなどの
有機高分子フィルムや透明なガラス板などの保護層形成
用シートを別に形成して蛍光体層の表面に適当な接着剤
を用いて設けたもの、あるいは無機化合物を蒸着などに
よって蛍光体層上に成膜したものなどが用いられる。ま
た、保護層中には酸化マグネシウム、酸化亜鉛、二酸化
チタン、アルミナ等の光散乱性微粒子、パーフルオロオ
レフィン樹脂粉末、シリコーン樹脂粉末等の滑り剤、お
よびポリイソシアネート等の架橋剤など各種の添加剤が
分散含有されていてもよい。保護層の層厚は一般に、高
分子物質からなる場合には約０．１〜２０μｍの範囲に
あり、ガラス等の無機化合物からなる場合には１００〜
１０００μｍの範囲にある。As the protective layer, a solution prepared by dissolving a transparent organic polymer substance such as a cellulose derivative, polymethylmethacrylate, or an organic solvent-soluble fluororesin in an appropriate solvent is applied on the phosphor layer. Or a sheet formed by separately forming a protective layer forming sheet such as an organic polymer film such as polyethylene terephthalate or a transparent glass plate and providing it on the surface of the phosphor layer with an appropriate adhesive. Alternatively, an inorganic compound deposited on the phosphor layer by vapor deposition or the like is used. Further, in the protective layer, various additives such as light-scattering fine particles of magnesium oxide, zinc oxide, titanium dioxide, alumina, etc., sliding agents such as perfluoroolefin resin powder, silicone resin powder, etc., and crosslinking agents such as polyisocyanate etc. May be dispersedly contained. The thickness of the protective layer is generally in the range of about 0.1 to 20 μm when it is made of a polymeric substance, and 100 to 100 when it is made of an inorganic compound such as glass.
It is in the range of 1000 μm.
【００５２】保護層の表面にはさらに、保護層の耐汚染
性を高めるためにフッ素樹脂塗布層を設けてもよい。フ
ッ素樹脂塗布層は、フッ素樹脂を有機溶媒に溶解（また
は分散）させて調製したフッ素樹脂溶液を保護層の表面
に塗布し、乾燥することにより形成することができる。
フッ素樹脂は単独で使用してもよいが、通常はフッ素樹
脂と膜形成性の高い樹脂との混合物として使用する。ま
た、ポリシロキサン骨格を持つオリゴマーあるいはパー
フルオロアルキル基を持つオリゴマーを併用することも
できる。フッ素樹脂塗布層には、干渉むらを低減させて
更に放射線画像の画質を向上させるために、微粒子フィ
ラーを充填することもできる。フッ素樹脂塗布層の層厚
は通常は０．５μｍ乃至２０μｍの範囲にある。フッ素
樹脂塗布層の形成に際しては、架橋剤、硬膜剤、黄変防
止剤などのような添加成分を用いることができる。特に
架橋剤の添加は、フッ素樹脂塗布層の耐久性の向上に有
利である。The surface of the protective layer may be further provided with a fluororesin coating layer in order to enhance the stain resistance of the protective layer. The fluororesin coating layer can be formed by applying a fluororesin solution prepared by dissolving (or dispersing) a fluororesin in an organic solvent onto the surface of the protective layer and drying.
Although the fluororesin may be used alone, it is usually used as a mixture of the fluororesin and a resin having high film forming property. Further, an oligomer having a polysiloxane skeleton or an oligomer having a perfluoroalkyl group can be used together. The fluororesin coating layer may be filled with a fine particle filler in order to reduce interference unevenness and further improve the quality of a radiation image. The layer thickness of the fluororesin coating layer is usually in the range of 0.5 μm to 20 μm. In forming the fluororesin coating layer, an additive component such as a cross-linking agent, a hardener, an anti-yellowing agent, etc. can be used. In particular, the addition of the crosslinking agent is advantageous for improving the durability of the fluororesin coating layer.
【００５３】上述のようにして本発明の放射線像変換パ
ネルが得られるが、本発明のパネルの構成は、公知の各
種のバリエーションを含むものであってもよい。たとえ
ば、得られる画像の鮮鋭度を向上させることを目的とし
て、上記の少なくともいずれかの層を、励起光を吸収し
輝尽発光光は吸収しないような着色剤によって着色して
もよい。Although the radiation image storage panel of the present invention is obtained as described above, the configuration of the panel of the present invention may include various known variations. For example, for the purpose of improving the sharpness of the obtained image, at least one of the above layers may be colored with a coloring agent that absorbs excitation light and does not absorb stimulated emission light.
【００５４】[0054]
【実施例】［実施例１］
（１）蒸発源の作製
ＣｓＢｒ１００ｇ（０．４７モル）およびＥｕＢｒ
x（ｘ＝２．２）１．５４０１ｇ（４．７×１０-3モ
ル）を秤量し、ミキサーで混合した。得られた混合物を
石英容器に入れ、これを電気炉の炉芯に入れて、初期真
空引き後、窒素ガスを大気圧まで導入し、温度５２５℃
にて１時間焼成した。次いで、５分間中間真空引きした
後、酸素を１３３Ｐａまで導入し、更に窒素ガスを導入
して大気圧にした状態で、１時間焼成を行った。焼成
後、真空状態で室温まで冷却し、乳鉢で粉砕して、Ｃｓ
Ｂｒ：0.01Ｅｕ蛍光体粉末を得た。この蛍光体粉末をジ
ルコニア製粉末成形用ダイス（内径：３５ｍｍ）に入
れ、粉末金型プレス成形機（テーブルプレスＴＢ−５
型、エヌピーエーシステム(株)製）にて５０ＭＰａの圧
力で加圧し、タブレット（直径：３５ｍｍ、厚み：２０
ｍｍ）に成形した。このとき、蛍光体粉末に掛かった圧
力は約４０ＭＰａであった。次に、このタブレットに真
空乾燥機にて温度２００℃で２時間の真空乾燥処理を施
した。得られたタブレットの密度は３．９ｇ／ｃｍ3で
あり、含水量は０．３重量％であった。EXAMPLES [Example 1] (1) Preparation of evaporation source CsBr 100 g (0.47 mol) and EuBr
1.5401 g (4.7 × 10 −3 mol) of x (x = 2.2) was weighed and mixed with a mixer. The obtained mixture was put in a quartz container, put in a furnace core of an electric furnace, and after the initial vacuuming, nitrogen gas was introduced up to atmospheric pressure at a temperature of 525 ° C.
