JPH0460151B2 - - Google Patents
Info
- Publication number
- JPH0460151B2 JPH0460151B2 JP24045584A JP24045584A JPH0460151B2 JP H0460151 B2 JPH0460151 B2 JP H0460151B2 JP 24045584 A JP24045584 A JP 24045584A JP 24045584 A JP24045584 A JP 24045584A JP H0460151 B2 JPH0460151 B2 JP H0460151B2
- Authority
- JP
- Japan
- Prior art keywords
- radiation image
- image conversion
- phosphor
- range
- radiation
- 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.)
- Expired
Links
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 143
- 230000005855 radiation Effects 0.000 claims description 137
- 238000006243 chemical reaction Methods 0.000 claims description 101
- 238000000034 method Methods 0.000 claims description 46
- 229910052693 Europium Inorganic materials 0.000 claims description 35
- OGPBJKLSAFTDLK-UHFFFAOYSA-N europium atom Chemical compound [Eu] OGPBJKLSAFTDLK-UHFFFAOYSA-N 0.000 claims description 33
- 239000000203 mixture Substances 0.000 claims description 25
- 150000004820 halides Chemical class 0.000 claims description 24
- 239000002131 composite material Substances 0.000 claims description 21
- 229910052794 bromium Inorganic materials 0.000 claims description 13
- 229910052801 chlorine Inorganic materials 0.000 claims description 13
- 229910052736 halogen Inorganic materials 0.000 claims description 8
- 150000002367 halogens Chemical class 0.000 claims description 8
- 230000001678 irradiating effect Effects 0.000 claims description 6
- 229910052791 calcium Inorganic materials 0.000 claims description 5
- 229910052731 fluorine Inorganic materials 0.000 claims description 5
- 229910052712 strontium Inorganic materials 0.000 claims description 5
- 229910052788 barium Inorganic materials 0.000 claims description 4
- 229910052784 alkaline earth metal Inorganic materials 0.000 claims description 3
- 150000001342 alkaline earth metals Chemical class 0.000 claims description 3
- 229910052751 metal Inorganic materials 0.000 claims description 3
- 239000002184 metal Substances 0.000 claims description 3
- 239000010410 layer Substances 0.000 description 50
- 239000011248 coating agent Substances 0.000 description 20
- 238000000576 coating method Methods 0.000 description 20
- 239000010408 film Substances 0.000 description 17
- -1 tin halide Chemical class 0.000 description 17
- 241001289141 Babr Species 0.000 description 16
- 230000005284 excitation Effects 0.000 description 16
- 239000011230 binding agent Substances 0.000 description 13
- 238000010304 firing Methods 0.000 description 12
- 238000004020 luminiscence type Methods 0.000 description 12
- 239000012298 atmosphere Substances 0.000 description 10
- 239000000243 solution Substances 0.000 description 10
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 9
- 239000000463 material Substances 0.000 description 9
- 230000001681 protective effect Effects 0.000 description 9
- 230000035945 sensitivity Effects 0.000 description 9
- 239000000126 substance Substances 0.000 description 9
- 229920000728 polyester Polymers 0.000 description 8
- 239000004065 semiconductor Substances 0.000 description 8
- 229910001615 alkaline earth metal halide Inorganic materials 0.000 description 7
- 239000000460 chlorine Substances 0.000 description 7
- YUOWTJMRMWQJDA-UHFFFAOYSA-J tin(iv) fluoride Chemical compound [F-].[F-].[F-].[F-].[Sn+4] YUOWTJMRMWQJDA-UHFFFAOYSA-J 0.000 description 7
- 239000000020 Nitrocellulose Substances 0.000 description 6
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 6
- 229920001220 nitrocellulos Polymers 0.000 description 6
- 239000002994 raw material Substances 0.000 description 6
- 238000003860 storage Methods 0.000 description 6
- 238000001035 drying Methods 0.000 description 5
- 238000002601 radiography Methods 0.000 description 5
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 4
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 4
- 239000011575 calcium Substances 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 238000000695 excitation spectrum Methods 0.000 description 4
- 150000002500 ions Chemical class 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- 229920000139 polyethylene terephthalate Polymers 0.000 description 4
- 239000005020 polyethylene terephthalate Substances 0.000 description 4
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 3
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 150000001252 acrylic acid derivatives Chemical class 0.000 description 3
- 239000000853 adhesive Substances 0.000 description 3
- 230000001070 adhesive effect Effects 0.000 description 3
- 239000007864 aqueous solution Substances 0.000 description 3
- NKQIMNKPSDEDMO-UHFFFAOYSA-L barium bromide Chemical compound [Br-].[Br-].[Ba+2] NKQIMNKPSDEDMO-UHFFFAOYSA-L 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 229920001577 copolymer Polymers 0.000 description 3
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 3
- 239000002270 dispersing agent Substances 0.000 description 3
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- 239000004408 titanium dioxide Substances 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 2
- 229910052684 Cerium Inorganic materials 0.000 description 2
- 108010010803 Gelatin Proteins 0.000 description 2
- 239000004952 Polyamide Substances 0.000 description 2
- 239000004372 Polyvinyl alcohol Substances 0.000 description 2
- YSMRWXYRXBRSND-UHFFFAOYSA-N TOTP Chemical compound CC1=CC=CC=C1OP(=O)(OC=1C(=CC=CC=1)C)OC1=CC=CC=C1C YSMRWXYRXBRSND-UHFFFAOYSA-N 0.000 description 2
- 229910052771 Terbium Inorganic materials 0.000 description 2
- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical compound ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 description 2
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 2
- 150000001298 alcohols Chemical class 0.000 description 2
- 229910001618 alkaline earth metal fluoride Inorganic materials 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- 229910001620 barium bromide Inorganic materials 0.000 description 2
- WDIHJSXYQDMJHN-UHFFFAOYSA-L barium chloride Chemical compound [Cl-].[Cl-].[Ba+2] WDIHJSXYQDMJHN-UHFFFAOYSA-L 0.000 description 2
- 229910001626 barium chloride Inorganic materials 0.000 description 2
- QVQLCTNNEUAWMS-UHFFFAOYSA-N barium oxide Chemical compound [Ba]=O QVQLCTNNEUAWMS-UHFFFAOYSA-N 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 239000006229 carbon black Substances 0.000 description 2
- 239000001569 carbon dioxide Substances 0.000 description 2
- 229910002092 carbon dioxide Inorganic materials 0.000 description 2
- 229910002091 carbon monoxide Inorganic materials 0.000 description 2
- 229920002301 cellulose acetate Polymers 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- FLKPEMZONWLCSK-UHFFFAOYSA-N diethyl phthalate Chemical compound CCOC(=O)C1=CC=CC=C1C(=O)OCC FLKPEMZONWLCSK-UHFFFAOYSA-N 0.000 description 2
- 229910001873 dinitrogen Inorganic materials 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 238000010894 electron beam technology Methods 0.000 description 2
- 238000000295 emission spectrum Methods 0.000 description 2
- 150000002178 europium compounds Chemical class 0.000 description 2
- 239000011888 foil Substances 0.000 description 2
- 229920000159 gelatin Polymers 0.000 description 2
- 239000008273 gelatin Substances 0.000 description 2
- 235000019322 gelatine Nutrition 0.000 description 2
- 235000011852 gelatine desserts Nutrition 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 229910052745 lead Inorganic materials 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 230000007935 neutral effect Effects 0.000 description 2
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 description 2
- 239000000049 pigment Substances 0.000 description 2
- 239000002985 plastic film Substances 0.000 description 2
- 229920006255 plastic film Polymers 0.000 description 2
- 239000004014 plasticizer Substances 0.000 description 2
- 229920002037 poly(vinyl butyral) polymer Polymers 0.000 description 2
- 229920002647 polyamide Polymers 0.000 description 2
- 229920000515 polycarbonate Polymers 0.000 description 2
- 239000004417 polycarbonate Substances 0.000 description 2
- 229920002689 polyvinyl acetate Polymers 0.000 description 2
