JPH07278540A - Green luminous fluorescent substance of rare earth elements oxysulfide and sensitized paper containing the same - Google Patents
Green luminous fluorescent substance of rare earth elements oxysulfide and sensitized paper containing the sameInfo
- Publication number
- JPH07278540A JPH07278540A JP6070394A JP7039494A JPH07278540A JP H07278540 A JPH07278540 A JP H07278540A JP 6070394 A JP6070394 A JP 6070394A JP 7039494 A JP7039494 A JP 7039494A JP H07278540 A JPH07278540 A JP H07278540A
- Authority
- JP
- Japan
- Prior art keywords
- phosphor
- rare earth
- intensifying screen
- fluorescent substance
- earth oxysulfide
- 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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- Non-Silver Salt Photosensitive Materials And Non-Silver Salt Photography (AREA)
- Luminescent Compositions (AREA)
- Silver Salt Photography Or Processing Solution Therefor (AREA)
Abstract
Description
【０００１】[0001]
【産業上の利用分野】本発明は緑色発光希土類酸硫化物
蛍光体及びこれを用いた増感紙に関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a green light emitting rare earth oxysulfide phosphor and an intensifying screen using the same.
【０００２】[0002]
【従来の技術】テルビウム（Ｔｂ）で付活した希土類酸
硫化物蛍光体は、Ｘ線励起により高輝度の緑色発光を呈
するところから、Ｘ線写真撮影に際し撮影系の感度を向
上させるためにＸ線フイルムと組み合わせて使用される
増感紙用として広く用いられている。2. Description of the Related Art A rare earth oxysulfide phosphor activated with terbium (Tb) emits green light with high brightness when excited by X-rays. Therefore, in order to improve the sensitivity of an imaging system during X-ray photography, X Widely used for intensifying screens used in combination with line film.
【０００３】ところで、増感紙においては写真感度が高
いことの外に鮮鋭度、粒状性等の写真画質が良好である
ことが好ましいが、Ｔｂで付活した緑色発光希土類酸硫
化物蛍光体（以下、希土類酸硫化物螢光体と言う）を蛍
光体層に用いた増感紙においては、写真感度は高いもの
の写真画質は必ずしも十分ではなく、写真画質のより一
層の向上が望まれている。By the way, it is preferable that the intensifying screen has good photographic image quality such as sharpness and graininess in addition to high photographic sensitivity, but a green light emitting rare earth oxysulfide phosphor activated by Tb ( Hereinafter, in the intensifying screen using a phosphor layer of a rare earth oxysulfide phosphor), although the photographic sensitivity is high, the photographic image quality is not always sufficient, and further improvement of the photographic image quality is desired. .
【０００４】また、高速のＸ線撮影においては残像を生
じさせないために出来る限り残光の短い増感紙が望まれ
るが、希土類酸硫化物蛍光体を用いた増感紙の残光特性
は必ずしも充分ではなく、その改良が望まれている。Further, in high-speed X-ray photography, an intensifying screen having as short a afterglow as possible is desired so as not to cause an afterimage, but the afterglow characteristic of the intensifying screen using a rare earth oxysulfide phosphor is not always required. It is not sufficient, and its improvement is desired.
【０００５】[0005]
【発明が解決しようとする課題】本発明の目的は、増感
紙の蛍光体層に用いた時に、従来の増感紙に比べてより
鮮鋭度の向上した増感紙が得られる希土類酸硫化物蛍光
体並びにより鮮鋭度の向上した増感紙を提供することに
ある。また本発明の目的は、上記の鮮鋭度の向上に加え
て、従来のものに比べて残光の低減された希土類酸硫化
物蛍光体並びに増感紙を提供することにある。SUMMARY OF THE INVENTION An object of the present invention is to provide a rare earth oxysulfide which, when used in a phosphor layer of an intensifying screen, can provide an intensifying screen having a sharpness higher than that of a conventional intensifying screen. It is intended to provide a fluorescent substance and an intensifying screen having improved sharpness. It is another object of the present invention to provide a rare earth oxysulfide phosphor and an intensifying screen having afterglow reduced as compared with the conventional one, in addition to the improvement of the sharpness.
【０００６】[0006]
【課題を解決するための手段】本発明者等は上記の目的
を達成するために、希土類酸硫化物蛍光体に添加する不
純物元素と、このような不純物元素を含有する蛍光体を
蛍光体層に用いた増感紙の鮮鋭度並びに残光特性との関
係について種々研究を重ねた結果、特定組成の希土類酸
硫化物蛍光体に特定量の亜鉛（Ｚｎ）を含有させること
により、この蛍光体を用いた増感紙の鮮鋭度が向上し、
更にこのＺｎを含有させた螢光体に特定量のセリウム
（Ｃｅ）、スカンジウム（Ｓｃ）、ネオジム（Ｎｄ）及
びイッテルビウム（Ｙｂ）の内の少なくとも１種を含有
させると残光が著しく低減し、これらの蛍光体を螢光体
層に用いることによって、従来の希土類酸硫化物蛍光体
を用いた増感紙に比べて鮮鋭度が向上し且つ残光の低減
した増感紙が得られることを見出し、本発明を完成し
た。SUMMARY OF THE INVENTION In order to achieve the above-mentioned object, the present inventors have made an impurity element added to a rare earth oxysulfide phosphor and a phosphor containing such an impurity element a phosphor layer. As a result of various studies on the relationship between the sharpness of the intensifying screen used for the above and the afterglow characteristics, the rare earth oxysulfide phosphor of a specific composition was made to contain a specific amount of zinc (Zn) The sharpness of the intensifying screen using
Furthermore, if at least one of cerium (Ce), scandium (Sc), neodymium (Nd) and ytterbium (Yb) is contained in the phosphor containing Zn, the afterglow is significantly reduced, By using these phosphors in the phosphor layer, it is possible to obtain an intensifying screen with improved sharpness and reduced afterglow as compared with intensifying screens using conventional rare earth oxysulfide phosphors. Heading, completed the present invention.
【０００７】即ち、本発明の希土類酸硫化物蛍光体は、
その組成式が （Ｇｄ1-X-Y-z ，Ｙx ，Ｔｂy ，Ｔｍz ）2 Ｏ2 Ｓ （但し、ｘ、ｙ及びｚはそれぞれ０≦ｘ≦０. ４、０.
０００１≦ｙ≦０. ０２及び０≦ｚ≦０. ００５なる条
件を満足する数である。以下同様である）で表され、更
に０. ３〜３０ｐｐｍの亜鉛（Ｚｎ）を含有することを
特徴とする。That is, the rare earth oxysulfide phosphor of the present invention is
The composition formula (Gd 1-XYz, Y x , Tb y, Tm z) 2 O 2 S ( where, x, respectively 0 ≦ y-and z x ≦ 0. 4,0.
It is a number that satisfies the conditions of 0001≤y≤0.02 and 0≤z≤0.005. The same shall apply hereinafter), and 0.3 to 30 ppm of zinc (Zn) is further contained.
【０００８】また本発明の希土類酸硫化物蛍光体は、そ
の組成式が （Ｇｄ1-X-Y-z ，Ｙx ，Ｔｂy ，Ｔｍz ）2 Ｏ2 Ｓ で表され、更に（イ）０. ３〜３０ｐｐｍの亜鉛（Ｚ
ｎ）と、（ロ）０. ０４〜０. ６ｐｐｍのセリウム（Ｃ
ｅ）及び／又は合計で０．０４〜１０ｐｐｍのスカンジ
ウム（Ｓｃ）、ネオジム（Ｎｄ）及びイッテルビウム
（Ｙｂ）の内の少なくとも１種とを含有することを特徴
とする。Further rare earth oxysulfide phosphor of the present invention has a composition formula represented by (Gd 1-XYz, Y x , Tb y, Tm z) 2 O 2 S, and (b) 0. 3 30 ppm zinc (Z
n) and (b) 0.04 to 0.6 ppm of cerium (C
e) and / or 0.04 to 10 ppm in total of at least one of scandium (Sc), neodymium (Nd) and ytterbium (Yb).
