JPH036289A - Manufacture of phosphor for x-ray intensifying screen - Google Patents
Manufacture of phosphor for x-ray intensifying screenInfo
- Publication number
- JPH036289A JPH036289A JP14053789A JP14053789A JPH036289A JP H036289 A JPH036289 A JP H036289A JP 14053789 A JP14053789 A JP 14053789A JP 14053789 A JP14053789 A JP 14053789A JP H036289 A JPH036289 A JP H036289A
- Authority
- JP
- Japan
- Prior art keywords
- phosphor
- dispersion
- intensifying screen
- water resistance
- silicon dioxide
- 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.)
- Granted
Links
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 title claims abstract description 83
- 238000004519 manufacturing process Methods 0.000 title claims description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 52
- 235000012239 silicon dioxide Nutrition 0.000 claims abstract description 26
- 239000000377 silicon dioxide Substances 0.000 claims abstract description 26
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 20
- 239000006185 dispersion Substances 0.000 claims abstract description 16
- 229910052710 silicon Inorganic materials 0.000 claims description 9
- 239000010703 silicon Substances 0.000 claims description 9
- 239000010409 thin film Substances 0.000 claims description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 25
- 239000000126 substance Substances 0.000 abstract description 10
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 abstract description 6
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 abstract description 6
- 230000001464 adherent effect Effects 0.000 abstract description 3
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 abstract description 3
- 150000003961 organosilicon compounds Chemical class 0.000 abstract 2
- 229910052681 coesite Inorganic materials 0.000 abstract 1
- 229910052906 cristobalite Inorganic materials 0.000 abstract 1
- 229910052682 stishovite Inorganic materials 0.000 abstract 1
- 229910052905 tridymite Inorganic materials 0.000 abstract 1
- 239000010408 film Substances 0.000 description 21
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 8
- 235000019441 ethanol Nutrition 0.000 description 7
- 230000001681 protective effect Effects 0.000 description 7
- 239000002245 particle Substances 0.000 description 6
- 230000007062 hydrolysis Effects 0.000 description 5
- 238000006460 hydrolysis reaction Methods 0.000 description 5
- 238000000034 method Methods 0.000 description 5
- 239000000853 adhesive Substances 0.000 description 4
- 230000001070 adhesive effect Effects 0.000 description 4
- 239000000839 emulsion Substances 0.000 description 4
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 3
- 229910052688 Gadolinium Inorganic materials 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- 235000011114 ammonium hydroxide Nutrition 0.000 description 3
- 230000007423 decrease Effects 0.000 description 3
- 238000010586 diagram Methods 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 229910052761 rare earth metal Inorganic materials 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 2
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 description 2
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 2
- 229910052946 acanthite Inorganic materials 0.000 description 2
- OJMOMXZKOWKUTA-UHFFFAOYSA-N aluminum;borate Chemical compound [Al+3].[O-]B([O-])[O-] OJMOMXZKOWKUTA-UHFFFAOYSA-N 0.000 description 2
- 230000003247 decreasing effect Effects 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 229910000037 hydrogen sulfide Inorganic materials 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 238000002601 radiography Methods 0.000 description 2
- 150000002910 rare earth metals Chemical class 0.000 description 2