- 239000011118 polyvinyl acetate Substances 0.000 description 2
- 229920002451 polyvinyl alcohol Polymers 0.000 description 2
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- KDYFGRWQOYBRFD-UHFFFAOYSA-N succinic acid Chemical compound OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 description 2
- 239000000725 suspension Substances 0.000 description 2
- 238000001291 vacuum drying Methods 0.000 description 2
- WSLDOOZREJYCGB-UHFFFAOYSA-N 1,2-Dichloroethane Chemical compound ClCCCl WSLDOOZREJYCGB-UHFFFAOYSA-N 0.000 description 1
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 1
- OEPOKWHJYJXUGD-UHFFFAOYSA-N 2-(3-phenylmethoxyphenyl)-1,3-thiazole-4-carbaldehyde Chemical compound O=CC1=CSC(C=2C=C(OCC=3C=CC=CC=3)C=CC=2)=N1 OEPOKWHJYJXUGD-UHFFFAOYSA-N 0.000 description 1
- XNWFRZJHXBZDAG-UHFFFAOYSA-N 2-METHOXYETHANOL Chemical compound COCCO XNWFRZJHXBZDAG-UHFFFAOYSA-N 0.000 description 1
- ZNQVEEAIQZEUHB-UHFFFAOYSA-N 2-ethoxyethanol Chemical compound CCOCCO ZNQVEEAIQZEUHB-UHFFFAOYSA-N 0.000 description 1
- PZBLUWVMZMXIKZ-UHFFFAOYSA-N 2-o-(2-ethoxy-2-oxoethyl) 1-o-ethyl benzene-1,2-dicarboxylate Chemical compound CCOC(=O)COC(=O)C1=CC=CC=C1C(=O)OCC PZBLUWVMZMXIKZ-UHFFFAOYSA-N 0.000 description 1
- 229910000838 Al alloy Inorganic materials 0.000 description 1
- DKPFZGUDAPQIHT-UHFFFAOYSA-N Butyl acetate Natural products CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 description 1
- GOJCZVPJCKEBQV-UHFFFAOYSA-N Butyl phthalyl butylglycolate Chemical compound CCCCOC(=O)COC(=O)C1=CC=CC=C1C(=O)OCCCC GOJCZVPJCKEBQV-UHFFFAOYSA-N 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- 229920002307 Dextran Polymers 0.000 description 1
- ZZSNKZQZMQGXPY-UHFFFAOYSA-N Ethyl cellulose Chemical compound CCOCC1OC(OC)C(OCC)C(OCC)C1OC1C(O)C(O)C(OC)C(CO)O1 ZZSNKZQZMQGXPY-UHFFFAOYSA-N 0.000 description 1
- 239000001856 Ethyl cellulose Substances 0.000 description 1
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 description 1
- 229910052688 Gadolinium Inorganic materials 0.000 description 1
- AEMRFAOFKBGASW-UHFFFAOYSA-N Glycolic acid Chemical class OCC(O)=O AEMRFAOFKBGASW-UHFFFAOYSA-N 0.000 description 1
- 229920000084 Gum arabic Polymers 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- NTIZESTWPVYFNL-UHFFFAOYSA-N Methyl isobutyl ketone Chemical compound CC(C)CC(C)=O NTIZESTWPVYFNL-UHFFFAOYSA-N 0.000 description 1
- UIHCLUNTQKBZGK-UHFFFAOYSA-N Methyl isobutyl ketone Natural products CCC(C)C(C)=O UIHCLUNTQKBZGK-UHFFFAOYSA-N 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 239000002202 Polyethylene glycol Substances 0.000 description 1
- 239000004642 Polyimide Substances 0.000 description 1
- 229920001328 Polyvinylidene chloride Polymers 0.000 description 1
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 description 1
- 241000978776 Senegalia senegal Species 0.000 description 1
- 229910008449 SnF 2 Inorganic materials 0.000 description 1
- 235000021355 Stearic acid Nutrition 0.000 description 1
- 229910052775 Thulium Inorganic materials 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 206010047571 Visual impairment Diseases 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- FJWGYAHXMCUOOM-QHOUIDNNSA-N [(2s,3r,4s,5r,6r)-2-[(2r,3r,4s,5r,6s)-4,5-dinitrooxy-2-(nitrooxymethyl)-6-[(2r,3r,4s,5r,6s)-4,5,6-trinitrooxy-2-(nitrooxymethyl)oxan-3-yl]oxyoxan-3-yl]oxy-3,5-dinitrooxy-6-(nitrooxymethyl)oxan-4-yl] nitrate Chemical compound O([C@@H]1O[C@@H]([C@H]([C@H](O[N+]([O-])=O)[C@H]1O[N+]([O-])=O)O[C@H]1[C@@H]([C@@H](O[N+]([O-])=O)[C@H](O[N+]([O-])=O)[C@@H](CO[N+]([O-])=O)O1)O[N+]([O-])=O)CO[N+](=O)[O-])[C@@H]1[C@@H](CO[N+]([O-])=O)O[C@@H](O[N+]([O-])=O)[C@H](O[N+]([O-])=O)[C@H]1O[N+]([O-])=O FJWGYAHXMCUOOM-QHOUIDNNSA-N 0.000 description 1
- 230000002745 absorbent Effects 0.000 description 1
- 239000002250 absorbent Substances 0.000 description 1
- 239000000205 acacia gum Substances 0.000 description 1
- 235000010489 acacia gum Nutrition 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- KXKVLQRXCPHEJC-UHFFFAOYSA-N acetic acid trimethyl ester Natural products COC(C)=O KXKVLQRXCPHEJC-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 239000012790 adhesive layer Substances 0.000 description 1
- 239000001361 adipic acid Substances 0.000 description 1
- 235000011037 adipic acid Nutrition 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 229910001864 baryta Inorganic materials 0.000 description 1
- HSUIVCLOAAJSRE-UHFFFAOYSA-N bis(2-methoxyethyl) benzene-1,2-dicarboxylate Chemical compound COCCOC(=O)C1=CC=CC=C1C(=O)OCCOC HSUIVCLOAAJSRE-UHFFFAOYSA-N 0.000 description 1
- 229910052797 bismuth Inorganic materials 0.000 description 1
- 229910052793 cadmium Inorganic materials 0.000 description 1
- 229920002678 cellulose Polymers 0.000 description 1
- 239000001913 cellulose Substances 0.000 description 1
- 229920006217 cellulose acetate butyrate Polymers 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 238000004040 coloring Methods 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 238000003745 diagnosis Methods 0.000 description 1
- 235000014113 dietary fatty acids Nutrition 0.000 description 1
- ASMQGLCHMVWBQR-UHFFFAOYSA-M diphenyl phosphate Chemical compound C=1C=CC=CC=1OP(=O)([O-])OC1=CC=CC=C1 ASMQGLCHMVWBQR-UHFFFAOYSA-M 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000000839 emulsion Substances 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- 235000019325 ethyl cellulose Nutrition 0.000 description 1
- 229920001249 ethyl cellulose Polymers 0.000 description 1
- QEDFUJZRPHEBFG-UHFFFAOYSA-K europium(3+);tribromide Chemical compound Br[Eu](Br)Br QEDFUJZRPHEBFG-UHFFFAOYSA-K 0.000 description 1
- 230000001747 exhibiting effect Effects 0.000 description 1
- 239000000194 fatty acid Substances 0.000 description 1
- 229930195729 fatty acid Natural products 0.000 description 1
- 150000004665 fatty acids Chemical class 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 230000004907 flux Effects 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 150000004676 glycans Chemical class 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 238000009434 installation Methods 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 229910052746 lanthanum Inorganic materials 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 150000002823 nitrates Chemical class 0.000 description 1
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 1
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 150000003014 phosphoric acid esters Chemical class 0.000 description 1
- 150000003021 phthalic acid derivatives Chemical class 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003229 poly(methyl methacrylate) Polymers 0.000 description 1
- 229920001225 polyester resin Polymers 0.000 description 1
- 239000004645 polyester resin Substances 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 229920001721 polyimide Polymers 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 239000004926 polymethyl methacrylate Substances 0.000 description 1
- 229920001282 polysaccharide Polymers 0.000 description 1
- 239000005017 polysaccharide Substances 0.000 description 1
- 229920002635 polyurethane Polymers 0.000 description 1
- 239000004814 polyurethane Substances 0.000 description 1
- 239000005033 polyvinylidene chloride Substances 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 108090000623 proteins and genes Proteins 0.000 description 1
- 102000004169 proteins and genes Human genes 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 239000010979 ruby Substances 0.000 description 1
- 229910001750 ruby Inorganic materials 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000007873 sieving Methods 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 239000002356 single layer Substances 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- GGCZERPQGJTIQP-UHFFFAOYSA-N sodium;9,10-dioxoanthracene-2-sulfonic acid Chemical compound [Na+].C1=CC=C2C(=O)C3=CC(S(=O)(=O)O)=CC=C3C(=O)C2=C1 GGCZERPQGJTIQP-UHFFFAOYSA-N 0.000 description 1
- 230000003595 spectral effect Effects 0.000 description 1
- 239000008117 stearic acid Substances 0.000 description 1
- 239000001384 succinic acid Substances 0.000 description 1
