EP0276566B1 - Radiographic element exhibiting reduced crossover - Google Patents
Radiographic element exhibiting reduced crossover Download PDFInfo
- Publication number
- EP0276566B1 EP0276566B1 EP19870311289 EP87311289A EP0276566B1 EP 0276566 B1 EP0276566 B1 EP 0276566B1 EP 19870311289 EP19870311289 EP 19870311289 EP 87311289 A EP87311289 A EP 87311289A EP 0276566 B1 EP0276566 B1 EP 0276566B1
- Authority
- EP
- European Patent Office
- Prior art keywords
- dye
- radiographic element
- further characterized
- element according
- radiographic
- 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
- 230000001747 exhibiting effect Effects 0.000 title description 2
- 239000000975 dye Substances 0.000 claims description 130
- 239000000839 emulsion Substances 0.000 claims description 57
- -1 silver halide Chemical class 0.000 claims description 53
- 229910052709 silver Inorganic materials 0.000 claims description 36
- 239000004332 silver Substances 0.000 claims description 36
- 239000000084 colloidal system Substances 0.000 claims description 21
- 238000012545 processing Methods 0.000 claims description 19
- 239000002245 particle Substances 0.000 claims description 12
- 230000003595 spectral effect Effects 0.000 claims description 10
- 230000003287 optical effect Effects 0.000 claims description 8
- 230000005855 radiation Effects 0.000 claims description 8
- 230000035945 sensitivity Effects 0.000 claims description 6
- 238000001228 spectrum Methods 0.000 claims description 4
- 230000005670 electromagnetic radiation Effects 0.000 claims description 2
- 238000001429 visible spectrum Methods 0.000 claims description 2
- AJDUTMFFZHIJEM-UHFFFAOYSA-N n-(9,10-dioxoanthracen-1-yl)-4-[4-[[4-[4-[(9,10-dioxoanthracen-1-yl)carbamoyl]phenyl]phenyl]diazenyl]phenyl]benzamide Chemical compound O=C1C2=CC=CC=C2C(=O)C2=C1C=CC=C2NC(=O)C(C=C1)=CC=C1C(C=C1)=CC=C1N=NC(C=C1)=CC=C1C(C=C1)=CC=C1C(=O)NC1=CC=CC2=C1C(=O)C1=CC=CC=C1C2=O AJDUTMFFZHIJEM-UHFFFAOYSA-N 0.000 claims 1
- CMCWWLVWPDLCRM-UHFFFAOYSA-N phenidone Chemical compound N1C(=O)CCN1C1=CC=CC=C1 CMCWWLVWPDLCRM-UHFFFAOYSA-N 0.000 claims 1
- 239000006097 ultraviolet radiation absorber Substances 0.000 claims 1
- 239000001043 yellow dye Substances 0.000 claims 1
- 239000010410 layer Substances 0.000 description 79
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 30
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 28
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 14
- 239000002244 precipitate Substances 0.000 description 13
- 239000000047 product Substances 0.000 description 13
- 238000010992 reflux Methods 0.000 description 13
- 125000001434 methanylylidene group Chemical group [H]C#[*] 0.000 description 12
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 11
- 238000001914 filtration Methods 0.000 description 11
- 125000000217 alkyl group Chemical group 0.000 description 10
- 239000002002 slurry Substances 0.000 description 10
- 239000000243 solution Substances 0.000 description 10
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 9
- 238000003384 imaging method Methods 0.000 description 9
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 8
- 238000013459 approach Methods 0.000 description 8
- 108010010803 Gelatin Proteins 0.000 description 7
- 238000000576 coating method Methods 0.000 description 7
- 229920000159 gelatin Polymers 0.000 description 7
- 239000008273 gelatin Substances 0.000 description 7
- 235000019322 gelatine Nutrition 0.000 description 7
- 235000011852 gelatine desserts Nutrition 0.000 description 7
- 239000000463 material Substances 0.000 description 7
- 238000011160 research Methods 0.000 description 7
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 6
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 6
- 230000002378 acidificating effect Effects 0.000 description 6
- 125000003118 aryl group Chemical group 0.000 description 6
- 229910052739 hydrogen Inorganic materials 0.000 description 6
- 239000000203 mixture Substances 0.000 description 6
- 239000007787 solid Substances 0.000 description 6
- 125000001424 substituent group Chemical group 0.000 description 6
- 239000006096 absorbing agent Substances 0.000 description 5
- 238000010521 absorption reaction Methods 0.000 description 5
- 229960000583 acetic acid Drugs 0.000 description 5
- 150000004646 arylidenes Chemical group 0.000 description 5
- 239000011248 coating agent Substances 0.000 description 5
- 238000002329 infrared spectrum Methods 0.000 description 5
- DZVCFNFOPIZQKX-LTHRDKTGSA-M merocyanine Chemical compound [Na+].O=C1N(CCCC)C(=O)N(CCCC)C(=O)C1=C\C=C\C=C/1N(CCCS([O-])(=O)=O)C2=CC=CC=C2O\1 DZVCFNFOPIZQKX-LTHRDKTGSA-M 0.000 description 5
- 238000000655 nuclear magnetic resonance spectrum Methods 0.000 description 5
- 238000003756 stirring Methods 0.000 description 5
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 4
- 125000003710 aryl alkyl group Chemical group 0.000 description 4
- 125000004432 carbon atom Chemical group C* 0.000 description 4
- 125000004122 cyclic group Chemical group 0.000 description 4
- 238000000921 elemental analysis Methods 0.000 description 4
- 239000012362 glacial acetic acid Substances 0.000 description 4
- 125000000623 heterocyclic group Chemical group 0.000 description 4
- 238000013508 migration Methods 0.000 description 4
- 230000005012 migration Effects 0.000 description 4
- 229910052757 nitrogen Inorganic materials 0.000 description 4
- 238000002360 preparation method Methods 0.000 description 4
- 239000011541 reaction mixture Substances 0.000 description 4
- CUGBBQWDGCXWNB-UHFFFAOYSA-N 4-(3-methyl-5-oxo-4h-pyrazol-1-yl)benzoic acid Chemical compound O=C1CC(C)=NN1C1=CC=C(C(O)=O)C=C1 CUGBBQWDGCXWNB-UHFFFAOYSA-N 0.000 description 3
- KAESVJOAVNADME-UHFFFAOYSA-N Pyrrole Chemical compound C=1C=CNC=1 KAESVJOAVNADME-UHFFFAOYSA-N 0.000 description 3
- RWRDLPDLKQPQOW-UHFFFAOYSA-N Pyrrolidine Chemical compound C1CCNC1 RWRDLPDLKQPQOW-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 125000003545 alkoxy group Chemical group 0.000 description 3
- 125000003277 amino group Chemical group 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 3
- 125000002091 cationic group Chemical group 0.000 description 3
- 230000009977 dual effect Effects 0.000 description 3
- FVAUCKIRQBBSSJ-UHFFFAOYSA-M sodium iodide Chemical compound [Na+].[I-] FVAUCKIRQBBSSJ-UHFFFAOYSA-M 0.000 description 3
- 125000000547 substituted alkyl group Chemical group 0.000 description 3
- 125000003107 substituted aryl group Chemical group 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- 238000005406 washing Methods 0.000 description 3
- LBUJPTNKIBCYBY-UHFFFAOYSA-N 1,2,3,4-tetrahydroquinoline Chemical compound C1=CC=C2CCCNC2=C1 LBUJPTNKIBCYBY-UHFFFAOYSA-N 0.000 description 2
- ZRHUHDUEXWHZMA-UHFFFAOYSA-N 1,4-dihydropyrazol-5-one Chemical compound O=C1CC=NN1 ZRHUHDUEXWHZMA-UHFFFAOYSA-N 0.000 description 2
- BGNGWHSBYQYVRX-UHFFFAOYSA-N 4-(dimethylamino)benzaldehyde Chemical compound CN(C)C1=CC=C(C=O)C=C1 BGNGWHSBYQYVRX-UHFFFAOYSA-N 0.000 description 2