It was baked for 1 hour. Then, after performing an intermediate vacuum for 5 minutes, oxygen was introduced up to 133 Pa, and nitrogen gas was further introduced to carry out firing at an atmospheric pressure for 1 hour. After firing, cool to room temperature in a vacuum, crush in a mortar, and add Cs
Br: 0.01Eu phosphor powder was obtained. This phosphor powder was put into a powder molding die (inner diameter: 35 mm) made of zirconia, and a powder mold press molding machine (table press TB-5
Type, manufactured by NPA System Co., Ltd.) at a pressure of 50 MPa, and tablets (diameter: 35 mm, thickness: 20)
mm). At this time, the pressure applied to the phosphor powder was about 40 MPa. Next, this tablet was subjected to vacuum drying treatment at a temperature of 200 ° C. for 2 hours with a vacuum dryer. The obtained tablet had a density of 3.9 g / cm 3 and a water content of 0.3% by weight.
【００５５】（２）蛍光体層の形成
支持体として、順にアルカリ洗浄、純水洗浄、およびＩ
ＰＡ洗浄を施した合成石英基板（サイズ：１００ｍｍ×
１００ｍｍ）を用意し、図１に示した蒸着装置内の基板
保持部材３に設置した。上記ＣｓＢｒ：Ｅｕ蒸発源を装
置内の電子銃用るつぼ９に装填した。装置内において、
シャッタ５の直径は１００ｍｍであり、シャッタ５と蒸
発源１０との間の距離は１５０ｍｍであった。(2) Formation of phosphor layer As a support, alkaline cleaning, pure water cleaning, and I
Synthetic quartz substrate washed with PA (size: 100 mm x
100 mm) was prepared and placed on the substrate holding member 3 in the vapor deposition apparatus shown in FIG. The above CsBr: Eu evaporation source was loaded into the crucible 9 for the electron gun in the apparatus. In the device,
The diameter of the shutter 5 was 100 mm, and the distance between the shutter 5 and the evaporation source 10 was 150 mm.
【００５６】その後、装置内を排気ポンプ１１により排
気して１×１０-3Ｐａの真空度とした。このとき、排気
ポンプ１１としてロータリーポンプ、メカニカルブース
タおよびターボ分子ポンプの組合せを用いた。次いで、
基板４の蒸着面とは反対側に位置したシーズヒータ２
で、基板４を２００℃に加熱した。シャッタ５を閉じた
状態で、電子銃７から加速電圧−４．０ｋＶで電子線を
発生させ、蒸発源１０に照射して蒸着を開始した。蒸着
開始後３０秒経過した時点でシャッタ５を開いて、Ｃｓ
Ｂｒ：Ｅｕ輝尽性蛍光体を基板４上に堆積させた。蒸着
開始後３分２０秒経過した時点でシャッタ５を再び閉じ
て、基板４上への蒸着を中止した。このとき、電子銃７
の電源の出力も下げた。蒸着雰囲気中の水分圧は４×１
０-3Ｐａであった。After that, the inside of the apparatus was evacuated by the exhaust pump 11 to a vacuum degree of 1 × 10 -3 Pa. At this time, a combination of a rotary pump, a mechanical booster and a turbo molecular pump was used as the exhaust pump 11. Then
The sheathed heater 2 located on the side opposite to the vapor deposition surface of the substrate 4.
Then, the substrate 4 was heated to 200 ° C. With the shutter 5 closed, an electron beam was generated from the electron gun 7 at an acceleration voltage of −4.0 kV, and the evaporation source 10 was irradiated with the electron beam to start vapor deposition. When 30 seconds have passed after the start of vapor deposition, the shutter 5 is opened and Cs
A Br: Eu stimulable phosphor was deposited on the substrate 4. When 3 minutes and 20 seconds had passed after the start of vapor deposition, the shutter 5 was closed again and the vapor deposition on the substrate 4 was stopped. At this time, the electron gun 7
The output of the power supply was also reduced. Moisture pressure in vapor deposition atmosphere is 4 × 1
It was 0 -3 Pa.
【００５７】次に、この石英基板をガス導入可能な真空
加熱装置に入れ、ロータリーポンプにより約１Ｐａまで
真空に引いて基板上の蒸着膜に吸着している水分等を除
去した後、窒素ガス雰囲気中、２００℃の温度で２時間
蒸着膜を熱処理した。真空下で基板を冷却し、十分に温
度が下がった時点で装置から基板を取り出した。基板上
には、蛍光体の柱状結晶がほぼ垂直方向に密に林立した
構造の蛍光体層が形成されていた。このようにして、支
持体と蛍光体層とからなる本発明に従う放射線像変換パ
ネルを製造した。Next, this quartz substrate was put in a vacuum heating apparatus capable of introducing gas, and a rotary pump was evacuated to about 1 Pa to remove water and the like adsorbed on the vapor deposition film on the substrate. The deposited film was heat-treated at a temperature of 200 ° C. for 2 hours. The substrate was cooled under vacuum, and when the temperature was sufficiently lowered, the substrate was taken out from the apparatus. On the substrate, a phosphor layer having a structure in which columnar crystals of phosphor were densely forested in a substantially vertical direction was formed. In this way, a radiation image conversion panel according to the present invention comprising a support and a phosphor layer was produced.
【００５８】［実施例２、３］実施例１の（２）蛍光体
層の形成において、蒸着開始後１分４０秒および２分３
０秒経過した時点でそれぞれシャッタ５を開いたこと以
外は実施例１と同様にして、本発明に従う放射線像変換
パネルを製造した。[Examples 2 and 3] (2) In the formation of the phosphor layer of Example 1, 1 minute 40 seconds and 2 minutes 3 after the start of vapor deposition.
A radiation image conversion panel according to the present invention was manufactured in the same manner as in Example 1 except that the shutter 5 was opened when 0 seconds had passed.
【００５９】［比較例１］実施例１の（２）蛍光体層の
形成において、シャッタを開いた状態で蒸着を開始し、
蒸発源が全て蒸発し終えた時点でシャッタを閉じたこと
以外は実施例１と同様にして、比較のための放射線像変
換パネルを製造した。蒸発開始から終了までに要した時
間は５分であった。[Comparative Example 1] In the formation of the phosphor layer (2) in Example 1, vapor deposition was started with the shutter open.
A radiation image conversion panel for comparison was manufactured in the same manner as in Example 1 except that the shutter was closed when all the evaporation sources had evaporated. The time required from the start of evaporation to the end was 5 minutes.