- 150000003467 sulfuric acid derivatives Chemical class 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 229920001059 synthetic polymer Polymers 0.000 description 1
- 229910052716 thallium Inorganic materials 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- HPGGPRDJHPYFRM-UHFFFAOYSA-J tin(iv) chloride Chemical compound Cl[Sn](Cl)(Cl)Cl HPGGPRDJHPYFRM-UHFFFAOYSA-J 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 238000002834 transmittance Methods 0.000 description 1
- 239000012780 transparent material Substances 0.000 description 1
- ILJSQTXMGCGYMG-UHFFFAOYSA-N triacetic acid Chemical compound CC(=O)CC(=O)CC(O)=O ILJSQTXMGCGYMG-UHFFFAOYSA-N 0.000 description 1
- ZIBGPFATKBEMQZ-UHFFFAOYSA-N triethylene glycol Chemical compound OCCOCCOCCO ZIBGPFATKBEMQZ-UHFFFAOYSA-N 0.000 description 1
- XZZNDPSIHUTMOC-UHFFFAOYSA-N triphenyl phosphate Chemical compound C=1C=CC=CC=1OP(OC=1C=CC=CC=1)(=O)OC1=CC=CC=C1 XZZNDPSIHUTMOC-UHFFFAOYSA-N 0.000 description 1
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
- 239000010937 tungsten Substances 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
- 229910052727 yttrium Inorganic materials 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
Landscapes
- Conversion Of X-Rays Into Visible Images (AREA)
- Radiography Using Non-Light Waves (AREA)
- Luminescent Compositions (AREA)
Description
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ãæŸå°ç·åå€æããã«ã«é¢ãããã®ã§ãããDETAILED DESCRIPTION OF THE INVENTION [Field of the Invention] The present invention relates to a radiation image conversion method and a radiation image conversion panel used in the method. More specifically, the present invention relates to a radiation image conversion method using a photostimulable divalent europium-activated composite halide phosphor, and a radiation image conversion panel used in the method.
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ç»ååãããã®ã§ããã[Background of the Invention] Conventionally, so-called radiography has been used as a method of obtaining radiation images as images, using a combination of a radiographic film having an emulsion layer made of a silver salt photosensitive material and an intensifying screen. law is being used. As an alternative to the conventional radiographic method, a radiation image conversion method using a stimulable phosphor is known, for example, as described in Japanese Patent Application Laid-Open No. 12145/1983. In this method, radiation transmitted through the subject or radiation emitted from the subject is absorbed into a stimulable phosphor, and then the phosphor is exposed to electromagnetic waves (excitation light) such as visible light or infrared rays in a time-series manner. By excitation, the radiation energy stored in the phosphor is emitted as fluorescence (stimulated luminescence), this fluorescence is read photoelectrically to obtain an electrical signal, and this electrical signal is converted into an image.
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ãéåžžã«é«ããã®ã§ããã The radiation image conversion method has the advantage that it is possible to obtain an X-ray image with a rich amount of information with a much lower exposure dose than when conventional radiography is used. Therefore, this radiation image conversion method has a very high utility value especially in direct medical radiography such as X-ray photography for the purpose of medical diagnosis.
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瀺ããã®ã§ããã Conventionally, divalent europium-activated alkaline earth metal fluoride halide phosphors (MãFX:
Eu 2+ , where Mã is at least one kind of alkaline earth metal selected from the group consisting of Ba, Sr, and Ca, and X is a halogen other than fluorine) has been proposed. This phosphor absorbs radiation such as X-rays and then emits light in the near-ultraviolet region (stimulated luminescence) when irradiated with electromagnetic waves in the visible light to infrared region.
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ããªãã As mentioned above, the radiation image conversion method utilizes the photostimulability of the phosphor, but the stimulable phosphor itself, other than this divalent europium-activated alkaline earth metal fluoride halide phosphor, does not have much effect. unknown.
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ïŒç¹é¡æ58â193162å·ïŒã The present applicant has already filed a patent application for a radiation image conversion method and a radiation image conversion panel using a new divalent europium-activated alkaline earth metal halide phosphor represented by the following compositional formula (Japanese Patent Application No. No. 193162).
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ïŒã瀺ããã®ã§ããã Compositional formula : M ã , Br, and at least one halogen selected from the group consisting of, and Xâ Xâ²; and a is 0.1âŠaâŠ
10.0 and x is a numerical value in the range 0<xâŠ0.2) This divalent europium activated alkaline earth metal halide phosphor can be used as described in the above application specification. From the X-ray diffraction pattern, the above
MãFX: It has been found that Eu 2+ phosphor is a different type of phosphor with a different crystal structure, and after irradiation with radiation such as X-rays, ultraviolet rays, and electron beams,
When excited with electromagnetic waves in the 1000nm wavelength range, 405n
It exhibits near-ultraviolet to blue light emission (stimulated light emission) with an emission maximum near m.
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ãéãé«ããã®ã§ããããšãæãŸããã The radiation image conversion method using the radiation image conversion panel made of the above-mentioned stimulable phosphor is a very advantageous image forming method as described above, but it is important that the sensitivity of this method be as high as possible. desirable. Generally, the sensitivity of a radiation image storage panel to radiation increases as the stimulated luminance of the phosphor used therein increases. Therefore, it is desired that the stimulable phosphor used in the panel has as high a stimulable luminance as possible.
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æäŸããããšããã®ç®çãšãããã®ã§ããã[Summary of the Invention] An object of the present invention is to provide a radiation image conversion method with improved sensitivity and a radiation image conversion panel used in the method.
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ããã In order to achieve the above object, the present inventors conducted various studies on the above-mentioned novel divalent europium-activated alkaline earth metal halide phosphor. As a result, it was discovered that a phosphor obtained by adding a specific amount of tin halide to the phosphor exhibits high-intensity stimulated luminescence, leading to the present invention.
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ãã That is, in the radiation image conversion method of the present invention, radiation transmitted through the subject or emitted from the subject is absorbed by a divalent europium-activated composite halide phosphor represented by the following compositional formula (), and then this It is characterized in that by irradiating the phosphor with electromagnetic waves in the wavelength range of 450 to 1000 nm, the radiation energy stored in the phosphor is emitted as fluorescence, and this fluorescence is detected.
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äœãå«æããããšãç¹åŸŽãšãããComposition formula ( ) : M ã is a metal; X and X' are both at least one halogen selected from the group consisting of Cl, Br, and Xâ X';X'' is F, Cl, Br;
and a is a numerical value in the range of 0.1âŠaâŠ10.0, b is a numerical value in the range of 0<bâŠ10 -3 , and x is 0<x âŠ0.2) Furthermore, the radiation image conversion panel of the present invention is a radiation image conversion panel substantially composed of a support and a stimulable phosphor layer provided on the support. The stimulable phosphor layer is characterized in that it contains a divalent europium-activated composite halide phosphor represented by the above compositional formula ().