- IOEKAWKOCVLXTC-UHFFFAOYSA-N 5-(3-methyl-5-oxo-4h-pyrazol-1-yl)benzene-1,3-dicarboxylic acid Chemical compound O=C1CC(C)=NN1C1=CC(C(O)=O)=CC(C(O)=O)=C1 IOEKAWKOCVLXTC-UHFFFAOYSA-N 0.000 description 2
- RPVVTFIXGGRKET-UHFFFAOYSA-N 5-hydrazinylbenzene-1,3-dicarboxylic acid Chemical compound NNC1=CC(C(O)=O)=CC(C(O)=O)=C1 RPVVTFIXGGRKET-UHFFFAOYSA-N 0.000 description 2
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 2
- OAKJQQAXSVQMHS-UHFFFAOYSA-N Hydrazine Chemical compound NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 description 2
- YNAVUWVOSKDBBP-UHFFFAOYSA-N Morpholine Chemical compound C1COCCN1 YNAVUWVOSKDBBP-UHFFFAOYSA-N 0.000 description 2
- ZCQWOFVYLHDMMC-UHFFFAOYSA-N Oxazole Chemical compound C1=COC=N1 ZCQWOFVYLHDMMC-UHFFFAOYSA-N 0.000 description 2
- GLUUGHFHXGJENI-UHFFFAOYSA-N Piperazine Chemical compound C1CNCCN1 GLUUGHFHXGJENI-UHFFFAOYSA-N 0.000 description 2
- NQRYJNQNLNOLGT-UHFFFAOYSA-N Piperidine Chemical compound C1CCNCC1 NQRYJNQNLNOLGT-UHFFFAOYSA-N 0.000 description 2
- WTKZEGDFNFYCGP-UHFFFAOYSA-N Pyrazole Chemical compound C=1C=NNC=1 WTKZEGDFNFYCGP-UHFFFAOYSA-N 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- 229910052775 Thulium Inorganic materials 0.000 description 2
- 239000012031 Tollens' reagent Substances 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 125000004104 aryloxy group Chemical group 0.000 description 2
- 125000004429 atom Chemical group 0.000 description 2
- WMUIZUWOEIQJEH-UHFFFAOYSA-N benzo[e][1,3]benzoxazole Chemical class C1=CC=C2C(N=CO3)=C3C=CC2=C1 WMUIZUWOEIQJEH-UHFFFAOYSA-N 0.000 description 2
- WZJYKHNJTSNBHV-UHFFFAOYSA-N benzo[h]quinoline Chemical compound C1=CN=C2C3=CC=CC=C3C=CC2=C1 WZJYKHNJTSNBHV-UHFFFAOYSA-N 0.000 description 2
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 2
- 238000004061 bleaching Methods 0.000 description 2
- 125000002843 carboxylic acid group Chemical group 0.000 description 2
- 125000001309 chloro group Chemical group Cl* 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 238000004042 decolorization Methods 0.000 description 2
- 238000000586 desensitisation Methods 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- 238000003801 milling Methods 0.000 description 2
- 229910017464 nitrogen compound Inorganic materials 0.000 description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 2
- 238000002601 radiography Methods 0.000 description 2
- VWDWKYIASSYTQR-UHFFFAOYSA-N sodium nitrate Chemical compound [Na+].[O-][N+]([O-])=O VWDWKYIASSYTQR-UHFFFAOYSA-N 0.000 description 2
- 159000000000 sodium salts Chemical class 0.000 description 2
- GEHJYWRUCIMESM-UHFFFAOYSA-L sodium sulfite Chemical compound [Na+].[Na+].[O-]S([O-])=O GEHJYWRUCIMESM-UHFFFAOYSA-L 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- 125000005504 styryl group Chemical group 0.000 description 2
- QGKMIGUHVLGJBR-UHFFFAOYSA-M (4z)-1-(3-methylbutyl)-4-[[1-(3-methylbutyl)quinolin-1-ium-4-yl]methylidene]quinoline;iodide Chemical compound [I-].C12=CC=CC=C2N(CCC(C)C)C=CC1=CC1=CC=[N+](CCC(C)C)C2=CC=CC=C12 QGKMIGUHVLGJBR-UHFFFAOYSA-M 0.000 description 1
- POTIYWUALSJREP-UHFFFAOYSA-N 1,2,3,4,4a,5,6,7,8,8a-decahydroquinoline Chemical compound N1CCCC2CCCCC21 POTIYWUALSJREP-UHFFFAOYSA-N 0.000 description 1
- LEDXVVSZBQRIKT-UHFFFAOYSA-N 1,2-diethylpyrazolidine-3,5-dione Chemical compound CCN1N(CC)C(=O)CC1=O LEDXVVSZBQRIKT-UHFFFAOYSA-N 0.000 description 1
- XDPKQGKEOCYMQC-UHFFFAOYSA-N 1,2-diphenylpyrazolidine-3,5-dione Chemical compound O=C1CC(=O)N(C=2C=CC=CC=2)N1C1=CC=CC=C1 XDPKQGKEOCYMQC-UHFFFAOYSA-N 0.000 description 1
- JGRCHNVLXORPNM-UHFFFAOYSA-N 1,2-oxazol-4-one Chemical class O=C1CON=C1 JGRCHNVLXORPNM-UHFFFAOYSA-N 0.000 description 1
- BCMCBBGGLRIHSE-UHFFFAOYSA-N 1,3-benzoxazole Chemical compound C1=CC=C2OC=NC2=C1 BCMCBBGGLRIHSE-UHFFFAOYSA-N 0.000 description 1
- SKBJXISEEPBDFX-UHFFFAOYSA-N 1,3-bis(2-methoxyethyl)-2-sulfanylidene-1,3-diazinane-4,6-dione Chemical compound COCCN1C(=O)CC(=O)N(CCOC)C1=S SKBJXISEEPBDFX-UHFFFAOYSA-N 0.000 description 1
- XUCMDLYIYOXEBF-UHFFFAOYSA-N 1,3-diethyl-1,3-diazinane-2,4,6-trione Chemical compound CCN1C(=O)CC(=O)N(CC)C1=O XUCMDLYIYOXEBF-UHFFFAOYSA-N 0.000 description 1
- SHBTUGJAKBRBBJ-UHFFFAOYSA-N 1,3-diethyl-2-sulfanylidene-1,3-diazinane-4,6-dione Chemical compound CCN1C(=O)CC(=O)N(CC)C1=S SHBTUGJAKBRBBJ-UHFFFAOYSA-N 0.000 description 1
- UHNIPFHBUDTBTN-UHFFFAOYSA-N 1,3-diethylimidazolidine-2,4-dione Chemical compound CCN1CC(=O)N(CC)C1=O UHNIPFHBUDTBTN-UHFFFAOYSA-N 0.000 description 1
- XJDDLMJULQGRLU-UHFFFAOYSA-N 1,3-dioxane-4,6-dione Chemical compound O=C1CC(=O)OCO1 XJDDLMJULQGRLU-UHFFFAOYSA-N 0.000 description 1
- UHKAJLSKXBADFT-UHFFFAOYSA-N 1,3-indandione Chemical compound C1=CC=C2C(=O)CC(=O)C2=C1 UHKAJLSKXBADFT-UHFFFAOYSA-N 0.000 description 1
- GCSBYWTVHSKTNC-UHFFFAOYSA-N 1,3-oxazolidin-5-one Chemical compound O=C1CNCO1 GCSBYWTVHSKTNC-UHFFFAOYSA-N 0.000 description 1
- ZOBPZXTWZATXDG-UHFFFAOYSA-N 1,3-thiazolidine-2,4-dione Chemical compound O=C1CSC(=O)N1 ZOBPZXTWZATXDG-UHFFFAOYSA-N 0.000 description 1
- KAMCBFNNGGVPPW-UHFFFAOYSA-N 1-(ethenylsulfonylmethoxymethylsulfonyl)ethene Chemical compound C=CS(=O)(=O)COCS(=O)(=O)C=C KAMCBFNNGGVPPW-UHFFFAOYSA-N 0.000 description 1
- PVOAHINGSUIXLS-UHFFFAOYSA-N 1-Methylpiperazine Chemical compound CN1CCNCC1 PVOAHINGSUIXLS-UHFFFAOYSA-N 0.000 description 1
- SGKUPLCQYHQBTN-UHFFFAOYSA-N 1-ethyl-1,3-diazinane-2,4,6-trione Chemical compound CCN1C(=O)CC(=O)NC1=O SGKUPLCQYHQBTN-UHFFFAOYSA-N 0.000 description 1
- PPXRSYKZGWZUQY-UHFFFAOYSA-N 1-ethyl-3-phenyl-2-sulfanylideneimidazolidin-4-one Chemical compound S=C1N(CC)CC(=O)N1C1=CC=CC=C1 PPXRSYKZGWZUQY-UHFFFAOYSA-N 0.000 description 1
- 125000001637 1-naphthyl group Chemical group [H]C1=C([H])C([H])=C2C(*)=C([H])C([H])=C([H])C2=C1[H] 0.000 description 1
- BAXOFTOLAUCFNW-UHFFFAOYSA-N 1H-indazole Chemical compound C1=CC=C2C=NNC2=C1 BAXOFTOLAUCFNW-UHFFFAOYSA-N 0.000 description 1
- SIKJAQJRHWYJAI-UHFFFAOYSA-O 1H-indol-1-ium Chemical compound C1=CC=C2[NH2+]C=CC2=C1 SIKJAQJRHWYJAI-UHFFFAOYSA-O 0.000 description 1
- XWIYUCRMWCHYJR-UHFFFAOYSA-N 1h-pyrrolo[3,2-b]pyridine Chemical compound C1=CC=C2NC=CC2=N1 XWIYUCRMWCHYJR-UHFFFAOYSA-N 0.000 description 1
- 150000001477 2,4-oxazolidinediones Chemical class 0.000 description 1
- JGRMXPSUZIYDRR-UHFFFAOYSA-N 2-(4-oxo-2-sulfanylidene-1,3-thiazolidin-3-yl)acetic acid Chemical compound OC(=O)CN1C(=O)CSC1=S JGRMXPSUZIYDRR-UHFFFAOYSA-N 0.000 description 1
- IMSODMZESSGVBE-UHFFFAOYSA-N 2-Oxazoline Chemical compound C1CN=CO1 IMSODMZESSGVBE-UHFFFAOYSA-N 0.000 description 1
- 125000001731 2-cyanoethyl group Chemical group [H]C([H])(*)C([H])([H])C#N 0.000 description 1
- OGNHTEFUCYVGFW-UHFFFAOYSA-M 2-ethenyl-1-methylpyridin-1-ium;4-methylbenzenesulfonate Chemical compound C[N+]1=CC=CC=C1C=C.CC1=CC=C(S([O-])(=O)=O)C=C1 OGNHTEFUCYVGFW-UHFFFAOYSA-M 0.000 description 1
- 125000000954 2-hydroxyethyl group Chemical group [H]C([*])([H])C([H])([H])O[H] 0.000 description 1
- 125000001622 2-naphthyl group Chemical group [H]C1=C([H])C([H])=C2C([H])=C(*)C([H])=C([H])C2=C1[H] 0.000 description 1
- 125000000094 2-phenylethyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])C([H])([H])* 0.000 description 1