【００６０】［実施例４］実施例１の（１）蒸発源の作
製において、ＥｕＢｒxの量を４．６２ｇ（１．４×１
０-2モル）に変更してＣｓＢｒ：0.03Ｅｕ蛍光体粉末を
得たこと以外は実施例１と同様にして、本発明に従う放
射線像変換パネルを製造した。Example 4 (1) In the production of the evaporation source of Example 1, the amount of EuBr x was 4.62 g (1.4 × 1).
0 Change -2 mol) CsBr: 0.03 EU except that to obtain a phosphor powder in the same manner as in Example 1, to produce a radiation image storage panel according to the present invention.
【００６１】［実施例５〜１０］実施例４において、シ
ャッタを開いた時点および／または再度閉じた時点をそ
れぞれ表１に示したように変更したこと以外は実施例４
と同様にして、本発明に従う各種の放射線像変換パネル
を製造した。[Embodiments 5 to 10] Embodiment 4 is different from Embodiment 4 except that the shutter opening time and / or the shutter closing time is changed as shown in Table 1.
Various radiation image conversion panels according to the present invention were manufactured in the same manner as in.
【００６２】［比較例２］実施例４において、シャッタ
を開いた状態で蒸着を開始し、蒸発源が全て蒸発し終え
た時点でシャッタを閉じたこと以外は実施例４と同様に
して、比較のための放射線像変換パネルを製造した。蒸
発開始から終了までに要した時間は５分であった。[Comparative Example 2] A comparative example was carried out in the same manner as in Example 4 except that the vapor deposition was started with the shutter open and the shutter was closed when all the evaporation sources had been vaporized. A radiation image conversion panel for was manufactured. The time required from the start of evaporation to the end was 5 minutes.
【００６３】［実施例１１］実施例１の（２）蛍光体層
の形成において、図１に示した蒸着装置の代わりにシャ
ッタと抵抗加熱ボートを有する抵抗加熱器を備えた装置
を用いて、ＣｓＢｒ：Ｅｕ蒸発源を抵抗加熱ボートに装
填し、１５０Ａの電流をボートに流して加熱したこと、
および蒸着開始後３分２０秒経過した時点でシャッタを
開き、そして蒸着開始後６分４０秒経過した時点でシャ
ッタを再び閉じたこと以外は実施例１と同様にして、本
発明に従う放射線像変換パネルを製造した。[Embodiment 11] (2) In the formation of the phosphor layer of Embodiment 1, an apparatus provided with a resistance heater having a shutter and a resistance heating boat is used instead of the vapor deposition apparatus shown in FIG. A CsBr: Eu evaporation source was loaded into a resistance heating boat, and a current of 150 A was applied to the boat for heating.
The radiation image conversion according to the present invention was performed in the same manner as in Example 1 except that the shutter was opened 3 minutes 20 seconds after the start of vapor deposition and the shutter was closed again 6 minutes 40 seconds after the start of vapor deposition. The panel was manufactured.
【００６４】［比較例３］実施例１１において、シャッ
タを開いた状態で蒸着を開始し、蒸発源が全て蒸発し終
えた時点でシャッタを閉じたこと以外は実施例１１と同
様にして、比較のための放射線像変換パネルを製造し
た。蒸発開始から終了までに要した時間は１０分であっ
た。[Comparative Example 3] A comparative example 3 was carried out in the same manner as in Example 11 except that the vapor deposition was started with the shutter open and the shutter was closed when all the evaporation sources had evaporated. A radiation image conversion panel for was manufactured. The time required from the start of evaporation to the end was 10 minutes.
【００６５】［実施例１２］実施例１の（１）蒸発源の
作製において、ＥｕＢｒxの量を４．６２ｇ（１．４×
１０-2モル）に変更したこと以外は実施例１と同様にし
て、ＣｓＢｒ：0.03Ｅｕ蛍光体粉末を得た。実施例１の
（２）蛍光体層の形成において、図１に示した蒸着装置
の代わりにシャッタと抵抗加熱ボートを有する抵抗加熱
器を備えた装置を用いて、ＣｓＢｒ：Ｅｕ蒸発源を抵抗
加熱ボートに装填し、１５０Ａの電流をボートに流して
加熱したこと、および蒸着開始後１分経過した時点でシ
ャッタを開き、そして蒸着開始後６分４０秒経過した時
点でシャッタを再び閉じたこと以外は実施例１と同様に
して、本発明に従う放射線像変換パネルを製造した。[Embodiment 12] In the production of the evaporation source (1) of Embodiment 1, the amount of EuBr x was 4.62 g (1.4 ×).
CsBr: 0.03Eu phosphor powder was obtained in the same manner as in Example 1 except that the amount was changed to 10 −2 mol). In (2) Phosphor layer formation of Example 1, a device provided with a resistance heater having a shutter and a resistance heating boat was used instead of the vapor deposition device shown in FIG. 1 to resistance-heat the CsBr: Eu evaporation source. Except that the boat was loaded, a current of 150 A was applied to the boat for heating, and the shutter was opened 1 minute after the start of vapor deposition and the shutter was closed again 6 minutes and 40 seconds after the vapor deposition was started. A radiographic image conversion panel according to the present invention was manufactured in the same manner as in Example 1.
【００６６】［実施例１３〜１５］実施例１２におい
て、シャッタを開いた時点および／または再度閉じた時
点をそれぞれ表２に示したように変更したこと以外は実
施例１２と同様にして、本発明に従う各種の放射線像変
換パネルを製造した。[Embodiments 13 to 15] This embodiment is the same as Embodiment 12 except that the shutter opening time and / or the shutter closing time is changed as shown in Table 2. Various radiation image conversion panels according to the invention were produced.
【００６７】［比較例４］実施例１２において、シャッ
タを開いた状態で蒸着を開始し、蒸発源が全て蒸発し終
えた時点でシャッタを閉じたこと以外は実施例１２と同
様にして、比較のための放射線像変換パネルを製造し
た。蒸発開始から終了までに要した時間は１０分であっ
た。[Comparative Example 4] A comparative example was carried out in the same manner as in Example 12 except that the vapor deposition was started with the shutter open and the shutter was closed when all the evaporation sources had been vaporized. A radiation image conversion panel for was manufactured. The time required from the start of evaporation to the end was 10 minutes.
【００６８】［放射線像変換パネルの性能評価１］得ら
れた各放射線像変換パネルの蛍光体層について、感度、
付活剤分布特性、柱状結晶性および支持体との接着性に
より評価を行った。[Performance Evaluation 1 of Radiation Image Conversion Panel] With respect to the obtained phosphor layer of each radiation image conversion panel, the sensitivity,
The evaluation was performed based on the activator distribution characteristics, columnar crystallinity, and adhesiveness with the support.