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ãæ°ããªç¥èŠã«åºã¥ããŠå®æããããã®ã§ããã The present invention adds a specific amount of tin halide (stannous halide) to the novel divalent europium-activated alkaline earth metal halide phosphor, thereby irradiating the phosphor with radiation such as X-rays. This was completed based on the new knowledge that stimulated luminescence brightness is significantly improved when excited by electromagnetic waves in the wavelength range of 450 to 1000 nm.
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瀺ãã Therefore, by using the divalent europium-activated composite halide phosphor represented by the above compositional formula (), the sensitivity of the radiation image conversion method can be improved. Furthermore, the radiation image conversion panel of the present invention made of the above-mentioned phosphor exhibits significantly improved sensitivity.
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ã§è¡šããããã[Structure of the Invention ] The divalent europium-activated composite halide phosphor used in the present invention has a compositional formula (): , Mã is at least one kind of alkaline earth metal selected from the group consisting of Ba, Sr and Ca; X and X' are both at least one kind of halogen selected from the group consisting of Cl, Br and, and Xâ Xâ²; Xâ³ is F, Cl, Br
and a is a numerical value in the range of 0.1âŠaâŠ10.0, b is a numerical value in the range of 0<bâŠ10 -3 , and x is 0<x It is a numerical value in the range âŠ0.2).
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ã®ã奜ãŸããã In terms of stimulated luminance in the phosphor represented by the above compositional formula (), the b value representing the amount of tin halide ( SnX''2 ) is 10 -5 âŠbâŠ5Ã
10 â4 , and Xâ³ is preferably F. Also, Mã in the compositional formula ()
The a value representing the ratio of X 2 and MãXâ² 2 is 0.25âŠaâŠ
It is preferably in the range of 6.0, more preferably in the range of 0.5âŠaâŠ2.0, and the x value representing the activation amount of europium is preferably in the range of 10 â5 âŠxâŠ10 â1 .
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æããã§ããã Figure 1 shows BaCl 2 / BaBr 2 / bSnF 2 : 0.001Eu 2+
b value and stimulated luminance of phosphor [after irradiation with 80KVp X-rays, semiconductor laser light (780nm)]
FIG. As is clear from Fig. 1 , BaCl 2ã»BaBr 2ã»
The bSnF 2 :0.001Eu 2+ phosphor exhibits stimulated luminescence with higher brightness than the phosphor to which no tin fluoride is added (b=0). The reason why the b value in the divalent europium-activated composite halide phosphor used in the radiation image conversion method of the present invention is defined in the range of 0<bâŠ10 -3 is as follows.
This is based on these facts. Furthermore, from FIG. 1, it is clear that phosphors having particularly b values in the range of 10 -5 âŠbâŠ5Ã10 -4 exhibit stimulated luminescence with extremely high brightness.
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ã確èªãããŠããã In addition, for the divalent europium-activated composite halide phosphor used in the present invention where Mã, X, X', It has been confirmed that there is a similar trend.
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ããã The stimulated emission spectrum and the stimulated excitation spectrum of the divalent europium-activated composite halide phosphor represented by the above compositional formula () are respectively the same as those of the divalent europium described in the specification of Japanese Patent Application No. 193162/1982. This is almost the same as the stimulated emission spectrum and stimulated excitation spectrum of the activated alkaline earth metal halide phosphor. The wavelength range of the photostimulated excitation spectrum is 450 to 1000 nm.
Therefore, in the radiation image conversion method of the present invention using this phosphor, the wavelength of the excitation light can be changed appropriately, that is, the excitation light source can be appropriately selected depending on the purpose.
For example, the photostimulation excitation spectrum of the above phosphor is approximately
Since the wavelength extends to 1000 nm, it is possible to use a compact semiconductor laser (having an emission wavelength in the infrared region) with a small driving power as a stimulable light source, and therefore it is possible to use a semiconductor laser (having an emission wavelength in the infrared region) as a stimulable light source. It becomes possible to downsize the device. In addition, in terms of the brightness of stimulated luminescence and the wavelength separation from the emitted light, the excitation light in the radiation image conversion method of the present invention is
Preferably, it is an electromagnetic wave in the wavelength range of 500 to 850 nm.
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ããã First, as phosphor raw materials, (1) at least two alkaline earth metal halides selected from the group consisting of barium halide, calcium halide, and strontium halide, (2) tin halide, and (3) halogen. At least one compound selected from the group consisting of compounds of europium such as compounds, oxides, nitrates, and sulfates is prepared. In some cases, ammonium halide or the like may also be used as a flux.
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ã«å¯Ÿå¿ããçžå¯Ÿæ¯ãšãªãããã«ç§€éæ··åããã When manufacturing a phosphor, first, using the above alkaline earth metal halide (1), tin halide (2), and europium compound (3), the composition formula (): Mã X 2ã»aMãXâ² 2ã»bSnXâ³ 2 :xEu âŠâŠ() (However, the definitions of Mã, Weigh and mix so that the ratio is the same.
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åæäœã¯äžèšã®æ¹æ³ã«éããããã®ã§ãªãã The above mixture operation is carried out, for example, in the form of a suspension. Then, by removing water from the suspension of this phosphor raw material mixture, a solid dry mixture is obtained. This moisture removal operation is carried out at room temperature or at a moderate temperature (e.g. 200°C).
(below), it is preferable to carry out drying under reduced pressure, vacuum drying, or both. Of course, the mixing operation is not limited to the above method.
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The pulverized material is filled into a heat-resistant container such as a quartz boat or an aluminum crucible, and fired in an electric furnace. The appropriate firing temperature is in the range of 400 to 1300°C, and the firing time varies depending on the amount of phosphor raw material mixture and the firing temperature, but in general
0.5 to 6 hours is appropriate. The firing atmosphere is
A neutral atmosphere such as a nitrogen gas atmosphere or an argon gas atmosphere, or a weakly reducing atmosphere such as a nitrogen gas atmosphere containing a small amount of hydrogen gas or a carbon dioxide atmosphere containing carbon monoxide is used. When the europium compound used contains trivalent europium, the trivalent europium is reduced to divalent europium during the firing process.
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It takes place over 12 hours.
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ã®äžè¬çãªæäœãè¡ãªã€ãŠãããã The powdered phosphor used in the present invention is obtained by the above firing. Note that the obtained powdered phosphor may be further subjected to various general operations in the production of phosphors, such as washing, drying, and sieving, as necessary.
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äœãåŸãããã By utilizing the manufacturing method described above, a divalent europium-activated composite halide phosphor represented by the above compositional formula () can be obtained.
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ãã¯ç©ççãªè¡æããä¿è·ããŠããã The basic structure of a radiation image storage panel is a support and at least one stimulable phosphor layer provided on one side of the support. The stimulable phosphor layer consists of a stimulable phosphor and a binder that contains and supports the stimulable phosphor in a dispersed state. Note that a transparent protective film is generally provided on the surface of the phosphor layer opposite to the support (the surface not facing the support) to protect the phosphor layer from chemical deterioration or Protects from physical impact.
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By excitation with electromagnetic waves (excitation light) in the wavelength range of It becomes possible to convert the image into an image.
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ïŒã«ãã€ãŠãã®ç»åã衚瀺ããã Next, when the radiation image conversion panel 13 is irradiated with electromagnetic waves in the wavelength range of 450 to 1000 nm using the light source 14, the accumulated radiation energy image formed on the radiation image conversion panel 13 is emitted as fluorescence. The emitted fluorescence is proportional to the intensity of the radiation energy absorbed by the phosphor layer of the radiation image conversion panel 13. This optical signal composed of the intensity of fluorescence is converted into an electrical signal by a photoelectric conversion device 15 such as a photomultiplier tube, and is reproduced as an image by an image reproduction device 16, and the image display device 1
7 displays this image.