- -1 silver halide Chemical class 0.000 description 2
- XUARKZBEFFVFRG-UHFFFAOYSA-N silver sulfide Chemical compound [S-2].[Ag+].[Ag+] XUARKZBEFFVFRG-UHFFFAOYSA-N 0.000 description 2
- 229940056910 silver sulfide Drugs 0.000 description 2
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 description 1
- 206010034972 Photosensitivity reaction Diseases 0.000 description 1
- 229910052771 Terbium Inorganic materials 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 229910052788 barium Inorganic materials 0.000 description 1
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 150000004820 halides Chemical class 0.000 description 1
- 230000036211 photosensitivity Effects 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- XTQHKBHJIVJGKJ-UHFFFAOYSA-N sulfur monoxide Chemical compound S=O XTQHKBHJIVJGKJ-UHFFFAOYSA-N 0.000 description 1
- 239000006228 supernatant Substances 0.000 description 1
- UQMOLLPKNHFRAC-UHFFFAOYSA-N tetrabutyl silicate Chemical compound CCCCO[Si](OCCCC)(OCCCC)OCCCC UQMOLLPKNHFRAC-UHFFFAOYSA-N 0.000 description 1
- LFQCEHFDDXELDD-UHFFFAOYSA-N tetramethyl orthosilicate Chemical compound CO[Si](OC)(OC)OC LFQCEHFDDXELDD-UHFFFAOYSA-N 0.000 description 1
- ZQZCOBSUOFHDEE-UHFFFAOYSA-N tetrapropyl silicate Chemical compound CCCO[Si](OCCC)(OCCC)OCCC ZQZCOBSUOFHDEE-UHFFFAOYSA-N 0.000 description 1
Landscapes
- Conversion Of X-Rays Into Visible Images (AREA)
- Luminescent Compositions (AREA)
Abstract
Description
【発明の詳細な説明】
［産業上の利用分野コ
本発明はＸ線増感紙用蛍光体の製造方法に係り、特に表
面に二酸化硅素薄膜を有するＸ線蛍光体の製造方法に関
する。DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to a method for manufacturing a phosphor for an X-ray intensifying screen, and more particularly to a method for manufacturing an X-ray phosphor having a silicon dioxide thin film on its surface.
［従来技術及び発明が解決しようとする課題］Ｘ線増感
紙は、主に医療用放射線撮影あるいは工業用放射線撮影
において、Ｘ線の吸収量を増し、Ｘ線像のコントラスト
を上げ、Ｘ線フィルムの感光性を増すためにＸ線フィル
ムの両側に密着して用いられる。[Prior Art and Problems to be Solved by the Invention] X-ray intensifying screens are used mainly in medical radiography or industrial radiography to increase the amount of X-ray absorption, increase the contrast of X-ray images, and It is used in close contact with both sides of the X-ray film to increase the photosensitivity of the film.
一般にこのＸ線増感紙は、増感紙ベースと、その上に塗
布された有機バインダー及び蛍光体を含む蛍光体層と、
この蛍光体層上を覆う１０μｍ程度の透明な保護膜とを
有する。 Ｘ線フィルムは、その両側に２０〜３０μｍ
程度の厚さで塗布された乳剤とを保護膜とが接するよう
に２枚１組のＸ線増感紙に挟まれて使用される。Ｘ線画
像の鮮鋭度の点から、このＸ線フィルムと増感紙とは密
着した状態であることが重要である。Generally, this X-ray intensifying screen includes an intensifying screen base, a phosphor layer containing an organic binder and a phosphor coated thereon,
It has a transparent protective film of about 10 μm covering the phosphor layer. The X-ray film has 20-30 μm on both sides.
It is used by sandwiching the emulsion coated to a certain thickness between a pair of X-ray intensifying screens so that the protective film is in contact with the emulsion. From the viewpoint of the sharpness of the X-ray image, it is important that the X-ray film and the intensifying screen are in close contact with each other.
また、前記保護膜は、発光の吸収、散乱が起こらないよ
うに透明であることが必要であるとともに、その厚みは
１０μｍ程度であることが好ましい。しかしながら保護
膜の膜厚が薄くなるに従って膜中にピンホールを生じや
すく、このピンホールを通って保護フィルムより内部に
水分が浸入すると、増感紙を変質させたり、Ｘ線フィル
ムの乳剤層に悪影響を与える恐れがある。Further, the protective film needs to be transparent so as not to absorb or scatter the emitted light, and preferably has a thickness of about 10 μm. However, as the thickness of the protective film becomes thinner, pinholes are more likely to form in the film, and if water penetrates into the inside of the protective film through these pinholes, it may change the quality of the intensifying screen or damage the emulsion layer of the X-ray film. There is a risk of adverse effects.