【００６９】（１）感度
放射線像変換パネルを室内光を遮蔽可能なカセッテに収
納し、これに管電圧８０ｋＶｐのＸ線を照射した。次い
で、パネルをカセッテから取り出し、パネル表面にレー
ザ光（波長：６３３ｎｍ）を照射してパネルから放出さ
れた輝尽発光光をフォトマルチプライヤで検出し、輝尽
発光量を測定した。得られた輝尽発光量を蛍光体層の層
厚で換算し、各比較例の発光量を１００としたときの相
対値を感度とした。(1) Sensitivity The radiation image conversion panel was housed in a cassette capable of shielding indoor light, and this was irradiated with X-rays having a tube voltage of 80 kVp. Next, the panel was taken out from the cassette, the surface of the panel was irradiated with laser light (wavelength: 633 nm), and stimulated emission light emitted from the panel was detected by a photomultiplier to measure the stimulated emission amount. The obtained stimulated luminescence amount was converted into the layer thickness of the phosphor layer, and the relative value when the luminescence amount of each comparative example was 100 was taken as the sensitivity.
【００７０】（２）付活剤（Ｅｕ）分布特性
放射線像変換パネルの蛍光体層を厚み方向にエッチング
しながら、二次イオン質量分析装置（ＳＩＭＳ）を用い
て一次イオンビームを照射し、蛍光体層からスパッタさ
れた二次イオンの質量分析を行って層厚方向のＥｕ濃度
分布を求め、Ｅｕ濃度の均一性を以下の基準にて評価し
た。
ＡＡ：極めて良好、 Ａ：良好、 Ｂ：やや不良、
Ｃ：不良であって実用上問題がある(2) Activator (Eu) distribution characteristic While the phosphor layer of the radiation image conversion panel is being etched in the thickness direction, the secondary ion mass spectrometer (SIMS) is used to irradiate the primary ion beam to emit fluorescence. The secondary ion sputtered from the body layer was subjected to mass spectrometry to obtain the Eu concentration distribution in the layer thickness direction, and the uniformity of the Eu concentration was evaluated according to the following criteria. AA: Extremely good, A: Good, B: Somewhat bad, C: Poor and practically problematic
【００７１】（３）柱状結晶性
放射線像変換パネルの蛍光体層を支持体ごと厚み方向に
切断し、チャージアップ防止のためにイオンスパッタに
より金（厚み：３００オングストローム）で被覆した
後、走査型電子顕微鏡（ＪＳＭ−５４００型、日本電子
(株)製）を用いて、蛍光体層の表面および切断面を観察
し、以下の基準にて評価した。
Ａ：良好、 Ｂ：やや不良、 Ｃ：不良であって実用上
問題がある(3) The phosphor layer of the columnar crystalline radiation image conversion panel was cut in the thickness direction together with the support, and covered with gold (thickness: 300 Å) by ion sputtering to prevent charge-up, and then scanned. Electron microscope (JSM-5400 type, JEOL
(Manufactured by KK), the surface and cut surface of the phosphor layer were observed and evaluated according to the following criteria. A: Good, B: Slightly bad, C: Bad and practically problematic
【００７２】（４）支持体（基板）との接着性：蛍光体
層の支持体からの剥離し易さにより判断し、以下の基準
にて評価した。
ＡＡ：極めて良好、 Ａ：良好、 Ｂ：やや不良、
Ｃ：不良であって実用上問題がある
得られた結果をまとめて表１および表２に示す。(4) Adhesiveness to Support (Substrate): Judgment was made based on the ease of peeling the phosphor layer from the support, and the evaluation was made according to the following criteria. AA: extremely good, A: good, B: somewhat bad, C: bad and practically problematic. The obtained results are summarized in Tables 1 and 2.
【００７３】[0073]
【表１】 [Table 1]
【００７４】[0074]
【表２】 [Table 2]
【００７５】表１及び表２の結果から、本発明に従って
蒸着開始直後と終了間際の一定時間シャッタを閉じるこ
とによりその間の期間のみ基板上に蒸着させて得られた
放射線像変換パネル（実施例１〜１５）はいずれも、蒸
着開始から終了まで基板上に蒸着させて得られた従来の
放射線像変換パネル（比較例１〜４）と比較して、蛍光
体層の層厚方向におけるＥｕ濃度分布が均一で良好であ
り、感度が向上することが明らかである。また、本発明
に従うパネルは柱状結晶性も向上していて、基板との接
着性も良好であった。From the results shown in Tables 1 and 2, the radiation image conversion panel obtained by depositing the substrate on the substrate only during the period during which the shutter was closed for a certain period of time immediately after the vapor deposition was started and immediately after the vapor deposition according to the present invention (Example 1). 15 to 15), compared with the conventional radiation image conversion panels (Comparative Examples 1 to 4) obtained by vapor deposition on the substrate from the start to the end of vapor deposition, the Eu concentration distribution in the layer thickness direction of the phosphor layer. Is uniform and good, and it is clear that the sensitivity is improved. In addition, the panel according to the present invention had improved columnar crystallinity and good adhesiveness to the substrate.
【００７６】［実施例１６］
（１）蒸発源の作製
実施例１と同様にして、ＣｓＢｒ：0.01Ｅｕ蛍光体のタ
ブレット（直径：３５ｍｍ、厚み：２０ｍｍ）を作製し
た。Example 16 (1) Preparation of Evaporation Source In the same manner as in Example 1, tablets of CsBr: 0.01Eu phosphor (diameter: 35 mm, thickness: 20 mm) were prepared.
【００７７】（２）蛍光体層の形成
支持体として、順にアルカリ洗浄、純水洗浄、およびＩ
ＰＡ洗浄を施した合成石英基板（サイズ：１００ｍｍ×
１００ｍｍ）を用意し、蒸着装置内の基板保持部材に設
置した。上記ＣｓＢｒ：Ｅｕ蒸発源を装置内の所定位置
に装填し、一方補給材料としてＣｓＢｒ粉末（平均粒
径：３０μｍ）を装置内の補給材料タンク２２に装填し
た（図３参照）。その後、装置内を真空排気装置により
排気して１×１０-3Ｐａの真空度とした。このとき、真
空排気装置としてロータリーポンプ、メカニカルブース
タ、ターボ分子ポンプの組合せを用いた。次いで、基板
の蒸着面とは反対側に位置したシーズヒータで、石英基
板を２００℃に加熱した。(2) Formation of Phosphor Layer As a support, alkaline cleaning, pure water cleaning, and I
Synthetic quartz substrate washed with PA (size: 100 mm x
100 mm) was prepared and installed on the substrate holding member in the vapor deposition apparatus. The above CsBr: Eu evaporation source was loaded in a predetermined position in the apparatus, while CsBr powder (average particle size: 30 μm) was loaded as a replenishing material in the replenishing material tank 22 in the apparatus (see FIG. 3). Then, the inside of the device was evacuated by a vacuum exhaust device to a vacuum degree of 1 × 10 −3 Pa. At this time, a combination of a rotary pump, a mechanical booster, and a turbo molecular pump was used as a vacuum exhaust device. Next, the quartz substrate was heated to 200 ° C. with a sheath heater located on the side opposite to the vapor deposition surface of the substrate.