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ãšãã§ãããšã®å©ç¹ãããã The operation of reading out the image information accumulated in a radiation image conversion panel as fluorescence is generally performed by scanning the panel in time series with a laser beam, and then transmitting the fluorescence emitted from the panel by this scanning through a suitable light condenser. This is done by detecting with a photodetector such as a photomultiplier tube and obtaining a time-series electrical signal. In order to obtain an image with better observation and interpretation performance, this readout may consist of a pre-reading operation by irradiating low-energy excitation light and a main-reading operation by irradiating high-energy excitation light (Japanese Patent Laid-Open No. 58 -Refer to Publication No. 67240). By performing this pre-read operation, there is an advantage that the read conditions for the main read operation can be suitably set.
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åããæ§æãããŠããŠãããã Furthermore, for example, solid-state photoelectric conversion elements such as photoconductors and photodiodes can be used as photoelectric conversion devices (Japanese Patent Application No. 58-86226, Japanese Patent Application No. 58-86227, Japanese Patent Application No. 58-219313, and Specifications of Application No. 58-219314 and JP-A-58-
(See Publication No. 121874). In this case, a large number of solid-state photoelectric conversion elements may be configured to cover the entire surface of the panel, and may be integrated with the panel, or may be arranged in close proximity to the panel. Further, the photoelectric conversion device may be a line sensor in which a plurality of photoelectric conversion elements are connected in a line,
Alternatively, it may be composed of one solid-state photoelectric conversion element corresponding to one pixel.
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ãå¯èœã§ããã In addition to a point light source such as a laser, the light source in the above case may be a line light source such as an array of light emitting diodes (LEDs), semiconductor lasers, etc. arranged in a row. By performing readout using such a device, it is possible to prevent loss of fluorescence emitted from the panel, and at the same time, increase the solid angle of light reception and increase the S/N ratio. Furthermore, since the obtained electrical signals are converted into time series not by time series irradiation of excitation light but by electrical processing of the photodetector, it is possible to increase the readout speed. .
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§ïŒã The radiation image conversion panel from which the image information has been read is irradiated with light in the wavelength range of the excitation light of the phosphor or heated to erase any remaining radiation energy. It is possible and preferable to do so (Japanese Patent Laid-open No. 1983
-11392 and Japanese Unexamined Patent Publication No. 12599/1983).
By performing this erasing operation, it is possible to prevent noise from occurring due to afterimages when the panel is used next time. Furthermore, by performing the erasing operation twice, once after reading and immediately before the next use, it is possible to prevent the generation of noise due to natural radioactivity, etc., and to perform erasing more efficiently (Japanese Patent Laid-Open Publication No.
(Refer to Publication No. 57-116300).
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æããããšãã§ããã In the radiation image conversion method of the present invention, the radiation used to obtain a radiation transmission image of the subject is capable of exhibiting stimulated luminescence when the phosphor is excited by the electromagnetic waves after being irradiated with this radiation. Any type of radiation may be used, and for example, commonly known radiation such as X-rays, electron beams, and ultraviolet rays can be used. Also,
When obtaining a radiation image of a subject, the radiation directly emitted from the subject may be any radiation that is similarly absorbed by the phosphor and serves as an energy source for stimulated luminescence. can include radiation such as gamma rays, alpha rays, beta rays, and neutron rays.
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In addition to light sources that emit light with a band spectral distribution in the wavelength range of 450 to 1000 nm, e.g.
Ar ion laser, Kr ion laser, Heâ
Light sources such as lasers such as Ne lasers, ruby lasers, semiconductor lasers, glass lasers, YAG lasers, dye lasers, and light emitting diodes can also be used. Among these, a laser is preferable as an excitation light source used in the present invention because it can irradiate a radiation image conversion panel with a laser beam having a high energy density per unit area. Among them, He-Ne laser is preferable in terms of stability and output.
laser, Ar ion laser and Kr ion laser. In addition, semiconductor lasers are preferable as excitation light sources because they are compact, require low driving power, and can be directly modulated, making it easy to stabilize laser output.
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æããããšãã§ããã The light source used for erasing may be one that emits light in the excitation wavelength range of the stimulable phosphor; examples include tungsten lamps, fluorescent lamps, halogen lamps, and high-pressure sodium lamps. can.
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èœãšãªãã The radiation image conversion method of the present invention includes: a storage section that absorbs and stores radiation energy in a stimulable phosphor; a photodetection (readout) section that irradiates the phosphor with excitation light and emits the radiation energy as fluorescence; It can also be applied to a built-in type radiation image conversion device in which an eraser for emitting the energy remaining in the phosphor is built into one device (Japanese Patent Application No. 57-84436 and Patent Application No. 66730-1989). (see specification). By using such a built-in device, the radiation image conversion panel (or the recording material containing the stimulable phosphor) can be reused and a stable and homogeneous image can be obtained. can. Further, by using a built-in type, the device can be made smaller and lighter, and its installation and movement become easier. Furthermore, by mounting this device on a mobile vehicle, it becomes possible to carry out circular radiography.
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æŸå°ç·åå€æããã«ã«ã€ããŠèª¬æããã Next, a radiation image conversion panel used in the radiation image conversion method of the present invention will be explained.
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ã«ããæ¯æäœäžã«åœ¢æããããšãã§ããã As described above, this radiation image conversion panel consists of a support substantially including a support and a support provided on the support containing a divalent europium-activated composite halide phosphor represented by the composition formula () in a dispersed state. and a stimulable phosphor layer made of a binder. The stimulable phosphor layer can be formed on the support, for example, by the following method.
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ãã Examples of binders for the phosphor layer include proteins such as gelatin, polysaccharides such as dextran, or natural polymeric substances such as gum arabic; and polyvinyl butyral, polyvinyl acetate, nitrocellulose, ethylcellulose, and vinylidene chloride. Binders represented by synthetic polymeric substances such as vinyl chloride copolymers, polyalkyl (meth)acrylates, vinyl chloride/vinyl acetate copolymers, polyurethanes, cellulose acetate butyrate, polyvinyl alcohol, linear polyesters, etc. can. Particularly preferred among such binders are nitrocellulose, linear polyesters, polyalkyl(meth)
acrylates, mixtures of nitrocellulose and linear polyesters, and mixtures of nitrocellulose and polyalkyl (meth)acrylates.
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ããã®æ··åç©ãæããããšãã§ããã Examples of solvents for preparing coating solutions include lower alcohols such as methanol, ethanol, n-propanol, and n-butanol; chlorine-containing hydrocarbons such as methylene chloride and ethylene chloride; and ketones such as acetone, methyl ethyl ketone, and methyl isobutyl ketone. ; esters of lower fatty acids and lower alcohols such as methyl acetate, ethyl acetate, and butyl acetate; ethers such as dioxane, ethylene glycol monoethyl ether, and ethylene glycol monomethyl ether; and mixtures thereof.
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ãã«ãªã©ãæããããšãã§ããã The coating liquid also contains a dispersant to improve the dispersibility of the phosphor in the coating liquid, and a dispersant to improve the bonding force between the binder and the phosphor in the phosphor layer after formation. Various additives such as plasticizers may be mixed. Examples of dispersants used for such purposes include phthalic acid, stearic acid, caproic acid, lipophilic surfactants, and the like. Examples of plasticizers include phosphoric acid esters such as triphenyl phosphate, tricresyl phosphate, and diphenyl phosphate; phthalic acid esters such as diethyl phthalate and dimethoxyethyl phthalate; and ethyl phthalyl ethyl glycolate and butyl phthalyl butyl glycolate. Glycolic acid esters; and polyesters of polyethylene glycol and aliphatic dibasic acids, such as polyesters of triethylene glycol and adipic acid and polyesters of diethylene glycol and succinic acid.
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ãªã©ãçšããããšã«ããè¡ãªãããšãã§ããã The coating solution containing the phosphor and binder prepared as described above is then uniformly applied to the surface of the support to form a coating film of the coating solution.
This coating operation can be carried out using conventional coating means such as a doctor blade, roll coater, knife coater, etc.