【０００９】更に、本発明の増感紙は支持体と、この支
持体上に設けられたＸ線用蛍光体及び該Ｘ線用蛍光体を
分散支持する結合剤からなる蛍光体層とを有する増感紙
において、該Ｘ線用蛍光体がそれぞれ上記各希土類酸硫
化物蛍光体からなることを特徴とする。Furthermore, the intensifying screen of the present invention has a support, and a phosphor layer comprising an X-ray phosphor provided on the support and a binder for dispersing and supporting the X-ray phosphor. In the intensifying screen, each of the X-ray phosphors is made of the above-mentioned rare earth oxysulfide phosphor.
【００１０】以下に、本発明を詳細に説明する：本発明
の希土類酸硫化物蛍光体は、蛍光体原料混合物に不純物
元素としてＺｎ、又はＺｎとＣｅ、Ｓｃ、Ｎｄ及びＹｂ
の内の少なくとも１種とを、それぞれＺｎ化合物、Ｃｅ
化合物、Ｓｃ化合物、Ｎｄ化合物及びＹｂ化合物として
特定量添加すること以外は、これらを含有しない組成式 （Ｇｄ1-X-Y-z ，Ｙx ，Ｔｂy ，Ｔｍz ）2 Ｏ2 Ｓ の蛍光体の製造方法と同様の方法で製造される。The present invention will be described in detail below. The rare earth oxysulfide phosphor of the present invention comprises Zn or Zn and Ce, Sc, Nd and Yb as an impurity element in a phosphor raw material mixture.
Of at least one of Zn compound and Ce
Compound, Sc compound, as except adding specific amount Nd compound and Yb compounds, composition formula does not contain these (Gd 1-XYz, Y x , Tb y, Tm z) 2 O 2 producing method of the phosphor S It is manufactured by the same method as.
【００１１】まず蛍光体原料として下記（１）〜（６）
の蛍光体原料が用いられる。（１）〜（６）の蛍光体原
料の内、（６）以外の原料は従来の組成式 （Ｇｄ1-X-Y-z ，Ｙx ，Ｔｂy ，Ｔｍz ）2 Ｏ2 Ｓ の蛍光体の製造に用いられる原料と同じである： （１）Ｇｄ2 Ｏ3 またはＧｄの硝酸塩、炭酸塩、硫酸
塩、蓚酸塩、ハロゲン化物等の高温でＧｄ2 Ｏ3 に変わ
り得るＧｄ化合物、（２）Ｙ2 Ｏ3 またはＹの硝酸塩、
炭酸塩、硫酸塩、蓚酸塩、ハロゲン化物等の高温でＹ2
Ｏ3 に変わり得るＹ化合物、（３）Ｔｂ4 Ｏ7 またはＴ
ｂの硝酸塩、炭酸塩、硫酸塩、蓚酸塩、ハロゲン化物等
の高温でＴｂ4 Ｏ7 に変わり得るＴｂ化合物、（４）Ｔ
ｍ2 Ｏ3 またはＴｍの硝酸塩、炭酸塩、硫酸塩、蓚酸
塩、ハロゲン化物等の高温でＴｍ2 Ｏ3 に変わり得るＴ
ｍ化合物、（５）硫黄（Ｓ）、（６）Ｚｎの酸化物、硫
化物、硝酸塩、炭酸塩、硫酸塩、ハロゲン化物等のＺｎ
化合物、又はこれらのＺｎ化合物とＣｅ化合物、Ｓｃ化
合物、Ｎｄ化合物及びＹｂ化合物の少なくとも１種。First, the following (1) to (6) are used as phosphor raw materials.
The phosphor raw material is used. (1) - of the phosphor material (6), (6) other than the raw material conventional composition formula (Gd 1-XYz, Y x , Tb y, Tm z) in the preparation of the phosphor of 2 O 2 S It is the same as the raw materials used: (1) Gd 2 O 3 or a Gd nitrate, carbonate, sulfate, oxalate, halide, etc., which can be converted to Gd 2 O 3 at a high temperature, (2) Y 2 O 3 or Y nitrate,
Y 2 at high temperature such as carbonates, sulfates, oxalates and halides
Y compound that can be converted to O 3 , (3) Tb 4 O 7 or T
(4) Tb compounds such as nitrates, carbonates, sulfates, oxalates, and halides of b which can be converted to Tb 4 O 7 at high temperature,
m 2 O 3 or Tm nitrate, carbonate, sulfate, oxalate, halide, etc. which can be converted to Tm 2 O 3 at high temperature
Zn of m compound, (5) sulfur (S), (6) Zn oxide, sulfide, nitrate, carbonate, sulfate, halide, etc.
Compound, or at least one of these Zn compound and Ce compound, Sc compound, Nd compound and Yb compound.
【００１２】上記の蛍光体原料（１）〜（５）を化学量
論的に組成式 （Ｇｄ1-X-Y-z ，Ｙx ，Ｔｂy ，Ｔｍz ）2 Ｏ2 Ｓ となるような量比で秤取し、これに所定量の上記の螢光
体原料（６）と炭酸ナトリウム( Ｎａ2 ＣＯ3 ）、燐酸
カリウム( Ｋ3 ＰＯ4 ）等の融剤を加え、十分に混合し
て蛍光体原料混合物を調製する。[0012] balance in the phosphor materials (1) to (5) a stoichiometric composition formula (Gd 1-XYz, Y x , Tb y, Tm z) 2 O 2 is S such an amount ratio of the Then, a predetermined amount of the above-mentioned phosphor raw material (6) and a fluxing agent such as sodium carbonate (Na 2 CO 3 ), potassium phosphate (K 3 PO 4 ), etc. are added and sufficiently mixed to obtain the phosphor raw material. Prepare the mixture.
【００１３】上記蛍光体原料（６）の内、Ｚｎ化合物は
Ｚｎ元素の含有量が組成式 （Ｇｄ1-X-Y-z ，Ｙx ，Ｔｂy ，Ｔｍz ）2 Ｏ2 Ｓ の蛍光体に対して０. ３〜３０ｐｐｍとなるような量で
使用されが、添加されたＺｎ化合物はその全量が得られ
る蛍光体中に固溶するのではなく、一部は蛍光体原料の
焼成中に焼成容器外に散逸したり、焼成後の洗浄処理に
より溶出するので、原料であるＺｎ化合物は蛍光体中に
含有させたい量よりも過剰の量で使用される。また、Ｃ
ｅ化合物、Ｓｃ化合物、Ｎｄ化合物及びＹｂ化合物の内
の少なくとも１種は、組成式 （Ｇｄ1-X-Y-z ，Ｙx ，Ｔｂy ，Ｔｍz ）2 Ｏ2 Ｓ の蛍光体に対してＣｅの含有量が０. ０４〜０. ６ｐｐ
ｍとなる量で、またＳｃ、Ｎｄ及びＹｂの内の少なくと
も１種の元素の合計含有量が０．０４〜１０ｐｐｍとな
る量で使用される。[0013] Of the phosphor materials (6), Zn compound content of Zn element composition formula of the phosphor of (Gd 1-XYz, Y x , Tb y, Tm z) 2 O 2 S 0 The amount of Zn compound added is 3 to 30 ppm, but the whole amount of the added Zn compound does not form a solid solution in the obtained phosphor, but a part of it is outside the firing container during firing of the phosphor raw material. The Zn compound, which is a raw material, is used in an excessive amount over the amount desired to be contained in the phosphor, because it is dissipated or is eluted by a cleaning treatment after firing. Also, C
e compound, Sc compound, at least one of Nd compound and Yb compounds, composition formula (Gd 1-XYz, Y x , Tb y, Tm z) Ce content of the phosphor of the 2 O 2 S Is 0.04 to 0.6 pp
It is used in an amount such that the total content of at least one of Sc, Nd and Yb is 0.04 to 10 ppm.