【００７８】ＣｓＢｒ粉末を補給材料タンク２２から送
りガイド２３を経て蒸発源１０に供給しながら、蒸発源
１０に電子銃７で加速電圧−４．０ｋＶの電子線を照射
して、基板上に輝尽性蛍光体を４μｍ／分の速度で堆積
させた。このとき、前もって蒸発源のみを蒸着させて得
られた蒸着膜のＥｕ濃度分布に基づいて、蒸発流のＥｕ
濃度が一定になるように補給速度を設定した補給速度制
御系２５からの制御により、補給調整部材２４を随時上
下に移動させて、ＣｓＢｒ粉末の補給速度を調整した。
蒸着雰囲気中の水分圧は４×１０-3Ｐａであった。While the CsBr powder is being supplied from the replenishment material tank 22 to the evaporation source 10 via the feed guide 23, the evaporation source 10 is irradiated with an electron beam with an accelerating voltage of −4.0 kV by the electron gun 7 to illuminate the substrate. The exhaustive phosphor was deposited at a rate of 4 μm / min. At this time, based on the Eu concentration distribution of the deposited film obtained by previously depositing only the evaporation source,
Under the control of the replenishment rate control system 25 in which the replenishment rate was set so that the concentration was constant, the replenishment adjustment member 24 was moved up and down at any time to adjust the CsBr powder replenishment rate.
The moisture pressure in the vapor deposition atmosphere was 4 × 10 −3 Pa.
【００７９】次に、この石英基板をガス導入可能な真空
加熱装置に入れ、ロータリーポンプにより約１Ｐａまで
真空に引いて基板上の蒸着膜に吸着している水分等を除
去した後、窒素ガス雰囲気中、２００℃の温度で２時間
蒸着膜を熱処理した。真空下で基板を冷却し、十分に温
度が下がった時点で装置から基板を取り出した。基板上
には、蛍光体の柱状結晶がほぼ垂直方向に密に林立した
構造の蛍光体層が形成されていた。このようにして、支
持体と蛍光体層とからなる本発明に従う放射線像変換パ
ネルを製造した。Next, this quartz substrate was placed in a vacuum heating apparatus capable of introducing gas, and a rotary pump was evacuated to about 1 Pa to remove water and the like adsorbed on the vapor-deposited film on the substrate. The deposited film was heat-treated at a temperature of 200 ° C. for 2 hours. The substrate was cooled under vacuum, and when the temperature was sufficiently lowered, the substrate was taken out from the apparatus. On the substrate, a phosphor layer having a structure in which columnar crystals of phosphor were densely forested in a substantially vertical direction was formed. In this way, a radiation image conversion panel according to the present invention comprising a support and a phosphor layer was produced.
【００８０】［実施例１７］実施例１６の（２）蛍光体
層の形成において、補給材料としてＣｓＢｒ：0.001Ｅ
ｕ蛍光体粉末（平均粒径：５０μｍ）を用いたこと以外
は実施例１６と同様にして、本発明に従う放射線像変換
パネルを製造した。[Embodiment 17] CsBr: 0.001E as a replenishing material in (2) Phosphor layer formation of Embodiment 16
A radiation image conversion panel according to the present invention was produced in the same manner as in Example 16 except that u phosphor powder (average particle size: 50 μm) was used.
【００８１】［実施例１８］実施例１６の（１）蒸発源
の作製において、ＣｓＢｒ：0.03Ｅｕ蛍光体のタブレッ
トを作製したこと以外は実施例１６と同様にして、本発
明に従う放射線像変換パネルを製造した。[Example 18] A radiation image conversion panel according to the present invention in the same manner as in Example 16 except that a tablet of CsBr: 0.03Eu phosphor was prepared in (1) Preparation of evaporation source of Example 16. Was manufactured.
【００８２】［実施例１９］実施例１６の（１）蒸発源
の作製において、ＣｓＢｒ：0.03Ｅｕ蛍光体のタブレッ
トを作製したこと、および（２）蛍光体層の形成におい
て、プラズマ発光分光器を用いて電子線照射中連続的に
Ｅｕ2+のプラズマ発光（青色光）を検出し、その発光強
度が一定になるように、補給速度制御系２５で補給調整
部材２４の位置を制御してＣｓＢｒ粉末の補給速度を調
整したこと以外は実施例１６と同様にして、本発明に従
う放射線像変換パネルを製造した。[Example 19] A plasma emission spectrometer was used in (1) the production of the evaporation source of Example 16 to produce a tablet of the CsBr: 0.03Eu phosphor, and (2) in the formation of the phosphor layer. Eu 2+ plasma emission (blue light) is continuously detected during electron beam irradiation using CsBr by controlling the position of the replenishment adjusting member 24 by the replenishment rate control system 25 so that the emission intensity becomes constant. A radiation image conversion panel according to the present invention was produced in the same manner as in Example 16 except that the powder supply rate was adjusted.
【００８３】［実施例２０］実施例１６の（１）蒸発源
の作製において、ＣｓＢｒ：0.03Ｅｕ蛍光体のタブレッ
トを作製したこと、および（２）蛍光体層の形成におい
て、補給材料としてＣｓＢｒ：0.001Ｅｕ蛍光体粉末
（平均粒径：５０μｍ）を用いたこと以外は実施例１６
と同様にして、本発明に従う放射線像変換パネルを製造
した。[Example 20] A tablet of CsBr: 0.03Eu phosphor was prepared in (1) Preparation of evaporation source of Example 16, and (2) CsBr: as a supplementary material in the formation of the phosphor layer. Example 16 except that 0.001 Eu phosphor powder (average particle size: 50 μm) was used
A radiation image conversion panel according to the present invention was manufactured in the same manner as in.