例えばＧｄ２Ｏ２Ｓ：Ｔｂ５Ｙ２０２Ｓ：ＴｂおよびＬ
ａ２０２ Ｓ ： Ｔｂ等の酸硫化物希土類蛍光体が用
いられたオルソフィルムタイプの増感紙の場合、この増
感紙を湿度の高い状態で保存すると、保：ｊｋ膜のピン
ホールから水分が流入し、この微全の水分により蛍光体
表面が加水分解を起こし、硫化水素ガスを発生する。こ
の硫化水素ガスはフィルム乳剤の一成分であるハロゲン
化銀と反応し、黒色の硫化銀を生成する。この黒色の硫
化銀はその部分の蛍光体の輝度を低下させ、使用に際し
誤判断を招く。For example Gd2O2S:Tb5Y202S:Tb and L
a202 S: In the case of an ortho film type intensifying screen that uses an oxysulfide rare earth phosphor such as Tb, if this intensifying screen is stored in a high humidity condition, moisture will flow in through the pinholes in the protective film. However, this tiny amount of water causes hydrolysis on the surface of the phosphor, generating hydrogen sulfide gas. This hydrogen sulfide gas reacts with silver halide, which is a component of the film emulsion, to produce black silver sulfide. This black silver sulfide reduces the brightness of the phosphor in that area, leading to misjudgment during use.
このようにＸ線増感紙用の蛍光体は耐水性を必要とする
。しかしながら従来のＸ線増感紙用蛍光体には十分な耐
水性がなかった。As described above, phosphors for X-ray intensifying screens require water resistance. However, conventional phosphors for X-ray intensifying screens did not have sufficient water resistance.
本発明は上記事情を鑑みてなされたもので、耐水性に優
れたＸ線増感紙用蛍光体を提供することを目的とする。The present invention has been made in view of the above circumstances, and an object of the present invention is to provide a phosphor for an X-ray intensifying screen that has excellent water resistance.
［発明を解決するための手段］
本発明者らは、Ｘ線増感紙用蛍光体の耐水性を改善する
ため、アルミニウム、亜鉛、マグネシウム、ストロンチ
ウム等のリン酸塩、ホウ酸塩、水酸化物、フッ化物等の
無機物質を付着剤として用い、蛍光体の表面処理を試み
た。そこで、いずれの場合も付着物質が蛍光体表面で粒
状に付着するため、蛍光体に十分な耐水性を付与するこ
とはできなかった。しかしながら、本発明者らは、付着
剤として有機硅素を用いることにより、蛍光体上に付着
物質の被膜が形成されることを見出し、本発明をなすに
至った。[Means for Solving the Invention] In order to improve the water resistance of a phosphor for an We attempted to treat the surface of phosphors using inorganic substances such as fluoride and fluoride as adhesives. In either case, the adhering substance adheres in the form of particles on the surface of the phosphor, making it impossible to impart sufficient water resistance to the phosphor. However, the present inventors have discovered that by using organic silicon as an adhesive, a film of the adherent substance is formed on the phosphor, and has accomplished the present invention.
本発明の方法は、アルコール中にＸ線増感紙用蛍光体を
分散し、蛍光体分散液を調製する工程と、該分散液のｐ
Ｈを８以上に調整し、かつ該分散液の温度を４０〜７０
℃に保持しながら、該分散液中の蛍光体１００重量部に
対し毎分０，１重量部以下の添加速度で有機硅素を添加
することにより蛍光体表面に二酸化硅素薄膜を形成する
工程とを含むことを特徴とする。The method of the present invention includes the steps of dispersing a phosphor for an X-ray intensifying screen in alcohol to prepare a phosphor dispersion, and
H is adjusted to 8 or more, and the temperature of the dispersion is adjusted to 40 to 70.
A step of forming a silicon dioxide thin film on the surface of the phosphor by adding organic silicon at a rate of 0.1 parts by weight or less per minute to 100 parts by weight of the phosphor in the dispersion while maintaining the temperature at ℃. It is characterized by containing.