【００１４】なお、上記螢光体原料（６）は他の原料に
比べて添加量が著しく少量なので、秤取精度が問題とな
る場合は、秤量が可能な一定量を秤取し、溶媒に溶解し
て希釈した後、所定量の溶液を分取して、他の螢光体原
料に添加しても良い。また、上記蛍光体原料の内、
（５）及び融剤を除く原料は予め鉱酸等で溶解し、同一
溶液から例えば蓚酸塩のような同一の塩として共沈させ
るようにすれば、添加されたＺｎ元素やＣｅ、Ｓｃ、Ｎ
ｄ及びＹｂの金属元素が蛍光体中に一層均一に分布し、
発光特性のばらつきが少なくなるのでより好ましい。Since the above-mentioned fluorescent material (6) is added in a remarkably small amount as compared with other raw materials, when weighing accuracy is a problem, a certain amount that can be weighed is weighed and used as a solvent. After dissolving and diluting, a predetermined amount of the solution may be fractionated and added to another phosphor material. Further, among the above phosphor raw materials,
(5) and the raw materials excluding the flux are previously dissolved in a mineral acid or the like and co-precipitated as the same salt such as oxalate from the same solution, so that the added Zn element or Ce, Sc, N
The metal elements of d and Yb are more evenly distributed in the phosphor,
It is more preferable because variation in light emission characteristics is reduced.
【００１５】次にこれらの蛍光体原料を耐熱性容器に詰
めて空気中で１１００〜１３００℃の温度で１〜１０時
間焼成し、粉砕、洗浄、乾燥、篩い分け等蛍光体製造に
おいて一般に行なわれている焼成後の各後処理操作を行
なって本発明の蛍光体を得ることができる。Next, these phosphor raw materials are packed in a heat-resistant container and fired in air at a temperature of 1100 to 1300 ° C. for 1 to 10 hours, followed by crushing, washing, drying, sieving and the like, which are generally carried out in the production of a phosphor. The phosphor of the present invention can be obtained by performing each post-treatment operation after firing.
【００１６】一方、本発明の増感紙は上述のようにして
製造された、特定量のＺｎ又はＺｎとＣｅ、Ｓｃ、Ｎｄ
及びＹｂの少なくとも１種とを含有する組成式 （Ｇｄ1-X-Y-z ，Ｙx ，Ｔｂy ，Ｔｍz ）2 Ｏ2 Ｓ の蛍光体を蛍光体層に使用するものであり、その構造は
従来の増感紙と同じものである。すなわち、本発明の増
感紙は本質的に紙、プラスチック等からなる支持体と、
この支持体上に設けられた、上記希土類酸硫化物蛍光体
を硝化綿、アクリル樹脂等の結合剤樹脂中に分散させた
蛍光体層とからなる。On the other hand, the intensifying screen of the present invention has a specific amount of Zn or Zn and Ce, Sc, Nd produced as described above.
And composition formula containing at least one Yb are those (Gd 1-XYz, Y x , Tb y, Tm z) phosphors 2 O 2 S used in the phosphor layer, the structure of the conventional It is the same as the intensifying screen. That is, the intensifying screen of the present invention comprises a support essentially consisting of paper, plastic, etc.,
It comprises a phosphor layer provided on this support, in which the above-mentioned rare earth oxysulfide phosphor is dispersed in a binder resin such as nitrification cotton or acrylic resin.
【００１７】蛍光体層は上記希土類酸硫化物蛍光体と硝
化綿等の結合剤樹脂とを適当量混合し、更にこれに溶剤
を適当量加えて最適粘度の蛍光体塗布液を調製し、この
蛍光体塗布液をロールコーター、ナイフコーター等によ
って支持体上に塗布し、乾燥して蛍光体層とする。蛍光
体層の蛍光体塗布重量は１０〜２００ｍｇ／ｃｍ2 が適
当であり、より好ましくは２０〜１５０ｍｇ／ｃｍ2 で
ある。一般に、多くの増感紙は蛍光体層上に蛍光体層を
保護するための保護膜を有しているが、本発明の増感紙
においても透明または染料等で着色された保護膜を設け
てもよい。For the phosphor layer, the above-mentioned rare earth oxysulfide phosphor is mixed with an appropriate amount of a binder resin such as nitrification cotton, and then an appropriate amount of a solvent is added thereto to prepare a phosphor coating solution having an optimum viscosity. The phosphor coating solution is coated on a support by a roll coater, knife coater or the like and dried to form a phosphor layer. The phosphor coating weight of the phosphor layer is suitably 10 to 200 mg / cm 2 , and more preferably 20 to 150 mg / cm 2 . Generally, many intensifying screens have a protective film on the phosphor layer for protecting the phosphor layer, but the intensifying screen of the present invention also has a protective film which is transparent or colored with a dye or the like. May be.
【００１８】図１はＺｎを含有する組成式 （Ｇｄ0.995 ，Ｔｂ0.005 ）2 Ｏ2 Ｓ の蛍光体を蛍光体層に用いた増感紙（曲線ａ）及びＺｎ
を含有する組成式 （Ｇｄ0.8 ，Ｙ0.194 ，Ｔｂ0.005 ，Ｔｍ0.001 ）2 Ｏ
2 Ｓ の蛍光体を感光体層に用いた増感紙（曲線ｂ）につい
て、それぞれの増感紙の蛍光体層に用いられている希土
類酸硫化物蛍光体中のＺｎの量と各増感紙の鮮鋭度との
関係を、各増感紙の写真感度を一定にして測定した結果
について例示するグラフである。図１において縦軸の鮮
鋭度指数［Ｍ］とは、Ｚｎを含まない希土類酸硫化物蛍
光体を用いた従来の増感紙の空間周波数２本／ｍｍにお
けるＭＴＦ値を〔ＭＴＦ(O) 〕とし、これと同一写真感
度で、かつＺｎを含有する希土類酸硫化物蛍光体を用い
た増感紙の空間周波数２本／ｍｍにおけるＭＴＦ値を
〔ＭＴＦ(Zn)〕とした時の、 〔Ｍ〕＝｛〔ＭＴＦ(Zn)〕／〔ＭＴＦ(O) 〕｝×１００ で定義される値であり、ＭＴＦ値が大きいほど鮮鋭度は
良好であるから、ここで定義される〔Ｍ〕の値が１００
より大きいほどＺｎを含有しない希土類酸硫化物蛍光体
を用いた従来の増感紙より鮮鋭度が良好であることを意
味する。FIG. 1 shows an intensifying screen (curve a) in which a phosphor having a composition formula (Gd 0.995 , Tb 0.005 ) 2 O 2 S containing Zn is used in the phosphor layer (curve a) and Zn.
Composition formula containing (Gd 0. 8, Y 0 . 194, Tb 0.005, Tm 0.001) 2 O
Regarding the intensifying screen (curve b) using the 2 S phosphor in the photoconductor layer, the amount of Zn in the rare earth oxysulfide phosphor used in the phosphor layer of each intensifying screen and each sensitization screen It is a graph which illustrates the relationship with the sharpness of paper about the result of having measured the photographic sensitivity of each intensifying screen constant. In FIG. 1, the sharpness index [M] on the vertical axis is the MTF value at a spatial frequency of 2 lines / mm of a conventional intensifying screen using a rare-earth oxysulfide phosphor containing no Zn [MTF (O)]. When the MTF value at a spatial frequency of 2 lines / mm of the intensifying screen using the rare earth oxysulfide phosphor containing Zn and having the same photographic sensitivity as [MTF (Zn)] is [MTF (Zn)], [M ] = {[MTF (Zn)] / [MTF (O)]} × 100. The larger the MTF value, the better the sharpness. Therefore, the value of [M] defined here. Is 100
A larger value means that the sharpness is better than that of a conventional intensifying screen using a rare earth oxysulfide phosphor containing no Zn.