【００８４】［実施例２１］実施例１６の（２）蛍光体
層の形成において、電子銃の代わりに抵抗加熱器を用い
て蒸発源を加熱したこと以外は実施例１６と同様にし
て、本発明に従う放射線像変換パネルを製造した。[Embodiment 21] This embodiment is the same as Embodiment 16 except that (2) the phosphor layer is formed in Embodiment 16 except that a resistance heater is used instead of the electron gun to heat the evaporation source. A radiation image conversion panel according to the invention was produced.
【００８５】［実施例２２］実施例１６の（１）蒸発源
の作製において、ＣｓＢｒ：0.03Ｅｕ蛍光体のタブレッ
トを作製したこと、および（２）蛍光体層の形成におい
て、電子銃の代わりに抵抗加熱器を用いて蒸発源を加熱
したこと以外は実施例１６と同様にして、本発明に従う
放射線像変換パネルを製造した。[Example 22] A tablet of CsBr: 0.03Eu phosphor was prepared in (1) Preparation of evaporation source of Example 16, and (2) In formation of phosphor layer, instead of an electron gun. A radiation image conversion panel according to the present invention was produced in the same manner as in Example 16 except that the evaporation source was heated using a resistance heater.
【００８６】［放射線像変換パネルの性能評価２］得ら
れた各放射線像変換パネルの蛍光体層について、前述と
同様にして感度、付活剤分布特性、柱状結晶性および支
持体との接着性により評価を行った。得られた結果をま
とめて表３に示す。[Performance Evaluation 2 of Radiation Image Conversion Panel] Regarding the obtained phosphor layer of each radiation image conversion panel, the sensitivity, activator distribution characteristics, columnar crystallinity and adhesiveness to the support were carried out in the same manner as described above. Was evaluated by. The results obtained are summarized in Table 3.
【００８７】[0087]
【表３】 [Table 3]
【００８８】表３の結果から、本発明に従って蒸発源に
蛍光体母体成分または低Ｅｕ含量の蛍光体を補給しなが
ら蒸着を行って得られた放射線像変換パネル（実施例１
６〜２２）はいずれも、従来の補給無しで得られた放射
線像変換パネル（比較例１〜４）と比較して、蛍光体層
の層厚方向におけるＥｕ濃度分布が均一で良好であり、
感度が向上することが明らかである。また、本発明に従
うパネルは柱状結晶性も向上していて、基板との接着性
も良好であった。From the results shown in Table 3, the radiation image conversion panel obtained by performing vapor deposition while replenishing the evaporation source with the phosphor matrix component or the phosphor having a low Eu content according to the present invention (Example 1).
6 to 22), compared with the conventional radiation image conversion panels obtained without replenishment (Comparative Examples 1 to 4), the Eu concentration distribution in the layer thickness direction of the phosphor layer is uniform and good,
It is clear that the sensitivity is improved. In addition, the panel according to the present invention had improved columnar crystallinity and good adhesiveness to the substrate.
【００８９】[0089]
【発明の効果】本発明によれば、蒸発源と基板との間に
シャッタを設け、蒸着開始直後、更には蒸着終了間際の
蒸発流を基板上に蒸着させないことにより、および／ま
たは蒸発源に蛍光体母体成分または付活剤含量の少ない
蛍光体を補給しながら蒸着を行うことにより、母体成分
と付活剤成分とで蒸気圧差があっても一元蒸着法で、厚
み方向に付活剤濃度の均一な蛍光体層を形成することが
できる。これにより、高感度の放射線像変換パネルが得
られる。また、柱状結晶性が良好であって、亀裂や剥離
の無い蛍光体層を形成することができるので、高画質の
放射線画像を与える放射線像変換パネルが得られる。According to the present invention, a shutter is provided between the evaporation source and the substrate so that the evaporation flow immediately after the start of vapor deposition and immediately before the end of vapor deposition is not vaporized on the substrate, and / or at the vapor source. By performing vapor deposition while replenishing the phosphor matrix component or the phosphor with a small activator content, even if there is a difference in vapor pressure between the matrix component and the activator component, the concentration of the activator in the thickness direction can be increased by the unitary vapor deposition method. It is possible to form a uniform phosphor layer. Thereby, a highly sensitive radiation image conversion panel can be obtained. Further, since the phosphor layer having good columnar crystallinity and free from cracks and peeling can be formed, a radiation image conversion panel which gives a high quality radiation image can be obtained.
【図１】本発明に用いられる蒸着装置の構成例を示す概
略断面図である。FIG. 1 is a schematic cross-sectional view showing a configuration example of a vapor deposition device used in the present invention.
【図２】図１のシャッタを示す概略斜視図である。FIG. 2 is a schematic perspective view showing the shutter of FIG.
【図３】本発明に用いられる蒸発源補給装置の構成例を
示す概略斜視図である。FIG. 3 is a schematic perspective view showing a configuration example of an evaporation source replenishing device used in the present invention.