本発明においては、有機硅素を添加する間、前記分散液
のｐＨ値を常に８以上に好ましく９以上に維持する。ｐ
Ｈ値が８未満であると、本発明に用いる二酸化硅素を生
ずるための有機硅素の加水分解が進行しにくくなり、蛍
光体表面に二酸化硅素薄膜が形成できない。また、有機
硅素の添加中、前記分散液の温度は４０〜７０℃に保持
する必要がある。この温度が４０℃未満であると有機硅
素の加水分解が進行しがたく、７０℃を越えると、アン
モニア水の蒸発が起こるため、ｐＨが低下する。また、
有機硅素の添加速度は、前記分散液中の蛍光体１００重
量部に対し毎分０．１重量部以下の有機硅素を滴下する
。有機硅素の１分間当りの添加量が０．１を量を越える
と、有機硅素の加水分解により生じた二酸化硅素が蛍光
体上で膜を形成せず粒状に付着してしまう。また、分散
液の濃度は蛍光体１００重量部に対し、ｉｏｏ重量部以
上が好ましく、１００重量部未満であると蛍光体が十分
分散せず不均一な膜を形成する傾向がある。In the present invention, the pH value of the dispersion is always maintained at 8 or higher, preferably at 9 or higher, during the addition of organosilicon. p
If the H value is less than 8, the hydrolysis of organic silicon to produce silicon dioxide used in the present invention will be difficult to proceed, making it impossible to form a silicon dioxide thin film on the surface of the phosphor. Further, during the addition of organic silicon, the temperature of the dispersion liquid must be maintained at 40 to 70°C. If this temperature is less than 40°C, hydrolysis of organosilicon will be difficult to proceed, and if it exceeds 70°C, evaporation of ammonia water will occur, resulting in a decrease in pH. Also,
The organic silicon is added at a rate of 0.1 part by weight or less per minute per 100 parts by weight of the phosphor in the dispersion. If the amount of organic silicon added per minute exceeds 0.1, silicon dioxide produced by hydrolysis of organic silicon will not form a film on the phosphor but will adhere in the form of particles. Further, the concentration of the dispersion liquid is preferably at least 100 parts by weight per 100 parts by weight of the phosphor, and if it is less than 100 parts by weight, the phosphor will not be sufficiently dispersed and a non-uniform film will tend to be formed.
本発明に用いるアルコールとしては、メチルアルコール
、エチルアルコール、プロピルアルコール、ブチルアル
コール等の低級アルコール好ましくはエチルアルコール
を使用することができる。As the alcohol used in the present invention, lower alcohols such as methyl alcohol, ethyl alcohol, propyl alcohol, and butyl alcohol, preferably ethyl alcohol can be used.
また、本発明に用いる蛍光体としては、Ｇ ｄ ２０２
Ｓ ： Ｔ ｂ ｓ Ｙ ２０２ Ｓ ： Ｔ ｂ
５（Ｇｄ、Ｙ）２０２ Ｓ ： Ｔｂ、Ｌａ２ ｏ２Ｓ
：Ｔｂ等の酸硫化物希土類蛍光体の他、Ｌａ０Ｂ ｒ
ＴｍＳＬａＯＢｒ：Ｔｂ等酸臭化物希土類蛍光体、Ｂａ
ＦＣ：Ｅｕ５ＢａＦＢｒ：Ｅｕ５ＢａＦＣ：Ｅｕ等のバ
リウムハライド蛍光体等、通常Ｘ線増感紙用に用いられ
るものを用いることができる。Further, as the phosphor used in the present invention, G d 202
S: T b s Y 202 S: T b
5 (Gd, Y) 202 S: Tb, La2 o2S
:In addition to oxysulfide rare earth phosphors such as Tb, La0B r
TmSLaOBr: Acid bromide rare earth phosphor such as Tb, Ba
A barium halide phosphor such as FC:Eu5BaFBr:Eu5BaFC:Eu, which is normally used for X-ray intensifying screens, can be used.