【００１９】図１から分るように、増感紙の蛍光体層に
使用される希土類酸硫化物蛍光体中に微量のＺｎを含有
させると、得られる増感紙の鮮鋭度が著しく向上する
が、Ｚｎ含有量がおよそ５ｐｐｍを越えると逆に鮮鋭度
は次第に低下し、Ｚｎ含有量が３０ｐｐｍより多いと、
Ｚｎを含有しない希土類酸硫化物蛍光体を用いた増感紙
よりも鮮鋭度は低くなる。なお、図１には組成の異なる
２つの希土類酸硫化物蛍光体を用いた増感紙について例
示したが、これ以外の組成の組成式 （Ｇｄ1-X-Y-z ，Ｙx ，Ｔｂy ，Ｔｍz ）2 Ｏ2 Ｓ の蛍光体を蛍光体層に用いた増感紙の場合も、蛍光体層
に用いられる蛍光体中のＺｎ含有量と増感紙の鮮鋭度と
の相関はほぼ図１に例示した増感紙の場合と同様であっ
た。As can be seen from FIG. 1, when a small amount of Zn is contained in the rare earth oxysulfide phosphor used in the phosphor layer of the intensifying screen, the sharpness of the obtained intensifying screen is remarkably improved. However, when the Zn content exceeds about 5 ppm, on the contrary, the sharpness gradually decreases, and when the Zn content is more than 30 ppm,
The sharpness is lower than that of the intensifying screen using the rare earth oxysulfide phosphor containing no Zn. Although exemplified for intensifying screen using two rare earth oxysulfide phosphor having different compositions in FIG. 1, the composition formula of the other composition (Gd 1-XYz, Y x , Tb y, Tm z) Also in the case of an intensifying screen using a phosphor of 2 O 2 S in the phosphor layer, the correlation between the Zn content in the phosphor used in the phosphor layer and the sharpness of the intensifying screen is illustrated in FIG. The same as the case of the intensifying screen.
【００２０】従って、鮮鋭度の観点から、増感紙の蛍光
体層に用いられる組成式 （Ｇｄ1-X-Y-z ，Ｙx ，Ｔｂy ，Ｔｍz ）2 Ｏ2 Ｓ の蛍光体中に含有させるＺｎの量は０. ３〜３０ｐｐｍ
とすることが好ましいが、０. ８〜１５ｐｐｍとするこ
とがより好ましく、１〜１０ｐｐｍとすることが特に好
ましい。[0020] Therefore, from the viewpoint of sharpness, the composition formula to be used in the phosphor layer of the intensifying screen (Gd 1-XYz, Y x , Tb y, Tm z) 2 O 2 Zn to be contained in the phosphor of the S The amount is 0.3-30ppm
However, it is more preferably 0.8 to 15 ppm, particularly preferably 1 to 10 ppm.
【００２１】図２はＣｅと一定量（３ｐｐｍ）のＺｎと
を含有する組成式 （Ｇｄ0.995 ，Ｔｂ0.005)2 Ｏ2 Ｓ の蛍光体を蛍光体層に用いた増感紙について、用いた各
蛍光体中のＣｅ含有量と、この増感紙の残光特性との関
係を各増感紙の写真感度を一定にして測定した結果につ
いて例示するグラフであり、図３は同じ増感紙について
蛍光体中のＣｅ含有量とこの蛍光体を螢光体層に用いた
増感紙の相対写真感度との関係を例示するグラフであ
る。図２において、縦軸は残光指数［Ｌ］、横軸は各増
感紙の蛍光体層に使用される組成式 （Ｇｄ0.995 ，Ｔｂ0.005)2 Ｏ2 Ｓ の蛍光体中のＣｅ含有量を示す。ここで残光指数［Ｌ］
とは、各増感紙にＸ線を照射し、照射を停止した後の残
光量［Ｌ' ］を、Ｃｅを含有しない組成式 （Ｇｄ0.995 ，Ｔｂ0.005 ）2 Ｏ2 Ｓ の蛍光体を用いた増感紙に対して同様にＸ線を照射し、
照射を停止した後の残光量［Ｌ0 ］に対する百分率で示
した値、即ち、 [ Ｌ］＝｛［Ｌ' ］／［Ｌ0 ］｝×１００ であり、ここで定義された［Ｌ］値が１００より小さい
ほどＣｅを含有しない蛍光体を用いた増感紙に比べて残
光量が少ないことを示す。FIG. 2 shows the intensifying screens in which a phosphor of the composition formula (Gd 0.995 , Tb 0.005 ) 2 O 2 S containing Ce and a fixed amount (3 ppm) of Zn was used in the phosphor layer. FIG. 3 is a graph exemplifying the result of measurement of the relationship between the Ce content in the phosphor and the afterglow characteristic of this intensifying screen with the photographic sensitivity of each intensifying screen being kept constant, and FIG. It is a graph which illustrates the relationship between Ce content in a fluorescent substance and the relative photographic sensitivity of the intensifying screen which used this fluorescent substance for the fluorescent substance layer. 2, the vertical axis represents the afterglow index [L], the horizontal axis represents the composition formula to be used in the phosphor layer of each intensifying screen (Gd 0.995, Tb 0.005) Ce content in the phosphor 2 O 2 S Indicates. Afterglow index [L]
Means the afterglow amount [L '] after irradiation of X-rays on each intensifying screen and stopping the irradiation, using the phosphor of the composition formula (Gd 0.995 , Tb 0.005 ) 2 O 2 S that does not contain Ce. Irradiate X-rays to the intensifying screen,
A value expressed as a percentage of the afterglow amount [L 0 ] after the irradiation is stopped, that is, [L] = {[L ′] / [L 0 ]} × 100, and the [L] value defined here Of less than 100 indicates that the amount of afterglow is smaller than that of an intensifying screen using a phosphor containing no Ce.
【００２２】図２からわかるように、Ｃｅを含有する組
成式 （Ｇｄ0.995 ，Ｔｂ0.005)2 Ｏ2 Ｓ の蛍光体を用いた増感紙においては、用いられる螢光体
中のＣｅの含有量が増すに従って残光量が次第に低減
し、Ｃｅの含有量が少なくとも０. ０４ｐｐｍになると
残光量はＣｅを含有しない場合に比べて５０％以上低減
し、Ｃｅの含有量が０. ３ｐｐｍより多い蛍光体を用い
た増感紙の残光はほとんど認められない。As can be seen from FIG. 2, in the intensifying screen using the phosphor of the composition formula (Gd 0.995 , Tb 0.005 ) 2 O 2 S containing Ce, the content of Ce in the fluorescent substance used. As the amount of afterglow gradually decreases, when the content of Ce reaches at least 0.04 ppm, the amount of afterglow is reduced by 50% or more as compared with the case where no Ce is contained, and the phosphor having a Ce content of more than 0.3 ppm is obtained. Almost no afterglow of the intensifying screen using is observed.
【００２３】一方、図３からわかるようにＣｅを含有す
る螢光体を用いた増感紙では、使用される蛍光体中のＣ
ｅの含有量が０. ４ｐｐｍより多くなると増感紙の写真
感度が低下し、これが０. ６ｐｐｍより多くなると蛍光
体に淡黄色の着色が現れて発光輝度が低下し、これを用
いた増感紙の写真感度はＣｅを含有しない蛍光体を用い
た増感紙に比べて５％以上低下するため実用上好ましく
ない。On the other hand, as shown in FIG. 3, in the intensifying screen using the phosphor containing Ce, the C in the phosphor used is
When the content of e is more than 0.4 ppm, the photographic sensitivity of the intensifying screen is lowered, and when it is more than 0.6 ppm, the phosphor is colored light yellow and the emission brightness is lowered, and the sensitization using this The photographic sensitivity of paper is 5% or more lower than that of an intensifying screen using a phosphor containing no Ce, which is not practically preferable.