１ 蒸着チャンバ ２ 基板加熱用ヒータ ４、４’ 基板 ５ シャッタ ７ 電子銃 ８ 電子線 １０ 蒸発源 ２１ 蒸発源補給系 ２２ 補給材料タンク ２３ 補給材料送りガイド ２４ 補給調整部材 ２５ 補給速度制御系 1 evaporation chamber 2 Substrate heating heater 4,4 'substrate 5 shutters 7 electron gun 8 electron beams 10 evaporation sources 21 Evaporation source supply system 22 Replenishment material tank 23 Replenishment Material Feeding Guide 24 Supply adjustment member 25 Replenishment speed control system
───────────────────────────────────────────────────── フロントページの続き (51)Int.Cl.7 識別記号 ＦＩ テーマコート゛(参考） Ｃ０９Ｋ 11/64 Ｃ０９Ｋ 11/64 11/85 11/85 Ｇ０１Ｔ 1/00 Ｇ０１Ｔ 1/00 Ｂ Ｆターム(参考） 2G083 AA03 BB01 CC03 DD02 DD12 DD15 EE02 EE03 4H001 CA08 XA03 XA04 XA09 XA11 XA12 XA13 XA17 XA19 XA20 XA21 XA28 XA29 XA30 XA31 XA35 XA37 XA38 XA39 XA48 XA49 XA53 XA55 XA56 XA57 XA58 XA59 XA60 XA61 XA62 XA63 XA64 XA65 XA66 XA67 XA68 XA69 XA70 XA71 YA63─────────────────────────────────────────────────── ─── Continuation of front page (51) Int.Cl. 7 Identification code FI theme code (reference) C09K 11/64 C09K 11/64 11/85 11/85 G01T 1/00 G01T 1/00 B F term (reference) ) 2G083 AA03 BB01 CC03 DD02 DD12 DD15 EE02 EE03 4H001 CA08 XA03 XA04 XA09 XA11 XA12 XA13 XA17 XA19 XA20 XA21 XA28 XA29 XA30 XA31 XA XA XA XA XA XA XA XA XA XA XA XA XAX AA XA XAX XAX YA63
Claims (12)
原料を含む蒸発源を加熱して発生する物質を基板上に蒸
着させることにより蛍光体層を形成する工程を含む放射
線像変換パネルの製造方法において、蒸着装置として蒸
発源と該基板との間に開閉可能なシャッタが備えられた
蒸着装置を用い、蒸発源として基本組成式（Ｉ）を有す
るユーロピウム付活アルカリ金属ハロゲン化物系輝尽性
蛍光体を含む蒸発源を用いて、該シャッタを閉じた状態
で蒸着を開始し、一定時間経過後にシャッタを開いて基
板上に該蛍光体を蒸着させることを特徴とする放射線像
変換パネルの製造方法。 ＭIＸ・ａＭIIＸ’2・ｂＭIIIＸ”3：ｚＥｕ ‥‥（Ｉ） ［ただし、ＭIはＬｉ、Ｎａ、Ｋ、Ｒｂ及びＣｓからな
る群より選ばれる少なくとも一種のアルカリ金属を表
し；ＭIIはＢｅ、Ｍｇ、Ｃａ、Ｓｒ、Ｂａ、Ｎｉ、Ｃ
ｕ、Ｚｎ及びＣｄからなる群より選ばれる少なくとも一
種のアルカリ土類金属又は二価金属を表し；ＭIIIはＳ
ｃ、Ｙ、Ｌａ、Ｃｅ、Ｐｒ、Ｎｄ、Ｐｍ、Ｓｍ、Ｅｕ、
Ｇｄ、Ｔｂ、Ｄｙ、Ｈｏ、Ｅｒ、Ｔｍ、Ｙｂ、Ｌｕ、Ａ
ｌ、Ｇａ及びＩｎからなる群より選ばれる少なくとも一
種の希土類元素又は三価金属を表し；Ｘ、Ｘ’及びＸ”
はそれぞれ、Ｆ、Ｃｌ、Ｂｒ及びＩからなる群より選ば
れる少なくとも一種のハロゲンを表し；そしてａ、ｂ及
びｚはそれぞれ、０≦ａ＜０．５、０≦ｂ＜０．５、０
＜ｚ＜１．０の範囲内の数値を表す］1. A radiation image conversion panel including a step of forming a phosphor layer by evaporating a substance generated by heating an evaporation source containing a phosphor or a phosphor raw material on a substrate in a vapor deposition apparatus. In the manufacturing method, a vapor deposition apparatus having a shutter that can be opened and closed between the vapor source and the substrate is used, and the europium-activated alkali metal halide-based photostimulation having the basic composition formula (I) is used as the vapor source. Of a radiation image conversion panel, characterized in that, by using an evaporation source containing a fluorescent substance, vapor deposition is started in a state in which the shutter is closed, and after a certain period of time, the shutter is opened to vaporize the fluorescent substance on the substrate. Production method. M I X · aM II X ′ 2 · bM III X ″ 3 : zEu (I) [wherein M I represents at least one alkali metal selected from the group consisting of Li, Na, K, Rb and Cs] M II is Be, Mg, Ca, Sr, Ba, Ni, C
represents at least one alkaline earth metal or divalent metal selected from the group consisting of u, Zn and Cd; M III is S
c, Y, La, Ce, Pr, Nd, Pm, Sm, Eu,
Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu, A
represents at least one rare earth element or trivalent metal selected from the group consisting of 1, Ga and In; X, X ′ and X ″
Each represents at least one halogen selected from the group consisting of F, Cl, Br, and I; and a, b, and z are 0 ≦ a <0.5, 0 ≦ b <0.5, 0, respectively.
<Represents a numerical value within the range of z <1.0]
Ｔとするとき、蒸着開始後１／１０Ｔ乃至１／２Ｔ経過
時にシャッタを開く請求項１に記載の放射線像変換パネ
ルの製造方法。2. The method for manufacturing a radiation image conversion panel according to claim 1, wherein the shutter is opened 1/10 T to 1/2 T after the start of vapor deposition, where T is the time required for all the vaporization sources to vaporize.
にシャッタを開く請求項２に記載の放射線像変換パネル
の製造方法。3. The method for manufacturing a radiation image conversion panel according to claim 2, wherein the shutter is opened when 1 / 5T to 1 / 2T has elapsed after the start of vapor deposition.
じて基板上への蛍光体の蒸着を中止する請求項１乃至３
のうちのいずれかの項に記載の放射線像変換パネルの製
造方法。4. The shutter is closed again after a certain period of time, and the vapor deposition of the phosphor on the substrate is stopped.
A method of manufacturing a radiation image storage panel according to any one of items 1 to 10.
Ｔとするとき、蒸着開始後１／２Ｔ乃至９／１０Ｔ経過
時にシャッタを閉じる（ただし、１／２Ｔ経過時にシャ
ッタを開くとき、１／２Ｔは含まない）請求項４に記載
の放射線像変換パネルの製造方法。5. When the time required for all the evaporation sources to evaporate is T, the shutter is closed after 1 / 2T to 9 / 10T has elapsed since the start of vapor deposition (however, when the shutter is opened after 1 / 2T, 1 / 2T is not included) The method for manufacturing a radiation image conversion panel according to claim 4.
にシャッタを閉じる請求項５に記載の放射線像変換パネ
ルの製造方法。6. The method for manufacturing a radiation image conversion panel according to claim 5, wherein the shutter is closed when 1 / 2T to 2 / 3T has elapsed after the start of vapor deposition.
補給しながら、蒸着を行う請求項１乃至６のうちのいず
れかの項に記載の放射線像変換パネルの製造方法。7. The method for manufacturing a radiation image conversion panel according to claim 1, wherein the vapor deposition is performed while supplying at least a matrix component of the phosphor to the evaporation source.
ｓＢｒであり、そしてｚが０．００１≦ｚ≦０．１の範
囲内の数値である請求項１乃至７のうちのいずれかの項
に記載の放射線像変換パネルの製造方法。8. In the basic composition formula (I), M I X is C
The method for manufacturing a radiation image conversion panel according to claim 1, wherein the radiation image conversion panel is sBr, and z is a numerical value within the range of 0.001 ≦ z ≦ 0.1.