本発明に用いる有機ケイ素としては、メチルシリケート
、エチルシリケート及びプロピルシリケート、ブチルシ
リケート等があるが、好ましくはエチルシリケートを用
いることができる。The organosilicon used in the present invention includes methyl silicate, ethyl silicate, propyl silicate, butyl silicate, etc., and preferably ethyl silicate can be used.
さらに、本発明に用いる有機硅素の添加量は、得られる
蛍光体１００重量部に対する二酸化硅素の付ｅｆｆｉが
０．０１〜５重量部となるように調整されていることが
好ましい。Further, the amount of organic silicon used in the present invention is preferably adjusted so that the effi of silicon dioxide added to 100 parts by weight of the obtained phosphor is 0.01 to 5 parts by weight.
［作用］
従来の蛍光体は、第１図すに示すように付着剤例えばホ
ウ酸アルミニウムによって処理すると、蛍光体上に物質
が粒状に付着してしまうため、耐水性が不十分である。[Function] As shown in FIG. 1, when a conventional phosphor is treated with an adhesive such as aluminum borate, the substance adheres to the phosphor in the form of particles, resulting in insufficient water resistance.
また、この粒状の付着物質の存在により輝度が低下する
。本発明の方法を用いると、第１図ａに示すように、そ
の表面に二酸化硅素の透明で均一な薄膜が付着した構造
を有する蛍光体を得ることができる。この均一な薄膜に
より、水の浸入を防ぐことができる。また、この均一な
薄膜は透明で、光を十分に透過させることができる。ま
た、二酸化硅素は水だけでなく、酸にも強いことから、
耐水性とともに耐酸性をも有する
［実施例］
以下、実施例を示し、本発明を具体的に説明する。Furthermore, the presence of this particulate adhesion substance reduces the brightness. By using the method of the present invention, it is possible to obtain a phosphor having a structure in which a transparent and uniform thin film of silicon dioxide is adhered to the surface of the phosphor, as shown in FIG. 1a. This uniform thin film can prevent water from entering. Moreover, this uniform thin film is transparent and can sufficiently transmit light. In addition, silicon dioxide is resistant not only to water but also to acids.
[Example] Having acid resistance as well as water resistance [Example] The present invention will be specifically explained below with reference to Examples.
実施例１
次の組成を有する溶液Ａを４つ調整し、これを撹拌しな
がら５０℃に加熱した。Example 1 Four solutions A having the following composition were prepared and heated to 50° C. with stirring.
溶液Ａ
エタノール ・・・２００ｇ１５％
アンモニア水 ・・・１０ｇ蛍光体（Ｇｄ
ＯＳ二Ｔｂ）・・・ｌｏｏｇまた、エタノール４０ｇに
対し、各々エチルシリケート２．５ｇ、５ｇ、７．５ｇ
、１２． ５ｇを混合し、溶液Ｂ１、Ｂ２、Ｂ３、Ｂ４
を調製した。なお、エチルシリケートとしては二酸化ケ
イ素換算含量４０重量％のものを使用した。たとえば溶
液Ｂ１はエチルシリケート２．５ｇ中１ｇの二酸化ケイ
素を含有している。Solution A Ethanol...200g15%
Ammonia water...10g phosphor (Gd
OS2Tb)...loog Also, for 40g of ethanol, 2.5g, 5g, and 7.5g of ethyl silicate, respectively.
, 12. Mix 5g, solutions B1, B2, B3, B4
was prepared. The ethyl silicate used had a silicon dioxide equivalent content of 40% by weight. For example, solution B1 contains 1 g of silicon dioxide in 2.5 g of ethyl silicate.
さらに、溶液Ｃとして５％アンモニア水を４つ用意した
。Furthermore, four 5% ammonia water solutions were prepared as solution C.