- UGWULZWUXSCWPX-UHFFFAOYSA-N 2-sulfanylideneimidazolidin-4-one Chemical compound O=C1CNC(=S)N1 UGWULZWUXSCWPX-UHFFFAOYSA-N 0.000 description 1
- RVBUGGBMJDPOST-UHFFFAOYSA-N 2-thiobarbituric acid Chemical compound O=C1CC(=O)NC(=S)N1 RVBUGGBMJDPOST-UHFFFAOYSA-N 0.000 description 1
- JQRFJIWNCCYNKU-UHFFFAOYSA-N 3-[3-(dimethylamino)propyl]-2-sulfanylidene-1,3-thiazolidin-4-one Chemical compound CN(C)CCCN1C(=O)CSC1=S JQRFJIWNCCYNKU-UHFFFAOYSA-N 0.000 description 1
- LICHZOBEUWVYSY-UHFFFAOYSA-N 3-azabicyclo[3.2.2]nonane Chemical compound C1CC2CCC1CNC2 LICHZOBEUWVYSY-UHFFFAOYSA-N 0.000 description 1
- IWLAXCIQVRFHQW-UHFFFAOYSA-N 3-ethyl-1,3-oxazolidine-2,4-dione Chemical compound CCN1C(=O)COC1=O IWLAXCIQVRFHQW-UHFFFAOYSA-N 0.000 description 1
- HPXUCPIEUHUFLS-UHFFFAOYSA-N 3-ethyl-1-phenylimidazolidine-2,4-dione Chemical compound O=C1N(CC)C(=O)CN1C1=CC=CC=C1 HPXUCPIEUHUFLS-UHFFFAOYSA-N 0.000 description 1
- UPCYEFFISUGBRW-UHFFFAOYSA-N 3-ethyl-2-sulfanylidene-1,3-thiazolidin-4-one Chemical compound CCN1C(=O)CSC1=S UPCYEFFISUGBRW-UHFFFAOYSA-N 0.000 description 1
- KJGKVKNUHXSXOH-UHFFFAOYSA-N 3-heptyl-1-phenyl-2-sulfanylideneimidazolidin-4-one Chemical compound S=C1N(CCCCCCC)C(=O)CN1C1=CC=CC=C1 KJGKVKNUHXSXOH-UHFFFAOYSA-N 0.000 description 1
- HMLWNNMYODLLJO-UHFFFAOYSA-N 3-methyl-1,3-thiazolidine-2,4-dione Chemical compound CN1C(=O)CSC1=O HMLWNNMYODLLJO-UHFFFAOYSA-N 0.000 description 1
- DVRWEKGUWZINTQ-UHFFFAOYSA-N 3-phenyl-2-sulfanylidene-1,3-thiazolidin-4-one Chemical compound O=C1CSC(=S)N1C1=CC=CC=C1 DVRWEKGUWZINTQ-UHFFFAOYSA-N 0.000 description 1
- IHKNLPPRTQQACK-UHFFFAOYSA-N 3-phenyl-4h-1,2-oxazol-5-one Chemical compound O1C(=O)CC(C=2C=CC=CC=2)=N1 IHKNLPPRTQQACK-UHFFFAOYSA-N 0.000 description 1
- JVQIKJMSUIMUDI-UHFFFAOYSA-N 3-pyrroline Chemical compound C1NCC=C1 JVQIKJMSUIMUDI-UHFFFAOYSA-N 0.000 description 1
- DXHWPUIXEDWFKD-UHFFFAOYSA-N 3h-benzo[g]indole Chemical compound C1=CC2=CC=CC=C2C2=C1CC=N2 DXHWPUIXEDWFKD-UHFFFAOYSA-N 0.000 description 1
- WFFZGYRTVIPBFN-UHFFFAOYSA-N 3h-indene-1,2-dione Chemical class C1=CC=C2C(=O)C(=O)CC2=C1 WFFZGYRTVIPBFN-UHFFFAOYSA-N 0.000 description 1
- PTSVWECGNJIPGQ-UHFFFAOYSA-N 4-[4-[3-[4-(dimethylamino)phenyl]prop-2-enylidene]-3-methyl-5-oxopyrazol-1-yl]benzoic acid Chemical compound C1=CC(N(C)C)=CC=C1C=CC=C1C(=O)N(C=2C=CC(=CC=2)C(O)=O)N=C1C PTSVWECGNJIPGQ-UHFFFAOYSA-N 0.000 description 1
- UULQWQZZJJLJPF-UHFFFAOYSA-N 4-[4-[[4-(dimethylamino)phenyl]methylidene]-3-methyl-5-oxopyrazol-1-yl]benzoic acid Chemical compound C1=CC(N(C)C)=CC=C1C=C1C(=O)N(C=2C=CC(=CC=2)C(O)=O)N=C1C UULQWQZZJJLJPF-UHFFFAOYSA-N 0.000 description 1
- RUKJCCIJLIMGEP-ONEGZZNKSA-N 4-dimethylaminocinnamaldehyde Chemical compound CN(C)C1=CC=C(\C=C\C=O)C=C1 RUKJCCIJLIMGEP-ONEGZZNKSA-N 0.000 description 1
- QBWUTXXJFOIVME-UHFFFAOYSA-N 4h-1,2-oxazol-5-one Chemical compound O=C1CC=NO1 QBWUTXXJFOIVME-UHFFFAOYSA-N 0.000 description 1
- HEIBIWZLPGRPMB-UHFFFAOYSA-N 5-[4-[[4-(dimethylamino)phenyl]methylidene]-3-methyl-5-oxopyrazol-1-yl]benzene-1,3-dicarboxylic acid Chemical compound C1=CC(N(C)C)=CC=C1C=C1C(=O)N(C=2C=C(C=C(C=2)C(O)=O)C(O)=O)N=C1C HEIBIWZLPGRPMB-UHFFFAOYSA-N 0.000 description 1
- KBZFDRWPMZESDI-UHFFFAOYSA-N 5-aminobenzene-1,3-dicarboxylic acid Chemical compound NC1=CC(C(O)=O)=CC(C(O)=O)=C1 KBZFDRWPMZESDI-UHFFFAOYSA-N 0.000 description 1
- 101100278747 Caenorhabditis elegans dve-1 gene Proteins 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- QXNVGIXVLWOKEQ-UHFFFAOYSA-N Disodium Chemical class [Na][Na] QXNVGIXVLWOKEQ-UHFFFAOYSA-N 0.000 description 1
- SNRUBQQJIBEYMU-UHFFFAOYSA-N Dodecane Natural products CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 description 1
- 239000004606 Fillers/Extenders Substances 0.000 description 1
- SIKJAQJRHWYJAI-UHFFFAOYSA-N Indole Chemical compound C1=CC=C2NC=CC2=C1 SIKJAQJRHWYJAI-UHFFFAOYSA-N 0.000 description 1
- QUYZZTTYATWSRY-UHFFFAOYSA-N N1C=CC=C2N=CC=C12 Chemical compound N1C=CC=C2N=CC=C12 QUYZZTTYATWSRY-UHFFFAOYSA-N 0.000 description 1
- WTKZEGDFNFYCGP-UHFFFAOYSA-O Pyrazolium Chemical compound C1=CN[NH+]=C1 WTKZEGDFNFYCGP-UHFFFAOYSA-O 0.000 description 1
- 206010070834 Sensitisation Diseases 0.000 description 1
- 229910052771 Terbium Inorganic materials 0.000 description 1
- ZIRKVBFILIEWBG-UHFFFAOYSA-N [P].O(Br)Br.[La] Chemical compound [P].O(Br)Br.[La] ZIRKVBFILIEWBG-UHFFFAOYSA-N 0.000 description 1
- RKAGKCQBSWAWSU-UHFFFAOYSA-N acenaphthyleno[1,2-d][1,3]thiazole Chemical compound C1=CC(C2=C3N=CS2)=C2C3=CC=CC2=C1 RKAGKCQBSWAWSU-UHFFFAOYSA-N 0.000 description 1
- 125000002777 acetyl group Chemical group [H]C([H])([H])C(*)=O 0.000 description 1
- RZUBARUFLYGOGC-MTHOTQAESA-L acid fuchsin Chemical compound [Na+].[Na+].[O-]S(=O)(=O)C1=C(N)C(C)=CC(C(=C\2C=C(C(=[NH2+])C=C/2)S([O-])(=O)=O)\C=2C=C(C(N)=CC=2)S([O-])(=O)=O)=C1 RZUBARUFLYGOGC-MTHOTQAESA-L 0.000 description 1
- 230000003213 activating effect Effects 0.000 description 1
- 125000002252 acyl group Chemical group 0.000 description 1
- 125000003342 alkenyl group Chemical group 0.000 description 1
- 125000004414 alkyl thio group Chemical group 0.000 description 1
- 239000011260 aqueous acid Substances 0.000 description 1
- 238000000149 argon plasma sintering Methods 0.000 description 1
- 125000004391 aryl sulfonyl group Chemical group 0.000 description 1
- 125000005110 aryl thio group Chemical group 0.000 description 1
- ZSIQJIWKELUFRJ-UHFFFAOYSA-N azepane Chemical compound C1CCCNCC1 ZSIQJIWKELUFRJ-UHFFFAOYSA-N 0.000 description 1
- HONIICLYMWZJFZ-UHFFFAOYSA-N azetidine Chemical compound C1CNC1 HONIICLYMWZJFZ-UHFFFAOYSA-N 0.000 description 1
- 125000005235 azinium group Chemical group 0.000 description 1
- 238000000498 ball milling Methods 0.000 description 1
- HNYOPLTXPVRDBG-UHFFFAOYSA-N barbituric acid Chemical compound O=C1CC(=O)NC(=O)N1 HNYOPLTXPVRDBG-UHFFFAOYSA-N 0.000 description 1
- BVVBQOJNXLFIIG-UHFFFAOYSA-N benzo[g][1,3]benzoxazole Chemical compound C1=CC=CC2=C(OC=N3)C3=CC=C21 BVVBQOJNXLFIIG-UHFFFAOYSA-N 0.000 description 1
- 125000003236 benzoyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C(*)=O 0.000 description 1
- 230000008033 biological extinction Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 125000001246 bromo group Chemical group Br* 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- AGOYDEPGAOXOCK-KCBOHYOISA-N clarithromycin Chemical compound O([C@@H]1[C@@H](C)C(=O)O[C@@H]([C@@]([C@H](O)[C@@H](C)C(=O)[C@H](C)C[C@](C)([C@H](O[C@H]2[C@@H]([C@H](C[C@@H](C)O2)N(C)C)O)[C@H]1C)OC)(C)O)CC)[C@H]1C[C@@](C)(OC)[C@@H](O)[C@H](C)O1 AGOYDEPGAOXOCK-KCBOHYOISA-N 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 125000004093 cyano group Chemical group *C#N 0.000 description 1