【００２４】なお、図２及び図３には第１の不純物元素
として３ｐｐｍのＺｎを含有し、第２の不純物元素とし
てＣｅを含有する組成式 （Ｇｄ0.995 ，Ｔｂ0.005)2 Ｏ2 Ｓ の蛍光体を用いた増感紙について、用いる蛍光体中のＣ
ｅ含有量と増感紙の残光量及び相対写真感度との関係を
例示したが、これらの相関は用いる組成式 （Ｇｄ1-X-Y-z ，Ｙx ，Ｔｂy ，Ｔｍz ）2 Ｏ2 Ｓ の蛍光体の組成及び第１の不純物元素であるＺｎの含有
量が変わってもほぼ同様であった。また、第２の不純物
元素としてＳｃ、Ｎｄ又はＹｂを用いる場合に、蛍光体
中のこれら第２の不純物元素の含有量とその蛍光体を用
いた増感紙の残光量との間には図２と類似の相関があ
り、Ｃｅを第２の不純物元素として用いた場合と同様
に、これら不純物元素含有量がおよそ０．０４ｐｐｍ以
上であると残光量の低減効果が認められたが、蛍光体中
の第２の不純物元素含有量を増加させた場合の増感紙の
写真感度の低下はＣｅを第２の不純物元素として用いた
場合ほど顕著ではなく、Ｃｅが共存する場合においても
Ｓｃ、Ｎｄ及びＹｂの含有量の合計がおよそ１０ｐｐｍ
以下であれば、これらの蛍光体を用いた増感紙の写真感
度の低下は実用上支障のない程度であった。2 and 3, fluorescence of a composition formula (Gd 0.995 , Tb 0.005 ) 2 O 2 S containing 3 ppm of Zn as the first impurity element and Ce as the second impurity element. Regarding the intensifying screen using the body, C in the phosphor used
has been illustrated the relationship between the residual quantity and the relative photographic speed of e content and intensifying screen, fluorescent these correlations using formula (Gd 1-XYz, Y x , Tb y, Tm z) 2 O 2 S It was almost the same even if the body composition and the content of Zn as the first impurity element were changed. In addition, when Sc, Nd or Yb is used as the second impurity element, there is a graph between the content of these second impurity elements in the phosphor and the afterglow amount of the intensifying screen using the phosphor. 2 has a similar correlation with 2, and as in the case of using Ce as the second impurity element, the effect of reducing the amount of afterglow was recognized when the content of these impurity elements was about 0.04 ppm or more. The decrease in the photographic sensitivity of the intensifying screen when the content of the second impurity element in the inside is not so remarkable as when Ce is used as the second impurity element, and even when Ce coexists, Sc, Nd And the total content of Yb is about 10 ppm
In the following cases, the reduction of the photographic sensitivity of the intensifying screen using these phosphors was practically unproblematic.
【００２５】従って、得られる増感紙の蛍光体層に用い
る組成式 （Ｇｄ1-X-Y-z ，Ｙx ，Ｔｂy ，Ｔｍz ）2 Ｏ2 Ｓ の蛍光体中の第２の不純物元素であるＣｅ、Ｓｃ、Ｎｄ
及びＹｂの内の少なくとも１種の含有量は、残光低減の
観点からは、０. ０４ｐｐｍ以上とすることが好まし
い。一方、増感紙の写真感度の低下抑制の観点からは第
２の不純物元素の含有量はＣｅの場合には０. ６ｐｐｍ
以下とし、Ｓｃ、Ｎｄ及びＹｂの場合にはその合計で１
０ｐｐｍ以下とすることが好ましく、より好ましくはＣ
ｅの場合には０．４ｐｐｍ以下とし、Ｓｃ、Ｎｄ及びＹ
ｂの場合にはその合計で５ｐｐｍ以下とする。[0025] Thus, the composition formula to be used in the phosphor layer of the intensifying screen obtained (Gd 1-XYz, Y x , Tb y, Tm z) 2 O 2 which is a second impurity element in the phosphor of the S Ce , Sc, Nd
From the viewpoint of afterglow reduction, the content of at least one of Yb and Yb is preferably 0.04 ppm or more. On the other hand, from the viewpoint of suppressing the deterioration of the photographic sensitivity of the intensifying screen, the content of the second impurity element is 0.6 ppm in the case of Ce.
Below, in the case of Sc, Nd and Yb, the total is 1
It is preferably 0 ppm or less, more preferably C
In the case of e, 0.4ppm or less, Sc, Nd and Y
In the case of b, the total is 5 ppm or less.
【００２６】[0026]
【実施例】以下、実施例及び比較例により本発明を説明
する： 実施例１〜４及び比較例１ 酸化ガドリニウム（Ｇｄ2 Ｏ3 ） ７２１. ４ｇ 酸化テルビウム（Ｔｂ4 Ｏ7 ） ３. ７４ｇ 酸化亜鉛（ＺｎＯ） ３３ｍｇ 炭酸ナトリウム（Ｎａ2 ＣＯ3 ） ３００ｇ リン酸カリウム（Ｋ3 ＰＯ4 ・３Ｈ2 Ｏ） ４０ｇ 硫黄（Ｓ） ２２０ｇ 上記原料を均一に混合し、アルミナルツボに詰めて、空
気中１２５０℃で５時間焼成した。得られた焼成物を充
分に水洗し、乾燥後、篩にかけて粒子径をそろえ、Ｚｎ
の含有量が１ｐｐｍである組成式 （Ｇｄ0.995 ，Ｔｂ0.005)2 Ｏ2 Ｓ の蛍光体｛蛍光体（１）｝を得た。EXAMPLES The present invention will be described below with reference to Examples and Comparative Examples: Examples 1 to 4 and Comparative Example 1 Gadolinium oxide (Gd 2 O 3 ) 721.4 g Terbium oxide (Tb 4 O 7 ) 3.74 g Oxidation Zinc (ZnO) 33 mg Sodium carbonate (Na 2 CO 3 ) 300 g Potassium phosphate (K 3 PO 4 .3H 2 O) 40 g Sulfur (S) 220 g The above raw materials are uniformly mixed and packed in an alumina crucible, and 1250 in air. Calcination was carried out for 5 hours. The fired product obtained is thoroughly washed with water, dried, and sieved to adjust the particle size.
A phosphor of the composition formula (Gd 0.995 , Tb 0.005 ) 2 O 2 S {phosphor (1)} having a content of 1 ppm was obtained.
【００２７】これとは別に、酸化亜鉛（ＺｎＯ）の使用
量をそれぞれ蛍光体（１）の場合の３倍、１０倍および
２０倍とする以外は、上記蛍光体（１）の製造と同様に
して表１に記載の組成を有する蛍光体（２）、（３）及
び（４）を製造した。Apart from this, the same procedure as in the production of the above phosphor (1) is carried out except that the amount of zinc oxide (ZnO) used is 3 times, 10 times and 20 times that of the phosphor (1). To produce phosphors (2), (3) and (4) having the compositions shown in Table 1.
【００２８】一方、比較のため、酸化亜鉛（ＺｎＯ）を
添加しない以外は、上記蛍光体（１）の製造と同様にし
てＺｎを含有しない組成式 （Ｇｄ0.995 ，Ｔｂ0.005)2 Ｏ2 Ｓ の蛍光体｛蛍光体（Ｒ１）｝を得た。On the other hand, for comparison, a composition formula (Gd 0.995 , Tb 0.005 ) 2 O 2 S containing no Zn was prepared in the same manner as in the production of the phosphor (1) except that zinc oxide (ZnO) was not added. A phosphor {phosphor (R1)} was obtained.