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ããã The support may be arbitrarily selected from various materials used as supports for intensifying screens (or intensifying screens) in conventional radiography or materials known as supports for radiation image conversion panels. can. Examples of such materials include:
Cellulose acetate, polyester, polyethylene terephthalate, polyamide, polyimide,
Films of plastic materials such as triacetate and polycarbonate, metal sheets such as aluminum foil and aluminum alloy foil, ordinary paper, baryta paper, resin coated paper, pigment paper containing pigments such as titanium dioxide, paper sized with polyvinyl alcohol, etc. etc. can be mentioned.
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å€æããã«ã«é©ããæ¯æäœã§ããã However, in consideration of the characteristics and handling of the radiation image storage panel as an information recording material, a particularly preferred material for the support in the present invention is plastic film. This plastic film may be kneaded with a light-absorbing substance such as carbon black, or may be kneaded with a light-reflecting substance such as titanium dioxide. The former is a support suitable for a high sharpness type radiation image conversion panel, and the latter is a support suitable for a high sensitivity type radiation image conversion panel.
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éãªã©ã«å¿ããŠä»»æã«éžæããããšãã§ããã In known radiation image conversion panels, a phosphor layer is provided in order to strengthen the bond between the support and the phosphor layer, or to improve the sensitivity or image quality (sharpness, granularity) of the radiation image conversion panel. A polymeric substance such as gelatin is coated on the surface of the side support to form an adhesion-imparting layer, or a light-reflecting layer made of a light-reflecting substance such as titanium dioxide, or a light-reflecting layer made of a light-absorbing substance such as carbon black. It is known to provide an absorbent layer or the like. The support used in the present invention can also be provided with these various layers, and their configurations can be arbitrarily selected depending on the purpose, use, etc. of the desired radiation image storage panel.
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ãŠãããã Furthermore, as disclosed in JP-A No. 58-200200, in order to improve the sharpness of the obtained image, the surface of the support on the phosphor layer side (the surface of the support on the phosphor layer side) When an adhesion-imparting layer, a light-reflecting layer, a light-absorbing layer, etc. are provided, minute irregularities may be formed on the surface (meaning the surface thereof).
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ã¯50ä¹è³500ÎŒïœãšããã®ã奜ãŸããã After forming the coating film on the support as described above, the coating film is dried to complete the formation of the stimulable phosphor layer on the support. The thickness of the phosphor layer varies depending on the characteristics of the intended radiation image conversion panel, the type of phosphor, the mixing ratio of the binder and the phosphor, etc.
Usually it is 20 ÎŒm to 1 mm. However, the thickness of this layer is preferably 50 to 500 ÎŒm.
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ããã Furthermore, the stimulable phosphor layer does not necessarily need to be formed by directly applying a coating solution onto a support as described above; After forming a phosphor layer by coating and drying, the phosphor layer may be pressed onto a support, or the support and the phosphor layer may be bonded together using an adhesive.
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äœã䜵çšããããšãã§ããã Although only one stimulable phosphor layer may be used, two or more layers may be stacked. In the case of multiple layers, at least one of the layers should contain a divalent europium-activated composite halide phosphor having the composition formula (), and the luminous efficiency against radiation increases sequentially toward the surface of the panel. A structure in which a plurality of phosphor layers are stacked may be used. Furthermore, in both the single-layer and multi-layer cases, a known stimulable phosphor can be used in combination with the above-mentioned phosphor.
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ãªã©ãæããããšãã§ããã Examples of such known stimulable phosphors include:
In addition to the above-mentioned phosphors, ZnS:Cu, Pb, BaO and
xAl 2 O 3 :Eu (however, 0.8âŠxâŠ10), and Mã
Oã»xSiO 2 :A (However, Mã is Mg, Ca, Sr,
Zn, Cd, or Ba, and A is Ce, Tb, Eu,
Tm, Pb, Tl, Bi, or Mn, and x is 0.5
âŠxâŠ2.5), (Ba 1-xy , Mgx, Cay) FX: aEu 2+ (However, X
is at least one of Cl and Br,
x and y are 0<x+yâŠ0.6 and xyâ 0, and a is 10-6 âŠaâŠ5à 10-2 ), and ing
LnOX: xA (Ln is La, Y, Gd, and
X is at least one of Cl and Br, A is at least one of Ce and Tb, and x is 0<x<0.1). can.
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ã«ã€ããŠãèšçœ®ããããšã奜ãŸããã In a normal radiation image storage panel, as mentioned above, a transparent protective film is attached to the surface of the phosphor layer on the side opposite to the side that contacts the support to physically and chemically protect the phosphor layer. I'm being kicked. Such a transparent protective film is preferably provided also in the radiation image conversion panel of the present invention.
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20ÎŒïœãšããã®ãæãŸããã The transparent protective film may be made of a transparent material such as a cellulose derivative such as cellulose acetate or nitrocellulose; or a synthetic polymer material such as polymethyl methacrylate, polyvinyl butyral, polyvinyl formal, polycarbonate, polyvinyl acetate, or vinyl chloride/vinyl acetate copolymer. It can be formed by coating the surface of the phosphor layer with a solution prepared by dissolving a polymeric substance in an appropriate solvent. Alternatively, it can also be formed by a method such as adhering a transparent thin film separately formed from polyethylene terephthalate, polyethylene, polyvinylidene chloride, polyamide, etc. to the surface of the phosphor layer using a suitable adhesive. The thickness of the transparent protective film formed in this way is about 0.1 to
It is desirable that the thickness be 20 ÎŒm.
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äžã«çœè²ç²äœãåæ£ãããŠããŠãããã In addition, JP-A-55-163500, JP-A-57-
As described in Japanese Patent No. 96300 and the like, the radiation image conversion panel of the present invention may be colored with a coloring agent, and the sharpness of the image obtained can be improved by coloring. Also, JP-A-55-
As described in Japanese Patent No. 146447, the radiation image conversion panel of the present invention may have white powder dispersed in its phosphor layer for the same purpose.
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ãããã ãããããã®åäŸã¯æ¬çºæãå¶éããã
ã®ã§ã¯ãªãã Examples and comparative examples of the present invention are described below. However, these examples do not limit the invention.
å®æœäŸ ïŒ
èåããªãŠã ïŒBaBr2ïŒã®æ°Žæº¶æ¶²ïŒ1.55Ã
10-3molïŒïœïŒ192.7ïœãå¡©åããªãŠã ïŒBaCl2ïŒ
ã®æ°Žæº¶æ¶²ïŒ1.18Ã10-3molïŒïœïŒ253.5ïœãããã³
èåãŠãŒãããŠã ïŒEuBr3ïŒã®æ°Žæº¶æ¶²ïŒ2.841Ã
10-4molïŒmlïŒ1.06mlãæ··åããããã®æ°Žæº¶æ¶²ã
60âã§ïŒæéæžå§ä¹Ÿç¥ããåŸãããã«150âã§ïŒ
æéã®ç空也ç¥ãè¡ãªã€ããExample 1 Aqueous solution of barium bromide (BaBr 2 ) (1.55Ã
10 -3 mol/g) 192.7g, barium chloride (BaCl 2 )
(1.18Ã10 -3 mol/g), and an aqueous solution of europium bromide (EuBr 3 ) (2.841Ã
10 -4 mol/ml) were mixed. This aqueous solution
After drying under reduced pressure at 60â for 3 hours, further drying at 150â for 3 hours.
Vacuum drying was performed for hours.
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0.0001SnF2ïŒ0.001Eu2+ïŒãåŸãã Next, 10 g of the obtained phosphor raw material mixture and 0.3 mg of tin fluoride (SnF 2 ) were thoroughly mixed and then filled into an alumina crucible, which was then placed in a high-temperature electric furnace and fired. Firing was performed at a temperature of 850° C. for 1.5 hours in a carbon dioxide atmosphere containing carbon monoxide. After the firing was completed, the fired product was taken out of the furnace and cooled. In this way, divalent europium-activated composite halide phosphors (BaCl 2ã»BaBr 2ã»
0.0001SnF 2 :0.001Eu 2+ ) was obtained.