- HJSLFCCWAKVHIW-UHFFFAOYSA-N cyclohexane-1,3-dione Chemical compound O=C1CCCC(=O)C1 HJSLFCCWAKVHIW-UHFFFAOYSA-N 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- FPVGTPBMTFTMRT-UHFFFAOYSA-L disodium;2-amino-5-[(4-sulfonatophenyl)diazenyl]benzenesulfonate Chemical compound [Na+].[Na+].C1=C(S([O-])(=O)=O)C(N)=CC=C1N=NC1=CC=C(S([O-])(=O)=O)C=C1 FPVGTPBMTFTMRT-UHFFFAOYSA-L 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 125000003438 dodecyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- QELUYTUMUWHWMC-UHFFFAOYSA-N edaravone Chemical compound O=C1CC(C)=NN1C1=CC=CC=C1 QELUYTUMUWHWMC-UHFFFAOYSA-N 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- XYIBRDXRRQCHLP-UHFFFAOYSA-N ethyl acetoacetate Chemical compound CCOC(=O)CC(C)=O XYIBRDXRRQCHLP-UHFFFAOYSA-N 0.000 description 1
- 229940093858 ethyl acetoacetate Drugs 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 125000004705 ethylthio group Chemical group C(C)S* 0.000 description 1
- 235000019233 fast yellow AB Nutrition 0.000 description 1
- RZILCCPWPBTYDO-UHFFFAOYSA-N fluometuron Chemical compound CN(C)C(=O)NC1=CC=CC(C(F)(F)F)=C1 RZILCCPWPBTYDO-UHFFFAOYSA-N 0.000 description 1
- 125000001153 fluoro group Chemical group F* 0.000 description 1
- 125000002485 formyl group Chemical group [H]C(*)=O 0.000 description 1
- 230000006870 function Effects 0.000 description 1
- ZZUFCTLCJUWOSV-UHFFFAOYSA-N furosemide Chemical compound C1=C(Cl)C(S(=O)(=O)N)=CC(C(O)=O)=C1NCC1=CC=CO1 ZZUFCTLCJUWOSV-UHFFFAOYSA-N 0.000 description 1
- DQZARQCHJNPXQP-UHFFFAOYSA-N gadolinium;sulfur monoxide Chemical class [Gd].S=O DQZARQCHJNPXQP-UHFFFAOYSA-N 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 239000012456 homogeneous solution Substances 0.000 description 1
- 150000001469 hydantoins Chemical class 0.000 description 1
- ZCQWOFVYLHDMMC-UHFFFAOYSA-O hydron;1,3-oxazole Chemical compound C1=COC=[NH+]1 ZCQWOFVYLHDMMC-UHFFFAOYSA-O 0.000 description 1
- KAESVJOAVNADME-UHFFFAOYSA-O hydron;1h-pyrrole Chemical compound [NH2+]1C=CC=C1 KAESVJOAVNADME-UHFFFAOYSA-O 0.000 description 1
- SMWDFEZZVXVKRB-UHFFFAOYSA-O hydron;quinoline Chemical compound [NH+]1=CC=CC2=CC=CC=C21 SMWDFEZZVXVKRB-UHFFFAOYSA-O 0.000 description 1
- 238000010348 incorporation Methods 0.000 description 1
- 125000002346 iodo group Chemical group I* 0.000 description 1
- 125000003253 isopropoxy group Chemical group [H]C([H])([H])C([H])(O*)C([H])([H])[H] 0.000 description 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- AWJUIBRHMBBTKR-UHFFFAOYSA-O isoquinolin-2-ium Chemical compound C1=[NH+]C=CC2=CC=CC=C21 AWJUIBRHMBBTKR-UHFFFAOYSA-O 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000000034 method Methods 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 125000002816 methylsulfanyl group Chemical group [H]C([H])([H])S[*] 0.000 description 1
- 125000004573 morpholin-4-yl group Chemical group N1(CCOCC1)* 0.000 description 1
- 125000002347 octyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 239000011236 particulate material Substances 0.000 description 1
- 239000012466 permeate Substances 0.000 description 1
- 125000000951 phenoxy group Chemical group [H]C1=C([H])C([H])=C(O*)C([H])=C1[H] 0.000 description 1
- YZTJYBJCZXZGCT-UHFFFAOYSA-N phenylpiperazine Chemical compound C1CNCCN1C1=CC=CC=C1 YZTJYBJCZXZGCT-UHFFFAOYSA-N 0.000 description 1
- 125000003170 phenylsulfonyl group Chemical group C1(=CC=CC=C1)S(=O)(=O)* 0.000 description 1
- 125000001476 phosphono group Chemical group [H]OP(*)(=O)O[H] 0.000 description 1
- 229920006267 polyester film Polymers 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 239000011241 protective layer Substances 0.000 description 1
- DNTVKOMHCDKATN-UHFFFAOYSA-N pyrazolidine-3,5-dione Chemical compound O=C1CC(=O)NN1 DNTVKOMHCDKATN-UHFFFAOYSA-N 0.000 description 1
- JUJWROOIHBZHMG-UHFFFAOYSA-O pyridinium Chemical compound C1=CC=[NH+]C=C1 JUJWROOIHBZHMG-UHFFFAOYSA-O 0.000 description 1
- 229910052761 rare earth metal Inorganic materials 0.000 description 1
- 150000002910 rare earth metals Chemical class 0.000 description 1
- 238000001953 recrystallisation Methods 0.000 description 1
- 230000003252 repetitive effect Effects 0.000 description 1
- KIWUVOGUEXMXSV-UHFFFAOYSA-N rhodanine Chemical compound O=C1CSC(=S)N1 KIWUVOGUEXMXSV-UHFFFAOYSA-N 0.000 description 1
- 150000003839 salts Chemical group 0.000 description 1
- 239000004576 sand Substances 0.000 description 1
- 238000010187 selection method Methods 0.000 description 1
- 230000008313 sensitization Effects 0.000 description 1
- 230000001235 sensitizing effect Effects 0.000 description 1
- ADZWSOLPGZMUMY-UHFFFAOYSA-M silver bromide Chemical compound [Ag]Br ADZWSOLPGZMUMY-UHFFFAOYSA-M 0.000 description 1
- 235000009518 sodium iodide Nutrition 0.000 description 1
- 239000004317 sodium nitrate Substances 0.000 description 1
- 235000010344 sodium nitrate Nutrition 0.000 description 1
- 235000010265 sodium sulphite Nutrition 0.000 description 1
- AXMCIYLNKNGNOT-UHFFFAOYSA-N sodium;3-[[4-[(4-dimethylazaniumylidenecyclohexa-2,5-dien-1-ylidene)-[4-[ethyl-[(3-sulfophenyl)methyl]amino]phenyl]methyl]-n-ethylanilino]methyl]benzenesulfonate Chemical compound [Na+].C=1C=C(C(=C2C=CC(C=C2)=[N+](C)C)C=2C=CC(=CC=2)N(CC)CC=2C=C(C=CC=2)S([O-])(=O)=O)C=CC=1N(CC)CC1=CC=CC(S(O)(=O)=O)=C1 AXMCIYLNKNGNOT-UHFFFAOYSA-N 0.000 description 1
- 125000004079 stearyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 125000000542 sulfonic acid group Chemical group 0.000 description 1
- GZCRRIHWUXGPOV-UHFFFAOYSA-N terbium atom Chemical compound [Tb] GZCRRIHWUXGPOV-UHFFFAOYSA-N 0.000 description 1
- FRNOGLGSGLTDKL-UHFFFAOYSA-N thulium atom Chemical compound [Tm] FRNOGLGSGLTDKL-UHFFFAOYSA-N 0.000 description 1
- 125000002023 trifluoromethyl group Chemical group FC(F)(F)* 0.000 description 1
- UJMBCXLDXJUMFB-UHFFFAOYSA-K trisodium;5-oxo-1-(4-sulfonatophenyl)-4-[(4-sulfonatophenyl)diazenyl]-4h-pyrazole-3-carboxylate Chemical compound [Na+].[Na+].[Na+].[O-]C(=O)C1=NN(C=2C=CC(=CC=2)S([O-])(=O)=O)C(=O)C1N=NC1=CC=C(S([O-])(=O)=O)C=C1 UJMBCXLDXJUMFB-UHFFFAOYSA-K 0.000 description 1
- PBYZMCDFOULPGH-UHFFFAOYSA-N tungstate Chemical compound [O-][W]([O-])(=O)=O PBYZMCDFOULPGH-UHFFFAOYSA-N 0.000 description 1
Images
Classifications
-
- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03C—PHOTOSENSITIVE MATERIALS FOR PHOTOGRAPHIC PURPOSES; PHOTOGRAPHIC PROCESSES, e.g. CINE, X-RAY, COLOUR, STEREO-PHOTOGRAPHIC PROCESSES; AUXILIARY PROCESSES IN PHOTOGRAPHY
- G03C5/00—Photographic processes or agents therefor; Regeneration of such processing agents
- G03C5/16—X-ray, infrared, or ultraviolet ray processes
-
- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03C—PHOTOSENSITIVE MATERIALS FOR PHOTOGRAPHIC PURPOSES; PHOTOGRAPHIC PROCESSES, e.g. CINE, X-RAY, COLOUR, STEREO-PHOTOGRAPHIC PROCESSES; AUXILIARY PROCESSES IN PHOTOGRAPHY
- G03C1/00—Photosensitive materials
- G03C1/76—Photosensitive materials characterised by the base or auxiliary layers
- G03C1/825—Photosensitive materials characterised by the base or auxiliary layers characterised by antireflection means or visible-light filtering means, e.g. antihalation
- G03C1/83—Organic dyestuffs therefor
- G03C1/832—Methine or polymethine dyes
-
- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03C—PHOTOSENSITIVE MATERIALS FOR PHOTOGRAPHIC PURPOSES; PHOTOGRAPHIC PROCESSES, e.g. CINE, X-RAY, COLOUR, STEREO-PHOTOGRAPHIC PROCESSES; AUXILIARY PROCESSES IN PHOTOGRAPHY
- G03C1/00—Photosensitive materials