【００２９】次に８重量部の上記蛍光体（１）、１重量
部の硝化綿及び有機溶剤を混合し、蛍光体塗布液を調製
した。この蛍光体塗布液を、表面にカーボンブラック光
吸収層を有するポリエチレンテレフタレート支持体上
に、乾燥後の蛍光体塗布重量が５７ｍｇ／ｃｍ2 となる
ようにナイフコーターを用いて均一に塗布し、乾燥させ
て蛍光体層を作製した。次いで、この蛍光体層の表面に
酢酸セルロースを溶剤に溶かした保護膜塗布液を、乾燥
後の膜厚がおよそ６μｍとなるように均一に塗布し、乾
燥させて透明保護膜を形成し、蛍光体（１）からなる蛍
光体層を有する増感紙｛増感紙（１）｝を得た。これと
は別に、蛍光体（１）に替えて蛍光体（２）〜（４）及
び蛍光体（Ｒ１）を用いること及び各増感紙の写真感度
がほぼ一定となるように各蛍光体塗布液の乾燥後の塗布
重量を表１に記載の通りとする以外は増感紙（１）の製
造と同様にして増感紙（２）〜（４）及び増感紙（Ｒ
１）を製造した。Next, 8 parts by weight of the above phosphor (1), 1 part by weight of nitrification cotton and an organic solvent were mixed to prepare a phosphor coating solution. This phosphor coating solution was uniformly applied onto a polyethylene terephthalate support having a carbon black light absorbing layer on its surface using a knife coater so that the applied weight of the phosphor after drying would be 57 mg / cm 2, and dried. Then, a phosphor layer was prepared. Next, a protective film coating solution prepared by dissolving cellulose acetate in a solvent is uniformly applied to the surface of the phosphor layer so that the film thickness after drying is about 6 μm, and dried to form a transparent protective film. An intensifying screen {intensifying screen (1)} having a phosphor layer composed of the body (1) was obtained. Separately, instead of the phosphor (1), the phosphors (2) to (4) and the phosphor (R1) are used, and each phosphor is coated so that the photographic sensitivity of each intensifying screen is substantially constant. Intensifying screens (2) to (4) and intensifying screens (R) were prepared in the same manner as in the production of intensifying screen (1) except that the coating weight after drying the liquid was as shown in Table 1.
1) was produced.
【００３０】実施例５〜１０ ７２１. ４ｇの酸化ガドリニウム（Ｇｄ2 Ｏ3 ）、３.
７４ｇの酸化テルビウム（Ｔｂ4 Ｏ7 ）、０. １２ｍｇ
の炭酸セリウム｛Ｃｅ2 （ＣＯ3 ）3 ｝及び３００ｍｇ
の酸化亜鉛を硝酸に溶解した後１０００ｇの蓚酸を添加
し、生成した沈殿を脱水、乾燥した後、１０００℃で１
時間焼成した。次いで、その得られた焼成物と 炭酸ナトリウム（Ｎａ2 ＣＯ3 ） ３００ｇ リン酸カリウム（Ｋ3 ＰＯ4 ・３Ｈ2 Ｏ） ４０ｇ 硫黄（Ｓ） ２２０ｇ とを充分に混合し、アルミナルツボに詰めて、空気中１
２５０℃で５時間焼成し、得られた焼成物を充分に水洗
し、乾燥した後、篩にかけて粒子径をそろえ、Ｚｎおよ
びＣｅの含有量がそれぞれ３ｐｐｍ及び０. １ｐｐｍで
ある組成式 （Ｇｄ0.995 ，Ｔｂ0.005)2 Ｏ2 Ｓ の蛍光体｛蛍光体（５）｝を得た。Examples 5-10 721.4 g gadolinium oxide (Gd 2 O 3 ) 3.
74 g of terbium oxide (Tb 4 O 7 ), 0.12 mg
Cerium carbonate {Ce 2 (CO 3 ) 3 } and 300 mg
1000 g of oxalic acid was added after the zinc oxide of 1 was dissolved in nitric acid, and the formed precipitate was dehydrated and dried, and then at 1000 ° C. for 1 hour.
Burned for hours. Then, the obtained calcined product was thoroughly mixed with sodium carbonate (Na 2 CO 3 ) 300 g potassium phosphate (K 3 PO 4 .3H 2 O) 40 g sulfur (S) 220 g and packed in an alumina crucible, In the air 1
The composition was calcined at 250 ° C. for 5 hours, the resulting calcined product was thoroughly washed with water, dried, and sieved to have a uniform particle size, and the composition formula (Gd 0.995 was 3 ppm and 0.1 ppm, respectively). , Tb 0.005 ) 2 O 2 S phosphor (phosphor (5)) was obtained.
【００３１】これとは別に、Ｃｅ2 （ＣＯ3 ）3 の添加
量を蛍光体（５）の場合の３倍量とする以外は蛍光体
（５）の製造と同様にして表１に記載の組成を有する蛍
光体（６）を得た。Apart from this, the same procedure as in the production of the phosphor (5) is shown in Table 1 except that the amount of Ce 2 (CO 3 ) 3 added is 3 times that of the phosphor (5). A phosphor (6) having a composition was obtained.
【００３２】また、Ｃｅ2 （ＣＯ3 ）3 の添加量を蛍光
体（５）の場合の２倍量とし、更にこれに０. １７ｍｇ
の酸化ネオジム（Ｎｄ2 Ｏ3 ）、又は０. ２４ｍｇの酸
化スカンジウム（Ｓｃ2 Ｏ3 ）、又は０．１７ｍｇの酸
化イッテルビウム（Ｙｂ2 Ｏ 3 ）を蛍光体原料として加
える以外は蛍光体（５）の製造と同様にして表１に記載
の組成を有する蛍光体（７）、（８）及び（９）を製造
した。Also, Ce2 (CO3 )3 Fluorescent addition amount
Double the amount of body (5) and add 0.17mg
Neodymium oxide (Nd2 O3 ), Or 0.24 mg of acid
Scandium oxide (Sc2 O3 ), Or 0.17 mg of acid
Ytterbium Chloride (Yb2 O 3 ) As a phosphor material
The same as in the production of phosphor (5) except that
Manufacture phosphors (7), (8) and (9) having the composition
did.
【００３３】更に、Ｃｅ2 （ＣＯ3 ）3 ０. １２ｍｇの
代りに１．７ｍｇの酸化ネオジム（Ｎｄ2 Ｏ3 ）及び
２．６ｍｇの酸化イッテルビウム（Ｙｂ2 Ｏ3 ）を用い
る以外は蛍光体（５）の製造と同様にして表１に記載の
組成を有する蛍光体（１０）を得た。Further, instead of Ce 2 (CO 3 ) 3 0.12 mg, 1.7 mg of neodymium oxide (Nd 2 O 3 ) and 2.6 mg of ytterbium oxide (Yb 2 O 3 ) were used. A phosphor (10) having the composition shown in Table 1 was obtained in the same manner as in the production of 5).
【００３４】次に、蛍光体（１）に替えて蛍光体（５）
〜（１０）を用い、各増感紙の写真感度がほぼ一定とな
るように各蛍光体塗布液の乾燥後の塗布重量を表１に記
載の通りとする以外は増感紙（１）と同様にして増感紙
（５）〜（１０）を製造した。Next, instead of the phosphor (1), the phosphor (5)
~ (10) and the intensifying screen (1) except that the coating weight after drying of each phosphor coating solution is as shown in Table 1 so that the photographic sensitivity of each intensifying screen is almost constant. Intensifying screens (5) to (10) were manufactured in the same manner.