å®æœäŸ ïŒ
å®æœäŸïŒã«ãããŠãåŒåã¹ãºã®æ·»å éã0.15mg
ã«å€ããããšä»¥å€ã¯å®æœäŸïŒã®æ¹æ³ãšåæ§ã®æäœ
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0.00005SnF2ïŒ0.001Eu2+ïŒãåŸããExample 2 In Example 1, the amount of tin fluoride added was 0.15 mg.
A divalent europium-activated composite halide phosphor (BaCl 2ã»BaBr 2ã»
0.00005SnF 2 :0.001Eu 2+ ) was obtained.
å®æœäŸ ïŒ
å®æœäŸïŒã«ãããŠãåŒåã¹ãºã®æ·»å éã3.1mg
ã«å€ããããšä»¥å€ã¯å®æœäŸïŒã®æ¹æ³ãšåæ§ã®æäœ
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äœïŒBaCl2ã»BaBr2ã»
0.001SnF2ïŒ0.001Eu2+ïŒãåŸããExample 3 In Example 1, the amount of tin fluoride added was 3.1 mg.
A divalent europium-activated composite halide phosphor (BaCl 2ã»BaBr 2ã»
0.001SnF 2 :0.001Eu 2+ ) was obtained.
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äœïŒBaCl2ã»BaBr2ïŒ
0.001Eu2+ïŒãåŸããComparative Example 1 Divalent europium-activated barium chloride bromide phosphor (BaCl 2 . BaBr2 :
0.001Eu 2+ ) was obtained.
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åèå
äœã«ç®¡é»å§80KVpã®ïŒžç·ãç
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èŒåºŠã枬å®ããããã®çµæã第ïŒå³ã«ãŸãš
ããŠç€ºãã Next, each of the phosphors obtained in Examples 1 to 3 and Comparative Example 1 was irradiated with X-rays at a tube voltage of 80 KVp and then excited with semiconductor laser light (780 nm), and the stimulated luminescence brightness was measured. The results are summarized in Figure 1.
第ïŒå³ã¯ãBaCl2ã»BaBr2ã»bSnF2ïŒ0.001Eu2+
èå
äœã«ãããåŒåã¹ãºã®å«æéïŒïœå€ïŒãšèŒå°œ
çºå
èŒåºŠãšã®é¢ä¿ã瀺ãã°ã©ãã§ããã Figure 1 shows BaCl 2 / BaBr 2 / bSnF 2 : 0.001Eu 2+
It is a graph showing the relationship between the content of tin fluoride (b value) in a phosphor and the stimulated luminance.
第ïŒå³ããæãããªããã«ãæ¬çºæã«çšããã
ãBaCl2ã»BaBr2ã»bSnF2ïŒ0.001Eu2+èå
äœã¯ã
ïœå€ãïŒïŒïœâŠ10-3ã®ç¯å²ã«ããå Žåã«èŒå°œçºå
èŒåºŠãåäžãããç¹ã«ãïœå€ã10-5âŠïœâŠïŒÃ
10-4ã®ç¯å²ã«ããèå
äœã¯é«èŒåºŠã®èŒå°œçºå
ã瀺
ãã As is clear from FIG. 1, the BaCl 2ã»BaBr 2ã»bSnF 2 :0.001Eu 2+ phosphor used in the present invention is
When the b value is in the range of 0<bâŠ10 â3 , the stimulated luminescence brightness is improved. In particular, the b value is 10 -5 âŠbâŠ5Ã
Phosphors in the 10 -4 range exhibit high brightness stimulated luminescence.
å®æœäŸ ïŒ
å®æœäŸïŒãïŒããã³æ¯èŒäŸïŒã§åŸãããåèå
äœãçšããŠä»¥äžã®ããã«ããŠæŸå°ç·åå€æããã«
ã補é ãããExample 4 Using each of the phosphors obtained in Examples 1 to 3 and Comparative Example 1, a radiation image conversion panel was manufactured as follows.
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å±€ã圢æããã Methyl ethyl ketone was added to a mixture of powdered divalent europium-activated composite halide phosphor and linear polyester resin, and the degree of nitrification was further increased to 11.5%.
of nitrocellulose was added to prepare a dispersion containing the phosphor in a dispersed state. Next, tricresyl phosphate, n-butanol, and methyl ethyl ketone were added to this dispersion, and the mixture was sufficiently stirred and mixed using a propeller mixer to ensure that the phosphor was uniformly dispersed and that the mixing ratio between the binder and the phosphor was adjusted. is 1:
10. A coating solution with a viscosity of 25 to 35 PS (25°C) was prepared. Next, the coating solution was uniformly applied using a doctor blade onto a titanium dioxide-mixed polyethylene terephthalate sheet (support, thickness: 250 Όm) placed horizontally on a glass plate. After coating, the support on which the coating film was formed was placed in a dryer, and the temperature inside the dryer was gradually raised from 25°C to 100°C to dry the coating film. In this way, a phosphor layer with a layer thickness of 250 Όm was formed on the support.
ãããŠããã®èå
äœå±€ã®äžã«ããªãšãã¬ã³ãã¬
ãã¿ã¬ãŒãã®éæãã€ã«ã ïŒåã¿ïŒ12ÎŒïœãããª
ãšã¹ãã«ç³»æ¥çå€ãä»äžãããŠãããã®ïŒãæ¥ç
å€å±€åŽãäžã«åããŠçœ®ããŠæ¥çããããšã«ããã
éæä¿è·èã圢æããã Then, a transparent film of polyethylene terephthalate (thickness: 12 ÎŒm, coated with a polyester adhesive) is placed on top of this phosphor layer with the adhesive layer side facing down, and bonded.
A transparent protective film was formed.
ãã®ããã«ããŠãæ¯æäœãèå
äœå±€ããã³éæ
ä¿è·èããæ§æãããåçš®ã®æŸå°ç·åå€æããã«
ã補é ããã In this manner, various radiation image conversion panels each comprised of a support, a phosphor layer, and a transparent protective film were manufactured.
å®æœäŸ ïŒ
å®æœäŸïŒã«ãããŠãåŒåã¹ãºã®ä»£ãã«å¡©åã¹ãº
ïŒSnCl2ã»2H2OïŒ0.44mgãçšããããšä»¥å€ã¯å®æœ
äŸïŒã®æ¹æ³ãšåæ§ã®æäœãè¡ãªãããšã«ãããäº
䟡ãŠãŒãããŠã 賊掻è€åããã²ã³åç©èå
äœ
ïŒBaCl2ã»BaBr2ã»0.0001SnCl2ïŒ0.001Eu2+ïŒãåŸ
ããExample 5 A divalent europium activated composite was prepared by performing the same procedure as in Example 1 except for using 0.44 mg of tin chloride (SnCl 2 2H 2 O) instead of tin fluoride. A halide phosphor (BaCl 2 .BaBr 2 .0.0001SnCl 2 :0.001Eu 2+ ) was obtained.
次ãã§ãåŸãããèå
äœãçšããŠå®æœäŸïŒã®æ¹
æ³ãšåæ§ãªåŠçãè¡ãªãããšã«ãããæ¯æäœãè
å
äœå±€ããã³éæä¿è·èããæ§æãããåçš®ã®æŸ
å°ç·åå€æããã«ã補é ããã Next, the obtained phosphor was subjected to the same treatment as in Example 4 to produce various radiation image conversion panels each comprised of a support, a phosphor layer, and a transparent protective film.
å®æœäŸ ïŒ
å®æœäŸïŒã«ãããŠãåŒåã¹ãºã®ä»£ãã«èåã¹ãº
ïŒSuBr2ïŒ0.55mgãçšããããšä»¥å€ã¯å®æœäŸïŒã®
æ¹æ³ãšåæ§ã®æäœãè¡ãªãããšã«ãããäºäŸ¡ãŠãŒ
ãããŠã 賊掻è€åããã²ã³åç©èå
äœïŒBaCl2ã»
BaBr2ã»0.0001SnBr2ïŒ0.001Eu2+ïŒãåŸããExample 6 Divalent europium-activated composite halide fluorescent Body ( BaCl2ã»
BaBr2ã»0.0001SnBr2 :0.001Eu2 + ) was obtained.