- G03C1/74—Applying photosensitive compositions to the base; Drying processes therefor
- G03C2001/7448—Dispersion
-
- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03C—PHOTOSENSITIVE MATERIALS FOR PHOTOGRAPHIC PURPOSES; PHOTOGRAPHIC PROCESSES, e.g. CINE, X-RAY, COLOUR, STEREO-PHOTOGRAPHIC PROCESSES; AUXILIARY PROCESSES IN PHOTOGRAPHY
- G03C2200/00—Details
- G03C2200/44—Details pH value
-
- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03C—PHOTOSENSITIVE MATERIALS FOR PHOTOGRAPHIC PURPOSES; PHOTOGRAPHIC PROCESSES, e.g. CINE, X-RAY, COLOUR, STEREO-PHOTOGRAPHIC PROCESSES; AUXILIARY PROCESSES IN PHOTOGRAPHY
- G03C2200/00—Details
- G03C2200/46—Details pKa value
Definitions
- the invention relates to radiography. More specifically, the invention relates to double coated silver halide radiographic elements of the type employed in combination with intensifying screens.
- silver halide photographic elements are capable of directly recording X ray exposures, they are more responsive to light within the visible spectrum. It has become an established practice to construct Duplitized@ (double coated) radiographic elements in which silver halide emulsion layers are coated on opposite sides of a film support and to sandwich the radiograph element between intensifying screen pairs during imaging.
- the intensifying screens contain phosphors that absorb X radiation and emit light. This light is transmitted to the silver halide emulsion layer on the adjacent face of the film support. The result is that diagnostic radiographic imaging is achieved at significantly reduced X-ray exposure levels.
- mordants have been employed to reduce dye migration, they have not been effective in preventing loss of photographic speed and have further proved disadvantageous in increasing the bulk of the water permeable layers of the radiographic elements, thereby increasing the processing time required to produce a processed element that is dry to the touch.
- the dissolved dye approach to crossover reduction is illustrated by Door- selaer U.K. Pat. Spec. 1,414,456 and Bollen et al U.K. Pat. Spec. 1,477,638 and 1,477,639.
- It is an object of the invention to provide a radiographic element which exhibits reduced crossover without objectionable dye stain comprised of a film support capable of transmitting radiation to which the radiographic element is responsive having opposed major faces, processing solution permeable hydrophilic colloid layers are present including, coated on each opposed major face, at least one silver halide emulsion layer capable of responding to electromagnetic radiation in the visible portion of spectrum and at least one other hydrophilic colloid layer interposed between the emulsion layer and the support, and a dye dispersed in at least one of the interposed hydrophilic colloid layers capable of (i) absorbing visible radiation to which the radiographic element is responsive to reduce crossover and (ii) capable of being decolorized in a processing solution.
- a radiographic element of the type described element is characterized in that the dye is, prior to processing, in the form of microcrystalline particles present in a concentration sufficient to reduce crossover to less than 10 percent and is capable of being substantially decolorized in less than 90 seconds during processing.
- the present invention offers significant and unexpected advantages over the prior state of the art. Crossover is reduced below levels heretofore successfully achieved in the art and without desensitization of latent image forming silver halide grains.
- the extremely low crossover levels realized have been made possible by discovering that dyes incorporated in a radiographic element in the form microcrystalline particles can be nevertheless satisfactorily decolorized during the very short processing interval conventionally employed in preparing radiographic images.
- the crossover reducing dyes in microcrystalline form migration of the dyes to latent image forming silver halide grains surfaces and resulting desensitization of these grains is obviated.
- the present invention permits simpler radiographic element construction than is possible with radiographic elements employing a nonimaging silver halide grains to provide dye adsorption surfaces.
- the microcrystalline form of the dyes allows superior spectral adsorption profiles to be realized as compared to the same or chromophorically similar dyes adsorbed to silver halide grain surfaces.
- crossover reduction advantages of the present invention are fully compatible with both the crossover reduction and other known advantages of high aspect ratio and thin, intermediate aspect ratio tabular grain silver halide emulsions.
- a radiographic element 100 is positioned between a pair of light emitting intensifying screens 201 and 202.
- the radiographic element support is comprised of a radiographic support element 101, typically transparent or blue tinted, capable of transmitting at least a portion of the light to which it is exposed and optional, similarly transmissive subbing layer units 103 and 105, each of which can be formed of one or more adhesion promoting layers.
- On the first and second opposed major faces 107 and 109 of the support formed by the subbing layer units are crossover reducing hydrophilic colloid layers 111 and 113, respectively.
- each of the emulsion layer units is formed of one or more hydrophilic colloid layers including at least one silver halide emulsion layer.
- Overlying the emulsion layer units 115 and 117 are optional protective overcoat layers 119 and 121, respectively. All of the protective layers and hydrophilic colloid layers are permeable to processing solutions.
- the assembly is imagewise exposed to X radiation.
- the X radiation is principally absorbed by the intensifying screens 201 and 202, which promptly emit light as a direct function of X ray exposure.
- the intensifying screens 201 and 202 which promptly emit light as a direct function of X ray exposure.
- the light recording latent image forming emulsion layer unit 115 is positioned adjacent this screen to receive the light which it emits. Because of the proximity of the screen 201 to the emulsion layer unit 115 only minimal light scattering occurs before latent image forming absorption occurs in this layer unit. Hence light emission from screen 201 forms a sharp image in emulsion layer unit 115.
- crossover reducing layers 111 and 113 are interposed between the screen 201 and the remote emulsion layer unit and are capable of intercepting and attenuating this remaining light. Both of these layers thereby con tribute to reducing cross- over exposure of emulsion layer unit 117 by the screen 201.
- the screen 202 produces a sharp image in emulsion layer unit 117, and the light absorbing layers 111 and 113 similarly reduce crossover exposure of the emulsion layer unit 115 by the screen 202.
- the crossover reducing layers on opposite sides of the support can be used to' absorb radiation from different regions of the spectrum.