【００３５】実施例１１〜１３及び比較例２ 酸化ガドリニウム（Ｇｄ2 Ｏ3 ） ５８００ｇ 酸化イットリウム（Ｙ2 Ｏ3 ） ８７６ｇ 酸化テルビウム（Ｔｂ4 Ｏ7 ） ３７. ４ｇ 酸化ツリウム（Ｔｍ2 Ｏ3 ） ７. ７ｇ 炭酸セリウム｛Ｃｅ2 （ＣＯ3 ）3 ｝ ３. ３ｍｇ 酸化ネオジム（Ｎｄ2 Ｏ3 ） ０. ８ｍｇ 酸化イッテルビウム（Ｙｂ2 Ｏ3 ） ０. ８ｍｇ 上記各原料を硝酸に溶解し、十分に撹拌しながらこれに
９０００ｇの蓚酸を加えて生成した沈殿を脱水、乾燥し
た後、１０００℃で３時間焼成した。次に得られた上記
焼成物と 塩基性炭酸亜鉛（５ＺｎＯ・２ＣＯ2 ・４Ｈ2 Ｏ）
０. ９ｇ 炭酸ナトリウム（Ｎａ2 ＣＯ3 ） ２７００ｇ リン酸カリウム（Ｋ3 ＰＯ4 ・３Ｈ2 Ｏ） ４００
ｇ 硫黄（Ｓ） ２０２０ｇ とを充分に混合し、アルミナルツボに詰めて、空気中１
２５０℃で６時間焼成し、得られた焼成物を充分に水洗
し、乾燥した後、篩にかけて粒子径をそろえ、３ｐｐｍ
のＺｎと０. ３ｐｐｍのＣｅとそれぞれ０. １ｐｐｍの
Ｎｄ及びＹｂとを含有する組成式 （Ｇｄ0.8 、Ｙ0.194 、Ｔｂ0.005 、Ｔｍ0.001)2 Ｏ2
Ｓ の蛍光体｛蛍光体（１１）｝を得た。Examples 11 to 13 and Comparative Example 2 Gadolinium oxide (Gd 2 O 3 ) 5800 g Yttrium oxide (Y 2 O 3 ) 876 g Terbium oxide (Tb 4 O 7 ) 37.4 g Thulium oxide (Tm 2 O 3 ) 7 .7 g Cerium carbonate {Ce 2 (CO 3 ) 3 } 3.3 mg Neodymium oxide (Nd 2 O 3 ) 0.8 mg Ytterbium oxide (Yb 2 O 3 ) 0.8 mg Dissolve each of the above raw materials in nitric acid and stir thoroughly On the other hand, 9000 g of oxalic acid was added thereto to dehydrate and dry the precipitate, which was then calcined at 1000 ° C. for 3 hours. Next, the above-obtained fired product and basic zinc carbonate (5ZnO · 2CO 2 · 4H 2 O)
0. 9 g of sodium carbonate (Na 2 CO 3) 2700g potassium phosphate (K 3 PO 4 · 3H 2 O) 400
g Sulfur (S) 2020g is thoroughly mixed and packed in an alumina crucible.
After calcining at 250 ° C. for 6 hours, the calcined product obtained is thoroughly washed with water, dried and sieved to obtain a uniform particle size of 3 ppm.
Of Zn, 0.3 ppm of Ce, and 0.1 ppm of Nd and Yb, respectively (Gd 0.8 , Y 0.194 , Tb 0.005 , Tm 0.001 ) 2 O 2
A phosphor of S 1 {phosphor (11)} was obtained.
【００３６】これとは別に、Ｃｅ2 （ＣＯ3 ）3 の添加
量を蛍光体（１１）の場合の２／３とし、Ｎｄ2 Ｏ3 も
Ｙｂ2 Ｏ3 も用いないか、またはＹｂ2 Ｏ3 を用いない
以外はそれぞれ蛍光体（１１）の製造と同様にして表１
に記載の組成を有する蛍光体（１２）及び（１３）を製
造した。Separately from this, the amount of Ce 2 (CO 3 ) 3 added is set to 2/3 of that in the case of the phosphor (11), and neither Nd 2 O 3 nor Yb 2 O 3 is used, or Yb 2 O. The same procedure as in the production of phosphor (11) except that 3 is not used is shown in Table 1.
Phosphors (12) and (13) having the composition described in 1. were produced.
【００３７】更に比較のため、５ＺｎＯ・２ＣＯ2 ・４
Ｈ2 Ｏ、Ｃｅ2 （ＣＯ3 ）3 、Ｎｄ 2 Ｏ3 及びＹｂ2 Ｏ
3 を用いない以外は蛍光体（１１）の製造と同様にし
て、Ｚｎ、Ｃｅ、Ｎｄ及びＹｂを含有しない組成式 （Ｇｄ0.8 、Ｙ0.194 、Ｔｂ0.005 、Ｔｍ0.001)2 Ｏ2
Ｓ の蛍光体｛蛍光体（Ｒ２）｝を得た。For comparison, 5ZnO.2CO2 ・ 4
H2 O, Ce2 (CO3 )3 , Nd 2 O3 And Yb2 O
3 In the same manner as in the production of the phosphor (11) except that
And a composition formula (Gd containing no Zn, Ce, Nd and Yb)0.8 , Y0.194 , Tb0.005 , Tm0.001)2 O2
A phosphor of S 2 {phosphor (R2)} was obtained.
【００３８】次に、蛍光体（１）に替えて蛍光体（１
１）〜（１３）及び蛍光体（Ｒ２）を用い、各増感紙の
写真感度がほぼ一定となるように各蛍光体塗布液の塗布
重量を表１に記載の通りとする以外は増感紙（１）と同
様にして増感紙（１１）〜（１３）及び増感紙（Ｒ２）
を製造した。Next, in place of the phosphor (1), the phosphor (1
1) to (13) and the phosphor (R2), except that the coating weight of each phosphor coating solution is as shown in Table 1 so that the photographic sensitivity of each intensifying screen is almost constant. Intensifying screens (11) to (13) and intensifying screens (R2) similar to the paper (1).
Was manufactured.
【００３９】上述のようにして得られた本発明の１３種
類の増感紙｛（１）〜（１３）｝及び比較例として製造
された２種類の増感紙｛（Ｒ１）及び（Ｒ２）｝の螢光
体塗布重量と、これらの各増感紙について測定された写
真感度（相対値）、鮮鋭度指数［Ｍ］及び残光指数
［Ｌ］を、本発明の螢光体（１）〜（１２）及び比較例
の各螢光体の組成と平均粒子径と共に表１に示す。The 13 types of intensifying screens {(1) to (13)} of the present invention obtained as described above and the two types of intensifying screens {(R1) and (R2) produced as comparative examples. } Of the fluorescent substance coating weight, the photographic sensitivity (relative value), the sharpness index [M] and the afterglow index [L] measured for each of these intensifying screens, are the fluorescent substance (1) of the present invention. Table 1 shows the composition and average particle diameter of each of the fluorescent materials of (12) to (12) and Comparative Example.
【００４０】[0040]
【表１】 [Table 1]
【００４１】なお、表１中、各螢光体の不純物元素含有
量はいづれもグロ−放電質量分析装置により実測した分
析値であり、鮮鋭度指数［Ｍ］及び残光指数［Ｌ］は前
述の定義により求めた値である。In Table 1, the content of the impurity element in each phosphor is an analytical value measured by a glow discharge mass spectrometer, and the sharpness index [M] and the afterglow index [L] are as described above. It is the value obtained by the definition of.
【００４２】表１の実施例１〜４の増感紙（１）〜
（４）と比較例１の増感紙（Ｒ１）との比較から分るよ
うに、写真感度が同一の場合、Ｚｎを含有する希土類酸
硫化物螢光体を用いた増感紙｛増感紙（１）〜（４）｝
は、Ｚｎを含有しない希土類酸硫化物螢光体を用いた増
感紙｛増感紙（Ｒ１）｝に比べていづれも鮮鋭度指数
［Ｍ］が１００より大であり、鮮鋭度が著しく向上し
た。Intensifying screens (1) to Examples 1 to 4 in Table 1
As can be seen from the comparison between (4) and the intensifying screen (R1) of Comparative Example 1, when the photographic sensitivities are the same, an intensifying screen using a rare earth oxysulfide phosphor containing Zn {intensifying Paper (1)-(4)}
Has a sharpness index [M] of more than 100, which is significantly higher than that of the intensifying screen (intensifying screen (R1)) using a rare earth oxysulfide phosphor containing no Zn. did.