加熱することによって発生する物質を基板上に蒸着させ
ることにより蛍光体層を形成する工程を含む放射線像変
換パネルの製造方法において、該蒸発源として基本組成
式（Ｉ）を有するユーロピウム付活アルカリ金属ハロゲ
ン化物系輝尽性蛍光体を含む蒸発源を用い、そして蒸発
源に少なくとも該蛍光体の母体成分を補給しながら、基
板上に蛍光体を蒸着させることを特徴とする放射線像変
換パネルの製造方法。 ＭIＸ・ａＭIIＸ’2・ｂＭIIIＸ”3：ｚＥｕ ‥‥（Ｉ） ［ただし、ＭIはＬｉ、Ｎａ、Ｋ、Ｒｂ及びＣｓからな
る群より選ばれる少なくとも一種のアルカリ金属を表
し；ＭIIはＢｅ、Ｍｇ、Ｃａ、Ｓｒ、Ｂａ、Ｎｉ、Ｃ
ｕ、Ｚｎ及びＣｄからなる群より選ばれる少なくとも一
種のアルカリ土類金属又は二価金属を表し；ＭIIIはＳ
ｃ、Ｙ、Ｌａ、Ｃｅ、Ｐｒ、Ｎｄ、Ｐｍ、Ｓｍ、Ｅｕ、
Ｇｄ、Ｔｂ、Ｄｙ、Ｈｏ、Ｅｒ、Ｔｍ、Ｙｂ、Ｌｕ、Ａ
ｌ、Ｇａ及びＩｎからなる群より選ばれる少なくとも一
種の希土類元素又は三価金属を表し；Ｘ、Ｘ’及びＸ”
はそれぞれ、Ｆ、Ｃｌ、Ｂｒ及びＩからなる群より選ば
れる少なくとも一種のハロゲンを表し；そしてａ、ｂ及
びｚはそれぞれ、０≦ａ＜０．５、０≦ｂ＜０．５、０
＜ｚ＜１．０の範囲内の数値を表す］9. A method of manufacturing a radiation image storage panel, comprising the step of forming a phosphor layer by depositing a substance generated by heating an evaporation source containing the phosphor or its raw material on a substrate. As a source, an evaporation source containing a europium-activated alkali metal halide-based stimulable phosphor having a basic composition formula (I) is used, and while the evaporation source is supplemented with at least a matrix component of the phosphor, fluorescence on a substrate A method of manufacturing a radiation image conversion panel, which comprises depositing a body. M I X · aM II X ′ 2 · bM III X ″ 3 : zEu (I) [wherein M I represents at least one alkali metal selected from the group consisting of Li, Na, K, Rb and Cs] M II is Be, Mg, Ca, Sr, Ba, Ni, C
represents at least one alkaline earth metal or divalent metal selected from the group consisting of u, Zn and Cd; M III is S
c, Y, La, Ce, Pr, Nd, Pm, Sm, Eu,
Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu, A
represents at least one rare earth element or trivalent metal selected from the group consisting of 1, Ga and In; X, X ′ and X ″
Each represent at least one halogen selected from the group consisting of F, Cl, Br and I; and a, b and z represent 0 ≦ a <0.5, 0 ≦ b <0.5, 0, respectively.
<Represents a numerical value within the range of z <1.0]
発量に応じて、少なくとも蛍光体母体成分の補給速度を
制御する請求項９に記載の放射線像変換パネルの製造方
法。10. The method of manufacturing a radiation image conversion panel according to claim 9, wherein at least the replenishment rate of the phosphor matrix component is controlled according to the amount of europium evaporated from the evaporation source.
ピウム含量よりも低いユーロピウム含量の該蛍光体を補
給する請求項９または１０に記載の放射線像変換パネル
の製造方法。11. The method for producing a radiation image conversion panel according to claim 9, wherein the evaporation source is supplemented with the phosphor having a europium content lower than that of the phosphor in the evaporation source.
ＣｓＢｒであり、そしてｚが０．００１≦ｚ≦０．１の
範囲内の数値である請求項９乃至１１のうちのいずれか
の項に記載の放射線像変換パネルの製造方法。12. The basic composition formula (I), M I X is CsBr, and any of claims 9 to 11 z is a number in the range of 0.001 ≦ z ≦ 0.1 The method for manufacturing a radiation image storage panel according to the item.
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|---|---|---|---|
| JP2002107054A JP2003302497A (en) | 2002-04-09 | 2002-04-09 | Manufacturing method of radiological image conversion panel |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2002107054A JP2003302497A (en) | 2002-04-09 | 2002-04-09 | Manufacturing method of radiological image conversion panel |
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| Publication Number | Publication Date |
|---|---|
| JP2003302497A true JP2003302497A (en) | 2003-10-24 |
Family
ID=29391195
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2006010479A (en) * | 2004-06-25 | 2006-01-12 | Konica Minolta Medical & Graphic Inc | Manufacturing method for radiation image conversion panel |
| JP2006152199A (en) * | 2004-12-01 | 2006-06-15 | Konica Minolta Medical & Graphic Inc | Radiation image conversion panel, its production method and production apparatus |
| JP2006193545A (en) * | 2005-01-11 | 2006-07-27 | Konica Minolta Medical & Graphic Inc | Method for producing radiation image conversion panel and vacuum deposition apparatus |
| JP2009503479A (en) * | 2005-07-26 | 2009-01-29 | シーメンス アクチエンゲゼルシヤフト | Radiation converter and manufacturing method of radiation converter |
-
2002
- 2002-04-09 JP JP2002107054A patent/JP2003302497A/en not_active Withdrawn
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2006010479A (en) * | 2004-06-25 | 2006-01-12 | Konica Minolta Medical & Graphic Inc | Manufacturing method for radiation image conversion panel |
| JP4569191B2 (en) * | 2004-06-25 | 2010-10-27 | コニカミノルタエムジー株式会社 | Manufacturing method of radiation image conversion panel |
| JP2006152199A (en) * | 2004-12-01 | 2006-06-15 | Konica Minolta Medical & Graphic Inc | Radiation image conversion panel, its production method and production apparatus |
| JP2006193545A (en) * | 2005-01-11 | 2006-07-27 | Konica Minolta Medical & Graphic Inc | Method for producing radiation image conversion panel and vacuum deposition apparatus |
| JP2009503479A (en) * | 2005-07-26 | 2009-01-29 | シーメンス アクチエンゲゼルシヤフト | Radiation converter and manufacturing method of radiation converter |
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