- a light absorbing dye can be present in one crossover reducing layer while an ultraviolet (UV) absorber is present in the remaining crossover reducing layer.
- UV ultraviolet
- the radiographic element 100 is removed from association with the intensifying screens 210 and 202 and processed in a conventional manner. That is, the radiographic element is brought into contact with an aqueous alkaline developer, such as a hydroquinone-Phenidone@(1-phenyi-3-pyrazoiidone) developer having a pH of 10.0, a specific form of which is illustrated in the examples below.
- the alkaline developer permeates the hydrophilic colloid layers, converting the silver halide emulsion layer latent image to a viewable silver image and simultaneously decolorizing the crossover reducing layers.
- Conventional post development steps such as stop bath contact, fixing, and washing can occur.
- the radiographic elements of this invention are fully compatible with conventional radiographic element processing, such as in an RP-X-Omat@ processor.
- the radiographic elements of the present invention offer advantages in crossover reduction by employing one or more crossover reducing layers comprised a hydrophilic colloid employed as a dispersing vehicle and a particulate dye.
- concentration of the dye present is chosen to impart an optical density of at least 1.00 at the peak wavelength of emulsion sensitivity. Since it is conventional practice to employ intensifying screen-radiographic element combinations in which the peak emulsion sensitivity matches the peak light emission by the intensifying screens, it follows that the dye also exhibits a density of at least 1.00 at the wavelength of peak emission of the intensifying screen.
- particulate dyes including combinations of particulate dyes, capable of imparting a density of 1.00 or more over the entire spectral region of significant sensitivity and emission.
- particulate dyes for radiographic elements to be used with blue emitting intensifying screens, such as those which employ calcium tungstate or thulium activated lanthanum oxybromide phosphors, it is generally preferred that the particulate dye be selected to produce an optical density of at least 1.00 over the entire spectral region of 400 to 500 nm.
- the particulate dye exhibit a density of at least 1.00 over the spectral region of 450 to 550 nm. To the extent the wavelength of emission of the screens or the sensitivities of the emulsion layers are restricted, the spectral region over which the particulate dye must also effectively absorb light is correspondingly reduced.
- particulate dye optical densities of 1.00 chosen as described above are effective to reduce crossover to less than 10 percent, it is specifically recognized that particulate dye densities can be increased until radiographic element crossover is effectively eliminated. For example, by increasing the particulate dye concentration so that it imparts a density of 10.0 to the radiographic element, crossover is reduced to only 1 percent.
- the size of the dye particles is chosen to facilitate coating and rapid decolorization of the dye. In general smaller dye particles lend themselves to more uniform coatings and more rapid decolorization.
- the dye particles employed in all instances have a mean diameter of less than 10.0 ⁇ m and preferably less than 1.0 ⁇ m. There is no theoretical limit on the minimum sizes the dye particles can take.
- the dye parti- des can be most conveniently formed by crystallization from solution in sizes ranging down to about 0.01 ⁇ .tm or less. Where the dyes are initially crystallized in form of particles larger than desired for use, conventional techniques for achieving smaller particle sizes can be employed, such as ball milling, roller milling, sand milling, and the like.
- hydrophilic colloids can take any of various conventional forms, such as any of the forms set forth in Research Disclosure, Vol. 176, December 1978, Item 17643, Section IX. Vehicles and vehicle extenders, the hydrophilic colloid layers are most commonly gelatin and gelatin derivatives. Hydrophilic colloids are typically coated as aqueous solutions in the pH range or from about 5 to 6, most typically from 5.5 to 6.0, to form radiographic element layers.
- the dyes which are selected for use in the practice of this invention are those which are capable of remaining in particulate form at those pH levels in aqueous solutions.
- Dyes which by reason of their chromophoric make up are inherently ionic, such as cyanine dyes, as well as dyes which contain substituents which are ionically dissociated in the above-noted pH ranges of coating may in individual instances be sufficiently insoluble to satisfy the requirements of this invention, but do not in general constitute preferred classes of dyes for use in the practice of the invention.
- dyes with sulfonic acid substituents are normally too soluble to satisfy the requirements of the invention.
- nonionic dyes with carboxylic acid groups (depending in some instances on the specific substitution location of the carboxylic acid group) are in general insoluble under aqueous acid coating conditions. Specific dye selections can be made from known dye characteristics or by observing solubilities in the pH range of from 5.5 to 6.0 at normal layer coating temperatures- e.g., at a reference temperature of 40 ° C.
- Preferred particulate dyes are nonionic polymethine dyes, which include the merocyanine, oxonol, hemioxonol, styryls, and arylidene dyes.
- the merocyanine dyes include, joined by a methine linkage, at least one basic heterocyclic nucleus and at least one acidic nucleus.
- Basic nuclei such as azolium or azinium nuclei, for example, include those derived from pyridinium, quinolinium, isoquinolinium, oxazolium, pyrazolium, pyrrolium, indolium, oxadiazo- lium, 3H- or 1 H-benzoindolium, pyrrolopyridinium, phenanthrothiazolium, and acenaphthothiazolium quaternary salts.
- Exemplary of the basic heterocyclic nuclei are those satisfying Formulae I and II. where
- Merocyanine dyes link one of the basic heterocyclic nuclei described above to an acidic keto methylene nucleus through a methine linkage as described above.
- Exemplary acidic nuclei are those which satisfy Formula III.
- Useful hemioxonol dyes exhibit a keto methylene nucleus as shown in Formula III and a nucleus as shown in Formula IV.
- Exemplary oxonol dyes exhibit two keto methylene nuclei as shown in Formula III joined through one or higher uneven number of methine groups.
- Useful arylidene dyes exhibit a keto methylene nucleus as shown in Formula III and a nucleus as shown in Formula V joined by a methine linkage as described above containing one or a higher uneven number of methine groups.
- G3 and G4 are as previously defined.
- a specifically preferred class of oxonol dyes for use in the practice of the invention are the oxonol dyes satisfying Formula VI. wherein
- Exemplary of specific preferred oxonol dyes are those set forth below in Table I.
- a specifically preferred class of arylidene dyes for use in the practice of the invention are the arylidene dyes satisfying Formula VII. wherein
- Exemplary of specific preferred arylidene dyes are those set forth below in Tables II and III.
- UV absorber either blended with the dye in each of crossover reducing layers 111 and 113 or confined to one crossover reducing layer with the dye being confined to the other crossover reducing layer.
- Any conventional UV absorber can be employed for this purpose.
- Illustrative useful UV absorbers are those disclosed in Research Disclosure, Item 18431, cited above, Section V, or Research Disclosure, Item 17643, cited above, Section Vl-ILC.
- Preferred UV absorbers are those which either exhibit minimal absorption in the visible portion of the spectrum or are decolorized on processing similarly as the crossover reducing dyes.
- the remaining features of the dual coated radiographic elements can take any convenient conventional form.
- Such conventional radiographic element features are illustrated, for example, in Research Disclosure, Item 18431, cited above.
- Other conventional features common to both silver halide radiographic elements and photographic elements are disclosed in Research Disclosure, Item 17643, cited above.
- Radiographic elements according to this invention having highly desirable imaging characteristics are those which employ one or more tabular grain silver halide emulsions.
- Preferred radiographic elements according to the present invention are those which employ one or more high aspect ratio tabular grain emulsions or thin, intermediate aspect ratio tabular grain emulsions.
- Preferred tabular grain emulsions for use in the radiographic elements of this invention are those in which tabular silver halide grains having a thickness of less than 0.5 ⁇ m (preferably less than 0.3 11m and optimally less than 0.2 11m) have an average aspect ratio of greater than 5:1 (preferably greater than 8:1 and optimally at least 12:1) and account for greater than 50 percent (preferably greater than 70 percent and optimally greater than 90 percent) of the total projected area of the silver halide grains present in the emulsion.
- Preferred blue and minus blue spectral sensitizing dyes as well as optimum chemical and spectral sensitizations of tabular silver halide grains are disclosed by Kofron et al U.S. Patent 4,439,520.
- the preferred radiographic elements of this invention are those which employ one or more of the crossover reducing layers described above in combination with tabular grain latent image forming emulsions.
- Preferred radiographic element and tabular grain silver halide emulsion features are disclosed in Abbott et al U.S. Patents 4,425,425 and 4,425,426 and Dickerson U.S. Patent 4,414,304.
- Radiographic elements can be constructed according to this invention in which tabular grain silver halide emulsion layers are coated nearer the support than nontabular grain silver halide emulsion layers to reduce crossover, as illustrated by Sugimoto European Patent Application 0,084,637.
- radiographic elements By employing tabular grain emulsions, which in themselves reduce crossover in combination with the crossover reducing layers provided by this invention radiographic elements exhibiting extremely low crossover levels can be achieved while also achieving high photographic speed, low levels of granularity, high silver covering power, and rapid processing capabilities deemed highly desirable in radiography.
- the following examples compare the performance of double coated radiographic elements exposed using blue emitting thulium activating lanthanum oxybromide phosphor intensifying screens.
- the radiographic elements were identical, except for the choice of the crossover reducing materials employed between the emulsion layer and the support on each major surface.
- the dye satisfying the requirements of the invention was Dye 1/A shown above in Table II.