前記溶液Ａを撹拌しながら５０〜５５℃に保ちつつ、溶
液Ｂ１及び溶液Ｃを撹拌している溶液Ａ中に滴下した。While stirring the solution A and keeping it at 50 to 55° C., solution B1 and solution C were dropped into the stirring solution A.
滴下時間は約１２分とし、滴下中はｐＨを９．２〜９．
４に保った。滴下終了後、蛍光体が十分沈降させ、その
後上澄み液を捨て、脱水し、１３０℃で１５時間乾燥し
た。得られた粒体をふるい分けし、蛍光体Ｄ１を得た。The dropping time was approximately 12 minutes, and the pH was maintained at 9.2-9.
I kept it at 4. After completion of the dropping, the phosphor was allowed to settle sufficiently, and then the supernatant liquid was discarded, dehydrated, and dried at 130° C. for 15 hours. The obtained particles were sieved to obtain phosphor D1.
さらにまた溶液Ｂ１を用いるかわりに溶液Ｂ２、Ｂ３、
Ｂ４を用い、その滴下時間を２４分、３６分、６０分と
し、それ以外は同様にして蛍光体Ｄ２、Ｂ３、Ｂ４を得
た。これらの４つの蛍光体は各々下記に示す特性を有す
る。Furthermore, instead of using solution B1, solutions B2, B3,
Phosphors D2, B3, and B4 were obtained in the same manner except that B4 was used and the dropping times were set to 24 minutes, 36 minutes, and 60 minutes. Each of these four phosphors has the characteristics shown below.
Ｄｉ Ｂ２ Ｂ３ Ｂ４
全蛍光体量に体する
二酸化ケイ素付着量
（重量％） ０．９４． １．８１３ ２．８２
４．８０耐水性 （％） ９８ １００ １
００ １００輝度低下（％） １ ４ ６
１２これに対し、二酸化ケイ素を付着させないＧｄ
ＯＳ：Ｔｂ蛍光体の耐水性は８５％であった。Di B2 B3 B4 Amount of silicon dioxide deposited in total amount of phosphor (% by weight) 0.94. 1.813 2.82
4.80 Water resistance (%) 98 100 1
00 100 Brightness reduction (%) 1 4 6
12 In contrast, Gd that does not attach silicon dioxide
The water resistance of the OS:Tb phosphor was 85%.
なお、耐水性は、以下のようにして評価した。In addition, water resistance was evaluated as follows.
まず、２００μｍの厚さの蛍光体層を有するＸ線増感紙
の蛍光体表面の一部に水分を強制的に吸収させ、保護膜
を設けずに直接Ｘ線フィルムを密着させて３日間放置す
る。その後Ｘ線フィルムを取り除き、水分を吸わせた部
分と水分を吸わせない部分とのＸ線発光輝度を測定した
。前記蛍光体ＤＩないしＢ４についてこの相対輝度（吸
湿成分の輝度／無吸湿成分の輝度）と、全蛍光体量に対
する二酸化硅素付着量との関係を第２図に示す。First, moisture was forcibly absorbed into a part of the phosphor surface of an X-ray intensifying screen with a 200 μm thick phosphor layer, and an X-ray film was directly attached without a protective film and left for 3 days. do. Thereafter, the X-ray film was removed, and the X-ray luminance was measured for the portions that had absorbed moisture and the portions that had not absorbed moisture. FIG. 2 shows the relationship between the relative brightness (brightness of hygroscopic component/brightness of non-hygroscopic component) of the phosphors DI to B4 and the amount of attached silicon dioxide relative to the total amount of phosphor.
第２図から明らかなように、二酸化ケイ素の付着量が多
いほど相対輝度が高く、耐水性に優れている。As is clear from FIG. 2, the greater the amount of silicon dioxide deposited, the higher the relative brightness and the better the water resistance.