次ãã§ãåŸãããèå
äœãçšããŠå®æœäŸïŒã®æ¹
æ³ãšåæ§ãªåŠçãè¡ãªãããšã«ãããæ¯æäœãè
å
äœå±€ããã³éæä¿è·èããæ§æãããåçš®ã®æŸ
å°ç·åå€æããã«ã補é ããã Next, the obtained phosphor was subjected to the same treatment as in Example 4 to produce various radiation image conversion panels each comprised of a support, a phosphor layer, and a transparent protective film.
次ã«ãå®æœäŸïŒãïŒã§åŸãããåæŸå°ç·åå€æ
ããã«ã«ç®¡é»å§80KVpã®ïŒžç·ãç
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å°äœã¬ãŒã¶ãŒå
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èŒåºŠïŒã枬å®ããããã®çµ
æã第ïŒè¡šã«ç€ºãã Next, after irradiating each radiation image conversion panel obtained in Examples 4 to 6 with X-rays with a tube voltage of 80 KVp, the sensitivity (stimulated luminance) of the panel when excited with semiconductor laser light (780 nm) was measured. It was measured. The results are shown in Table 1.
第ïŒè¡š çžå¯Ÿæ床 BaCl2ã»BaBr2ã»0.0001SnF2ïŒ 0.001Eu2+èå äœäœ¿çšã®ããã« 121 BaCl2ã»BaBr2ã»0.00005SnF2ïŒ 0.001Eu2+èå äœäœ¿çšã®ããã« 119 BaCl2ã»BaBr2ã»0.001SnF2ïŒ 0.001Eu2+èå äœäœ¿çšã®ããã« 101 BaCl2ã»BaBr2ã»0.0001SnCl2ïŒ 0.001Eu2+èå äœäœ¿çšã®ããã« 103 BaCl2ã»BaBr2ã»0.0001SnBr2ïŒ 0.001Eu2+èå äœäœ¿çšã®ããã« 103 BaCl2ã»BaBr2ïŒ0.001Eu2+ èå äœäœ¿çšã®ããã« 100 Table 1 Relative sensitivity BaCl 2ã»BaBr 2ã»0.0001SnF 2 : Panel using 0.001Eu 2+ phosphor 121 BaCl 2ã»BaBr 2ã»0.00005SnF 2 : Panel using 0.001Eu 2+ phosphor 119 BaCl 2ã»BaBr 2ã»0.001SnF 2 : Panel using 0.001Eu 2+ phosphor 101 BaCl 2ã»BaBr 2ã»0.0001SnCl 2 : Panel using 0.001Eu 2+ phosphor 103 BaCl 2ã»BaBr 2ã»0.0001SnBr 2 : 0.001Eu 2+ fluorescence Panel using phosphor 103 Panel using BaCl 2ã»BaBr 2 :0.001Eu 2+ phosphor 100
第ïŒå³ã¯ãæ¬çºæã«çšããããèå
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ã§ããBaCl2ã»BaBr2ã»bSF2ïŒ0.001Eu2+èå
äœ
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ã説æããæŠç¥å³ã§ããã
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FIG. 1 is a graph showing the relationship between the b value and the stimulated luminance of a BaCl 2 .BaBr 2 .bSF 2 :0.001Eu 2+ phosphor, which is a specific example of the phosphor used in the present invention. FIG. 2 is a schematic diagram illustrating the radiation image conversion method of the present invention. 11: Radiation generator, 12: Subject, 13:
Radiation image conversion panel, 14: light source, 15: photoelectric conversion device, 16: image reproduction device, 17: image display device, 18: filter.
Claims (1)
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ç¯å²ç¬¬ïŒïŒé èšèŒã®æŸå°ç·åå€æããã«ã[Claims] 1. After the radiation transmitted through the subject or emitted from the subject is absorbed by a divalent europium-activated composite halide phosphor represented by the following compositional formula (), this phosphor is 1. A radiation image conversion method characterized by emitting radiation energy stored in the phosphor as fluorescence by irradiating the phosphor with electromagnetic waves in a wavelength range of ~1000 nm, and detecting this fluorescence. Composition formula ( ) : M ã is a metal; X and X' are both at least one halogen selected from the group consisting of Cl, Br, and Xâ X';X'' is F, Cl, Br;
and a is a numerical value in the range of 0.1âŠaâŠ10.0, b is a numerical value in the range of 0<bâŠ10 -3 , and x is 0<x (a numerical value in the range of âŠ0.2) 2 b in the composition formula () is 10 -5 âŠbâŠ5Ã
10. The radiation image conversion method according to claim 1, wherein the value is in the range of 10 -4 . 3. The radiation image conversion method according to claim 1, wherein X'' in the compositional formula () is F. 4. A in the compositional formula () is a numerical value in the range of 0.25âŠaâŠ6.0. 5. The radiation image conversion method according to claim 1, characterized in that Mã in the compositional formula () is Ba. 6. The radiation image conversion method according to claim 1, characterized in that X and X' in the compositional formula () are each Cl or Br.7 . 5. The radiation image conversion method according to claim 1, characterized in that the value is a numerical value in the range of âŠxâŠ10 -1 . 8. The radiation image conversion method according to claim 1, characterized in that the electromagnetic wave is an electromagnetic wave in a wavelength range of 500 to 850 nm. 9. A radiation image conversion method according to claim 1, wherein the electromagnetic wave is a laser beam. 10. A support and a method for converting a radiation image according to claim 1, wherein the electromagnetic wave is a laser beam. In a radiation image conversion panel substantially composed of a stimulable phosphor layer provided in A radiation image conversion panel characterized by containing: Compositional formula (): MãX 2ã»aMãXâ² 2ã»bSnXâ³ 2 :xEu 2+ ...() (However, Mã is Ba, Sr and at least one alkaline earth metal selected from the group consisting of Ca; X and X' are both at least one halogen selected from the group consisting of Cl, Br, and Xâ X'; Xâ³ is F, Cl, Br
and a is a numerical value in the range of 0.1âŠaâŠ10.0, b is a numerical value in the range of 0<bâŠ10 -3 , and x is 0<x 11 b in the composition formula () is 10 -5 âŠbâŠ5Ã
11. The radiation image conversion panel according to claim 10, wherein the radiation image conversion panel has a numerical value in the range of 10 -4 . 12. The radiation image conversion panel according to claim 10, characterized in that Xâ³ in the compositional formula () is F. 13. A in the compositional formula () is 0.25âŠaâŠ6.0
11. The radiation image conversion panel according to claim 10, wherein the radiation image conversion panel has a numerical value in the range of . 14. The radiation image conversion panel according to claim 10, wherein M in the compositional formula () is Ba. 15. The radiation image conversion panel according to claim 10, wherein X and X' in the compositional formula () are each Cl or Br. 16 x in composition formula () is 10 -5 âŠxâŠ10 -1
11. The radiation image conversion panel according to claim 10, wherein the radiation image conversion panel has a numerical value in the range of .
Priority Applications (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP24045584A JPS61120886A (en) | 1984-11-16 | 1984-11-16 | Radiation image converting method and radiation image converting panel for said method |
| US07/492,436 US5198679A (en) | 1984-11-16 | 1989-03-06 | Phosphor and image storage panel |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP24045584A JPS61120886A (en) | 1984-11-16 | 1984-11-16 | Radiation image converting method and radiation image converting panel for said method |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS61120886A JPS61120886A (en) | 1986-06-07 |
| JPH0460151B2 true JPH0460151B2 (en) | 1992-09-25 |
Family
ID=17059749
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP24045584A Granted JPS61120886A (en) | 1984-11-16 | 1984-11-16 | Radiation image converting method and radiation image converting panel for said method |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS61120886A (en) |
-
1984
- 1984-11-16 JP JP24045584A patent/JPS61120886A/en active Granted
Also Published As
| Publication number | Publication date |
|---|---|
| JPS61120886A (en) | 1986-06-07 |
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| LAPS | Cancellation because of no payment of annual fees |