- the dye was employed in a particulate form, the mean diameter of the dye particles being 0.08 1 1m.
- C-1 Tartrazine Yellow
- M-1 cationic mordant poly(1-methyl-2-vinylpyridinium p-toluene sulfonate
- CLS Carey Lea Silver
- One control element was constructed with the same hydrophilic colloid layers, but without a crossover reducing material being present. This element is referred to as C-0.
- An emulsion layer was coated over each hydrophilic colloid layer.
- the blue recording silver bromide emulsion layer was coated at a coverage of 2.2 g/m 2 silver and 2.2 g/m 2 gelatin.
- hydrophilic colloid layers (including the emulsion layers) were hardened with bis(vinylsulfonylmethyl) ether at 1.0% of the gelatin weight.
- samples of the dual coated radiographic elements were exposed with a single intensifying screen placed in contact with one emulsion layer. Black paper was placed against the other emulsion side of the sample.
- the X-radiation source was a Picker VTX653 3-phase X-ray machine, with a Dunlee High-Speed PX1431-CQ-150 kVp 0.7/1.4mm focus tube.
- Exposure was made at 70 kVp, 32mAs, at a distance of 1.40 m. Filtration was with 3 mm AI equivalent (1.25 inherent + 1.75 al); Half Value Layer (HVL) - 2.6 mm Al. A 26 step AI wedge was used, differing in thickness by 2 mm per step.
- the film was in contact with the developer in each instance for less than 90 seconds.
- Percent crossover is reported in Table IV below. Relative speed reported in Table IV is the speed of the emulsion layer nearest the support.
- This example demonstrates the satisfactory performance of a bleachable particulate dye to reduce crossover without producing dye stain in the processed radiographic element and with only minimal impact on imaging speed.
- the control crossover reducing materials were unacceptable because of their high dye stain, and the control dye was unacceptable in producing an increased loss in imaging speed.
- the control dye required the further incorporation of a mordant, which added to the drying load on the processor. Without the mordant being present the imaging speed loss would have been significantly higher.
- Examples 1 through 6 The procedure of Examples 1 through 6 was repeated, except that magenta dyes were substituted for testing, green sensitized radiographic emulsions were employed, and green emitting intensifying screens, Kodak Lanex Regular@ screens, were employed.
- the dye satisfying the requirements of the invention was Dye 4/A shown above the Table II.
- the dye was employed in a particulate form, the mean diameter of the dye particles being 0.2 ⁇ m.
- Acid Magenta (C.I. Acid Violet 19-C.I. 42,685), hereinafter referred to as C-2, was selected as a control exemplary of dyes which are water soluble and bleachable taught by the art to be used as a crossover reducing dye in a double coated radiographic element.
- C-2 Acid Magenta
- M-1 cationic mordant M-1 was employed in a 5 parts mordant to 1 part dye weight ratio.
- C-3 1,3-Bis[i-(4-sulfonylphenyl)-3-carboxy-2-pyrazolin-5-one-4] trimethine oxonol, disodium salt, hereinafter referred to as C-3, was selected as a control exemplary of magenta dyes which are water soluble and nonbleachable.
- Dye C-3 differed from dye 10 disclosed on page 5 of U.K. Pat. Spec. 1,414,456 only in that the nuclei were joined by 3 methine groups instead of 5 (to shift absorption into the desired green spectral region). To reduce wandering of the dye cationic mordant M-1 was again employed in a 5 parts mordant to 1 part dye weight ratio.
- the precipitate containing the dye was then purified through a number of washing and dissolu- tion/recrystallization steps.
- the precipitate was first slurried in 500 ml refluxing glacial acetic acid, cooled to room temperature, filtered, washed with 250 ml acetic acid, 250 ml H 2 0, 250 ml methanol, and then dried. It was then dissolved in 100 ml hot dimethylsulfoxide and cooled to 40 ° C. 300 ml methanol was added, upon which a red precipitate formed, which was filtered, washed with methanol, acetone, and ligroin, and dried.
- This precipitate was dissolved in 200 ml methanol and 6 ml (4.38 g) triethylamine and heated to reflux. 4.8 ml of concentrated hydrochloric acid was added and a fine red precipitate was formed. The solution was filtered while hot and the precipitate was washed with methanol and acetone and dried. The precipitate was then dissolved in a refluxing mixture of 200 ml ethanol and 6.0 ml (4.38 g) triethylamine. 9.0 g of sodium iodide dissolved in 50 ml methanol was added. Upon cooling to room temperature, a red precipitate formed. The mixture was chilled in ice for one hour, then filtered. The precipitate was washed with ethanol, ligroin and dried to yield the sodium salt of the dye.
- the sodium salt of the dye was dissolved in 200 ml water with rapid stirring. 6.0 ml concentrated hydrochloric acid was added and a fluffy red precipitate formed. The mixture was filtered and the precipitate was washed with water, methanol, acetone, and ligroin, and dried to yield Dye 1/0.
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Description
- The invention relates to radiography. More specifically, the invention relates to double coated silver halide radiographic elements of the type employed in combination with intensifying screens.
- While silver halide photographic elements are capable of directly recording X ray exposures, they are more responsive to light within the visible spectrum. It has become an established practice to construct Duplitized@ (double coated) radiographic elements in which silver halide emulsion layers are coated on opposite sides of a film support and to sandwich the radiograph element between intensifying screen pairs during imaging. The intensifying screens contain phosphors that absorb X radiation and emit light. This light is transmitted to the silver halide emulsion layer on the adjacent face of the film support. The result is that diagnostic radiographic imaging is achieved at significantly reduced X-ray exposure levels.
- An art recognized difficulty with employing double coated radiographic elements as described above is that some light emitted by each screen passes through the transparent film support to expose the silver halide emulsion layer on the opposite side of the support to light. This results in reduced image sharpness, and the effect is referred to in the art as crossover.
- A variety of approaches have been suggested to reduce crossover, as illustrated by Research Disclosure, Vol. 184, August 1979, Item 18431, Section V. Cross-Over Exposure Control. Research Disclosure is published by Kenneth Mason Publications, Ltd., Emsworth, Hampshire PO10 7DD, England.
- One approach to reducing crossover has been to dissolve a filter dye in one or more of the hydro philic colloid layers forming the radiographic element. Such dyes must, of course, be selected to minimize residual density (stain) in the image bearing radiographic element. A pervasive problem with dissolved dyes has been their migration to the latent image forming silver halide grains, whether coated directly in the image forming emulsion layers or in underlying layers. This has resulted in loss of photographic speed, which, or course, runs directly counter to the general aim in adopting a double coated radiographic element format in the first instance. Thus, where this approach has been followed, a balance of reduced photographic speed and residual crossover has been accepted. Although mordants have been employed to reduce dye migration, they have not been effective in preventing loss of photographic speed and have further proved disadvantageous in increasing the bulk of the water permeable layers of the radiographic elements, thereby increasing the processing time required to produce a processed element that is dry to the touch. The dissolved dye approach to crossover reduction is illustrated by Door- selaer U.K. Pat. Spec. 1,414,456 and Bollen et al U.K. Pat. Spec. 1,477,638 and 1,477,639.
- To reduce dye migration to the image forming silver halide grains a variant approach has been to absorb the dye to the surfaces of silver halide grains other than those employed in imaging. This approach reduces speed loss, but has the disadvantage of requiring silver halide grains to be present in addition to those required for latent image formation. Further, an added silver halide grain population increases vehicle requirements and correspondingly increases drying times. Millikan et al U.K. Pat. Spec. 1,426,277 illustrates this approach applied to a specialized photographic imaging system in which a silver halide grain population is present in addition to the grain population which is relied upon to produce a latent image.
- The most successful approach to crossover reduction yet realized by the art has been to employ double coated radiographic elements containing spectrally sensitized high aspect ratio tabular grain emulsions or thin intermediate aspect ratio tabular grain emulsions, illustrated by Abbott et al U.S. Patents 4,425,425 and 4,425,426, respectively. Crossover levels below 20 percent (but well above 10 percent) are reported.
- It is an object of the invention to provide a radiographic element which exhibits reduced crossover without objectionable dye stain comprised of a film support capable of transmitting radiation to which the radiographic element is responsive having opposed major faces, processing solution permeable hydrophilic colloid layers are present including, coated on each opposed major face, at least one silver halide emulsion layer capable of responding to electromagnetic radiation in the visible portion of spectrum and at least one other hydrophilic colloid layer interposed between the emulsion layer and the support, and a dye dispersed in at least one of the interposed hydrophilic colloid layers capable of (i) absorbing visible radiation to which the radiographic element is responsive to reduce crossover and (ii) capable of being decolorized in a processing solution.
- This object is achieved by a radiographic element of the type described element is characterized in that the dye is, prior to processing, in the form of microcrystalline particles present in a concentration sufficient to reduce crossover to less than 10 percent and is capable of being substantially decolorized in less than 90 seconds during processing.