【００４３】また、実施例５〜１０の増感紙（５）〜
（１０）と比較例１の増感紙（Ｒ１）との比較、及び実
施例１１〜１３の増感紙（１１）〜（１３）と比較例２
の増感紙（Ｒ２）との比較から分るように、写真感度が
同一の場合、ＺｎとＺｎの外にＣｅ、Ｎｄ、Ｓｃ及びＹ
ｂの内の少なくとも１種の不純物元素とを含有する希土
類酸硫化物螢光体を用いた増感紙｛増感紙（５）〜（１
３）｝はいづれも、これらの不純物元素を含有しない希
土類酸硫化物螢光体を用いた増感紙｛増感紙（Ｒ１）及
び（Ｒ２）｝に比べて鮮鋭度指数［Ｍ］が１００より大
であり、鮮鋭度が著しく向上すると共に、残光指数
［Ｌ］が２３以下であり、残光も実用上支障とならない
程度にまで著しく低減した。Further, the intensifying screens (5) of Examples 5 to 10
Comparison between (10) and the intensifying screen (R1) of Comparative Example 1, and intensifying screens (11) to (13) of Examples 11 to 13 and Comparative Example 2
As can be seen from the comparison with the intensifying screen (R2) of No. 2, when the photographic sensitivity is the same, in addition to Zn and Zn, Ce, Nd, Sc and Y are added.
Intensifying screen using a rare earth oxysulfide phosphor containing at least one impurity element of b (intensifying screen (5) to (1
3)}, the sharpness index [M] is 100 as compared with the intensifying screens {intensifying screens (R1) and (R2)} using the rare earth oxysulfide phosphors that do not contain these impurity elements. The afterglow index [L] was 23 or less, and the afterglow was also significantly reduced to such an extent as not to hinder practical use.
【００４４】[0044]
【発明の効果】上述のように本発明の希土類酸硫化物螢
光体を螢光体層に用いた増感紙は従来の希土類酸硫化物
螢光体を用いた増感紙と比べ、画質、特に鮮鋭度が著し
く向上すると共に、残光が著しく低減される。As described above, the intensifying screen using the rare earth oxysulfide phosphor of the present invention in the phosphor layer has a higher image quality than the intensifying screen using the conventional rare earth oxysulfide phosphor. Especially, the sharpness is remarkably improved and the afterglow is remarkably reduced.
【図１】本発明の希土類酸硫化物螢光体中のＺｎ含有量
とこの螢光体を用いた増感紙の鮮鋭度特性との関係を示
すグラフである。FIG. 1 is a graph showing the relationship between the Zn content in the rare earth oxysulfide phosphor of the present invention and the sharpness characteristic of an intensifying screen using this phosphor.
【図２】本発明の希土類酸硫化物螢光体中のＣｅ含有量
とこの螢光体を用いた増感紙の残光特性との関係を示す
グラフである。FIG. 2 is a graph showing the relationship between the Ce content in the rare earth oxysulfide phosphor of the present invention and the afterglow characteristics of an intensifying screen using this phosphor.
【図３】本発明の希土類酸硫化物螢光体中のＣｅ含有量
とこの螢光体を用いた増感紙の写真感度特性との関係を
示すグラフである。FIG. 3 is a graph showing the relationship between the Ce content in the rare earth oxysulfide phosphor of the present invention and the photographic sensitivity characteristics of an intensifying screen using this phosphor.
Claims (3)
０００１≦ｙ≦０. ０２及び０≦ｚ≦０. ００５なる条
件を満足する数である）で表され、更に０. ３〜３０ｐ
ｐｍの亜鉛（Ｚｎ）を含有することを特徴とする緑色発
光希土類酸硫化物蛍光体。1. A composition formula (Gd 1-XYz, Y x , Tb y, Tm z) 2 O 2 S ( where, x, y and z are each 0 ≦ x ≦ 0. 4,0.
0001≤y≤0.02 and 0≤z≤0.005), and 0.3 to 30p
A green light-emitting rare earth oxysulfide phosphor containing pm of zinc (Zn).
０００１≦ｙ≦０. ０２及び０≦ｚ≦０. ００５なる条
件を満足する数である）で表され、更に（イ）０. ３〜
３０ｐｐｍの亜鉛（Ｚｎ）と、（ロ）０. ０４〜０. ６
ｐｐｍのセリウム（Ｃｅ）及び／又は合計で０．０４〜
１０ｐｐｍのスカンジウム（Ｓｃ）、ネオジム（Ｎｄ）
及びイッテルビウム（Ｙｂ）の内の少なくとも１種とを
含有することを特徴とする緑色発光希土類酸硫化物蛍光
体。2. A composition formula (Gd 1-XYz, Y x , Tb y, Tm z) 2 O 2 S ( where, x, y and z are each 0 ≦ x ≦ 0. 4,0.
0001 ≤ y ≤ 0.02 and 0 ≤ z ≤ 0.005), and (a) 0.3-
30 ppm zinc (Zn), and (b) 0.04 to 0.6
ppm cerium (Ce) and / or 0.04 to total
10ppm scandium (Sc), neodymium (Nd)
And at least one of ytterbium (Yb), a green light emitting rare earth oxysulfide phosphor.
線用蛍光体及び該Ｘ線用蛍光体を分散支持する結合剤か
らなる蛍光体層とを有する増感紙において、上記Ｘ線用
蛍光体が請求項１又は２記載の緑色発光希土類酸硫化物
蛍光体であることを特徴とする増感紙。3. A support and X provided on the support.
An intensifying screen having a fluorescent substance for X-rays and a fluorescent substance layer comprising a binder that dispersively supports the fluorescent substance for X-rays, wherein the fluorescent substance for X-rays is the green-emitting rare earth oxysulfide of claim 1 or 2. An intensifying screen characterized by being a phosphor.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP6070394A JPH07278540A (en) | 1994-04-08 | 1994-04-08 | Green luminous fluorescent substance of rare earth elements oxysulfide and sensitized paper containing the same |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP6070394A JPH07278540A (en) | 1994-04-08 | 1994-04-08 | Green luminous fluorescent substance of rare earth elements oxysulfide and sensitized paper containing the same |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH07278540A true JPH07278540A (en) | 1995-10-24 |
Family
ID=13430194
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP6070394A Pending JPH07278540A (en) | 1994-04-08 | 1994-04-08 | Green luminous fluorescent substance of rare earth elements oxysulfide and sensitized paper containing the same |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH07278540A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6676854B2 (en) | 2001-06-25 | 2004-01-13 | Kasei Optonix, Ltd. | Gadorinium oxysulfide phosphor for digital radiography, radiographic image conversion screen and radiograph-forming device |
| CN105602564A (en) * | 2016-03-03 | 2016-05-25 | 盐城工学院 | Zn reinforced rare earth sulfur oxide up-conversion luminescent material and preparation method thereof |
-
1994
- 1994-04-08 JP JP6070394A patent/JPH07278540A/en active Pending
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6676854B2 (en) | 2001-06-25 | 2004-01-13 | Kasei Optonix, Ltd. | Gadorinium oxysulfide phosphor for digital radiography, radiographic image conversion screen and radiograph-forming device |
| DE10228138B4 (en) * | 2001-06-25 | 2017-07-13 | Kasei Optonix, Ltd. | Gadolinium oxysulfide phosphor for digital radiography, radiographic image conversion screen and radiograph-forming device |
| CN105602564A (en) * | 2016-03-03 | 2016-05-25 | 盐城工学院 | Zn reinforced rare earth sulfur oxide up-conversion luminescent material and preparation method thereof |
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