また、第３図に、実施例１で得られた４つの蛍光体と、
従来の付着剤（ホウ酸アルミニウム）で処理した蛍光体
の蛍光体粉体に各々直接Ｘ線を照射し、その発光輝度と
、全蛍光体量に対する付着物質の付着量との関係を、各
々実線Ｃ１実線ｄに示す。この図から明らかなように付
着量の増加にともなっていずれの蛍光体も輝度の低下か
見られるが、本発明に係る蛍光体においては、二酸化硅
素付着量の増加に対する輝度の低下が少ないことがわか
る。In addition, FIG. 3 shows the four phosphors obtained in Example 1,
The phosphor powder of each phosphor treated with a conventional adhesive (aluminum borate) is directly irradiated with X-rays, and the relationship between the luminance and the amount of adhering substance attached to the total amount of phosphor is shown as a solid line. It is shown by C1 solid line d. As is clear from this figure, the brightness of all phosphors decreases as the amount of attached silicon dioxide increases, but in the phosphor of the present invention, the decrease in brightness with respect to the increase in the amount of silicon dioxide attached is small. Recognize.
実施例２
蛍光体としてＹ２０□Ｓ：Ｔｂ１００ｇを用いる以外は
実施例１の蛍光体Ｄ１と同様にして蛍光体を得た。得ら
れた蛍光体は全蛍光体量に対し０．９０重二％の二酸化
ケイ素が付着しており、耐水性１００％、輝度低下１％
であった。また二酸化ケイ素を付着させないＹ２０□Ｓ
：Ｔｂ蛍光体の耐水性は９５％であった。Example 2 A phosphor was obtained in the same manner as the phosphor D1 of Example 1 except that 100 g of Y20□S:Tb was used as the phosphor. The obtained phosphor has 0.90% silicon dioxide attached to the total amount of phosphor, has 100% water resistance and 1% reduction in brightness.
Met. Also, Y20□S does not attach silicon dioxide.
: The water resistance of the Tb phosphor was 95%.
実施例３
蛍光体として（Ｇｄ、Ｙ）２ ｏ２ Ｓ ：Ｔｂ１００
ｇを用いる以外は実施例１の蛍光体Ｄ１と同様にして蛍
光体を得た。得られた蛍光体は全蛍光体量に対し０．９
０重量％の二酸化ケイ素が付着しており、耐水性９５％
、輝度低下２％であった。また二酸化ケイ素を付着させ
ない（Ｇｄ、Ｙ） ２０□Ｓ：Ｔｂ蛍光体の耐水性は７
７％であった。Example 3 As a phosphor (Gd, Y)2 o2 S: Tb100
A phosphor was obtained in the same manner as phosphor D1 of Example 1 except that g was used. The obtained phosphor was 0.9% of the total amount of phosphor.
0wt% silicon dioxide attached, 95% water resistance
, the brightness decreased by 2%. Also, silicon dioxide is not attached (Gd, Y) The water resistance of the 20□S:Tb phosphor is 7
It was 7%.
実施例４
蛍光体としてＬａ２０２ Ｓ ： Ｔｂ２１００ｇを用
いる以外は実施例１の蛍光体Ｄ１と同様にして蛍光体を
１）た。得られた蛍光体は全蛍光体量に対し０．８７重
−％の二酸化ケイ素が付着しており、耐水性９１９６、
輝度低下２％であった。また二酸化ケイ素を付着させな
いＬａ２０２ Ｓ ： Ｔｂ蛍光体の耐水性は５６％で
あった。Example 4 A phosphor was prepared in the same manner as the phosphor D1 of Example 1 except that 2100 g of La202S:Tb was used as the phosphor. The obtained phosphor has 0.87% by weight of silicon dioxide attached to the total amount of phosphor, and has a water resistance of 9196,
The brightness decreased by 2%. Furthermore, the water resistance of the La202S:Tb phosphor to which no silicon dioxide was attached was 56%.
［発明の効果］
本発明の方法を用いることにより、付着物質による輝度
の低下が少なく、優れた耐水性を有する蛍光体を得るこ
とができる。このような蛍光体はまた、耐水性を有する
ことにより、蛍光体の加水分解による化学変化を防ぎ、
均一な輝度を有する蛍光体を提供することができる。こ
のように本発明に係る蛍光体を用いると、輝度が高く、
Ｘ線フィルムに好適なＸ線増感紙を提供することができ
る。[Effects of the Invention] By using the method of the present invention, it is possible to obtain a phosphor having excellent water resistance and less reduction in brightness due to attached substances. Such phosphors also have water resistance, which prevents chemical changes due to hydrolysis of the phosphor.
A phosphor with uniform brightness can be provided. As described above, when the phosphor according to the present invention is used, the brightness is high;
An X-ray intensifying screen suitable for X-ray film can be provided.
第１ａ図は、本発明の一実施例に係る蛍光体の粒子の構
造を示す図、第１ｂ図は、従来の蛍光体の粒子の構造を
示す図、第２図は、本発明に係る蛍光体の二酸化硅素付
着量と、相対輝度（吸湿させた蛍光体の輝度／吸湿させ
ない蛍光体の輝度）との関係を表わす図、第３図は、本
発明に係る蛍光体及びホウ酸アルミニウムを付着させた
蛍光体の、輝度低下と二酸化硅素の付着量との関係を表
わす図である。FIG. 1a is a diagram showing the structure of particles of a phosphor according to an embodiment of the present invention, FIG. 1b is a diagram showing a structure of particles of a conventional phosphor, and FIG. Figure 3 shows the relationship between the amount of silicon dioxide deposited on the body and the relative brightness (brightness of the phosphor that has absorbed moisture/brightness of the phosphor that has not absorbed moisture). FIG. 4 is a diagram showing the relationship between the luminance reduction and the amount of silicon dioxide deposited on the phosphor.
Claims (1)
分散液を調製する工程と、該分散液のｐＨを８以上に調
整し、かつ該分散液の温度を４０〜７０℃に保持しなが
ら、該分散液中の蛍光体１００重量部に対し毎分０．１
重量部以下の添加速度で有機硅素を添加することにより
蛍光体表面に二酸化硅素薄膜を形成する工程とを含むＸ
線増感紙用蛍光体の製造方法。A step of dispersing a phosphor for an X-ray intensifying screen in alcohol to prepare a phosphor dispersion, adjusting the pH of the dispersion to 8 or higher, and maintaining the temperature of the dispersion at 40 to 70°C. At the same time, 0.1 parts per minute per 100 parts by weight of the phosphor in the dispersion.
A step of forming a silicon dioxide thin film on the surface of the phosphor by adding organic silicon at a rate of addition of parts by weight or less.
A method for producing a phosphor for a line intensifying screen.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP1140537A JPH07119412B2 (en) | 1989-06-02 | 1989-06-02 | Method for producing phosphor for X-ray intensifying screen |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP1140537A JPH07119412B2 (en) | 1989-06-02 | 1989-06-02 | Method for producing phosphor for X-ray intensifying screen |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH036289A true JPH036289A (en) | 1991-01-11 |
| JPH07119412B2 JPH07119412B2 (en) | 1995-12-20 |
Family
ID=15270979
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP1140537A Expired - Fee Related JPH07119412B2 (en) | 1989-06-02 | 1989-06-02 | Method for producing phosphor for X-ray intensifying screen |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH07119412B2 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2000160155A (en) * | 1998-09-24 | 2000-06-13 | Konica Corp | Rare-earth metal activated alkaline earth metal fluorohalide-based phosphorescent fluorescent substance, its moistureproof treatment, radiological image converting panel and production of phosphorescent fluorescent substance |
-
1989
- 1989-06-02 JP JP1140537A patent/JPH07119412B2/en not_active Expired - Fee Related
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2000160155A (en) * | 1998-09-24 | 2000-06-13 | Konica Corp | Rare-earth metal activated alkaline earth metal fluorohalide-based phosphorescent fluorescent substance, its moistureproof treatment, radiological image converting panel and production of phosphorescent fluorescent substance |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH07119412B2 (en) | 1995-12-20 |
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