- The present invention offers significant and unexpected advantages over the prior state of the art. Crossover is reduced below levels heretofore successfully achieved in the art and without desensitization of latent image forming silver halide grains. The extremely low crossover levels realized have been made possible by discovering that dyes incorporated in a radiographic element in the form microcrystalline particles can be nevertheless satisfactorily decolorized during the very short processing interval conventionally employed in preparing radiographic images. By employing the crossover reducing dyes in microcrystalline form migration of the dyes to latent image forming silver halide grains surfaces and resulting desensitization of these grains is obviated. Further, the present invention permits simpler radiographic element construction than is possible with radiographic elements employing a nonimaging silver halide grains to provide dye adsorption surfaces. Still further, the microcrystalline form of the dyes allows superior spectral adsorption profiles to be realized as compared to the same or chromophorically similar dyes adsorbed to silver halide grain surfaces.
- Finally, the crossover reduction advantages of the present invention are fully compatible with both the crossover reduction and other known advantages of high aspect ratio and thin, intermediate aspect ratio tabular grain silver halide emulsions.
- Referring to Figure 1, in the assembly shown a
radiographic element 100 according to this invention is positioned between a pair of light emitting intensifyingscreens radiographic support element 101, typically transparent or blue tinted, capable of transmitting at least a portion of the light to which it is exposed and optional, similarly transmissivesubbing layer units major faces hydrophilic colloid layers 111 and 113, respectively. Overlying thecrossover reducing layers 111 and 113 are light recording latent image forming silver halideemulsion layer units emulsion layer units protective overcoat layers - In use, the assembly is imagewise exposed to X radiation. The X radiation is principally absorbed by the intensifying
screens screen 201, the light recording latent image formingemulsion layer unit 115 is positioned adjacent this screen to receive the light which it emits. Because of the proximity of thescreen 201 to theemulsion layer unit 115 only minimal light scattering occurs before latent image forming absorption occurs in this layer unit. Hence light emission fromscreen 201 forms a sharp image inemulsion layer unit 115. - However, not all of the light emitted by
screen 201 is absorbed withinemulsion layer unit 115. This remaining light, unless otherwise absorbed, will reach the remoteemulsion layer unit 117, resulting in a highly unsharp image being formed in this remote emulsion layer unit. Bothcrossover reducing layers 111 and 113 are interposed between thescreen 201 and the remote emulsion layer unit and are capable of intercepting and attenuating this remaining light. Both of these layers thereby con tribute to reducing cross- over exposure ofemulsion layer unit 117 by thescreen 201. - In an exactly analogous manner the
screen 202 produces a sharp image inemulsion layer unit 117, and thelight absorbing layers 111 and 113 similarly reduce crossover exposure of theemulsion layer unit 115 by thescreen 202. It is apparent that either of the two crossover reducing layers employed alone can effectively reduce crossover exposures from both screens. Thus, only one light absorbing layer is required. In a variant form the crossover reducing layers on opposite sides of the support can be used to' absorb radiation from different regions of the spectrum. For example, a light absorbing dye can be present in one crossover reducing layer while an ultraviolet (UV) absorber is present in the remaining crossover reducing layer. For manufacturing convenience dual coated radiographic elements most commonly employ identical coatings on opposite major faces of the support. - Following exposure to produce a stored latent image, the
radiographic element 100 is removed from association with the intensifyingscreens 210 and 202 and processed in a conventional manner. That is, the radiographic element is brought into contact with an aqueous alkaline developer, such as a hydroquinone-Phenidone@(1-phenyi-3-pyrazoiidone) developer having a pH of 10.0, a specific form of which is illustrated in the examples below. The alkaline developer permeates the hydrophilic colloid layers, converting the silver halide emulsion layer latent image to a viewable silver image and simultaneously decolorizing the crossover reducing layers. Conventional post development steps, such as stop bath contact, fixing, and washing can occur. Since the crossover reducing layers can be decolorized in less than 90 seconds following contact with an aqueous alkaline processing solution of pH 10.0, the radiographic elements of this invention are fully compatible with conventional radiographic element processing, such as in an RP-X-Omat@ processor. - The radiographic elements of the present invention offer advantages in crossover reduction by employing one or more crossover reducing layers comprised a hydrophilic colloid employed as a dispersing vehicle and a particulate dye. The concentration of the dye present is chosen to impart an optical density of at least 1.00 at the peak wavelength of emulsion sensitivity. Since it is conventional practice to employ intensifying screen-radiographic element combinations in which the peak emulsion sensitivity matches the peak light emission by the intensifying screens, it follows that the dye also exhibits a density of at least 1.00 at the wavelength of peak emission of the intensifying screen. Since neither screen emissions nor emulsion sensitivities are confined to a single wavelength, it is preferred to choose particulate dyes, including combinations of particulate dyes, capable of imparting a density of 1.00 or more over the entire spectral region of significant sensitivity and emission. For radiographic elements to be used with blue emitting intensifying screens, such as those which employ calcium tungstate or thulium activated lanthanum oxybromide phosphors, it is generally preferred that the particulate dye be selected to produce an optical density of at least 1.00 over the entire spectral region of 400 to 500 nm. For radiographic elements intended to be used with green emitting intensifying screens, such as those employing rare earth (e.g., terbium) activated gadolinium oxysulfide or oxyhalide phosphors, it is preferred that the particulate dye exhibit a density of at least 1.00 over the spectral region of 450 to 550 nm. To the extent the wavelength of emission of the screens or the sensitivities of the emulsion layers are restricted, the spectral region over which the particulate dye must also effectively absorb light is correspondingly reduced.
- While particulate dye optical densities of 1.00 chosen as described above are effective to reduce crossover to less than 10 percent, it is specifically recognized that particulate dye densities can be increased until radiographic element crossover is effectively eliminated. For example, by increasing the particulate dye concentration so that it imparts a density of 10.0 to the radiographic element, crossover is reduced to only 1 percent.
- Since there is a direct relationship between the dye concentration and the optical density produced for a given dye or dye combination, precise optical density selections can be achieved by routine selection procedures. Because dyes vary widely in their extinction coefficients and absorption profiles, it is recognized that the weight or even molar concentrations of particulate dyes will vary from one dye or dye combination selection to the next.
- The size of the dye particles is chosen to facilitate coating and rapid decolorization of the dye. In general smaller dye particles lend themselves to more uniform coatings and more rapid decolorization. The dye particles employed in all instances have a mean diameter of less than 10.0 µm and preferably less than 1.0 µm. There is no theoretical limit on the minimum sizes the dye particles can take. The dye parti- des can be most conveniently formed by crystallization from solution in sizes ranging down to about 0.01 ¡.tm or less. Where the dyes are initially crystallized in form of particles larger than desired for use, conventional techniques for achieving smaller particle sizes can be employed, such as ball milling, roller milling, sand milling, and the like.
- An important criterion in dye selection is their ability to remain in particulate form in hydrophilic colloid layers of radiographic elements. While the hydrophilic colloids can take any of various conventional forms, such as any of the forms set forth in Research Disclosure, Vol. 176, December 1978, Item 17643, Section IX. Vehicles and vehicle extenders, the hydrophilic colloid layers are most commonly gelatin and gelatin derivatives. Hydrophilic colloids are typically coated as aqueous solutions in the pH range or from about 5 to 6, most typically from 5.5 to 6.0, to form radiographic element layers. The dyes which are selected for use in the practice of this invention are those which are capable of remaining in particulate form at those pH levels in aqueous solutions.
- Dyes which by reason of their chromophoric make up are inherently ionic, such as cyanine dyes, as well as dyes which contain substituents which are ionically dissociated in the above-noted pH ranges of coating may in individual instances be sufficiently insoluble to satisfy the requirements of this invention, but do not in general constitute preferred classes of dyes for use in the practice of the invention. For example, dyes with sulfonic acid substituents are normally too soluble to satisfy the requirements of the invention. On the other hand, nonionic dyes with carboxylic acid groups (depending in some instances on the specific substitution location of the carboxylic acid group) are in general insoluble under aqueous acid coating conditions. Specific dye selections can be made from known dye characteristics or by observing solubilities in the pH range of from 5.5 to 6.0 at normal layer coating temperatures- e.g., at a reference temperature of 40°C.
- Preferred particulate dyes are nonionic polymethine dyes, which include the merocyanine, oxonol, hemioxonol, styryls, and arylidene dyes.
- The merocyanine dyes include, joined by a methine linkage, at least one basic heterocyclic nucleus and at least one acidic nucleus. Basic nuclei, such as azolium or azinium nuclei, for example, include those derived from pyridinium, quinolinium, isoquinolinium, oxazolium, pyrazolium, pyrrolium, indolium, oxadiazo- lium, 3H- or 1 H-benzoindolium, pyrrolopyridinium, phenanthrothiazolium, and acenaphthothiazolium quaternary salts.
-
- Z3 represents the elements needed to complete a cyclic nucleus derived from basic heterocyclic nitrogen compounds such as oxazoline, oxazole, benzoxazole, the naphthoxazoles (e.g., naphth[2,1-d]oxazole, naphth[2,3-d]oxazole, and naphth[1,2-d]oxazole), oxadazole, 2- or 4-pyridine, 2- or 4-quinoline, 1- or 3-isoquinoline, benzoquinoline, 1 H- or 3H-benzoindole, and pyrazole, which nuclei may be substituted on the ring by one or more of a wide variety of substituents such as hydroxy, the halogens (e.g., fluoro, chloro, bromo, and iodo), alkyl groups or substituted alkyl groups (e.g., methyl, ethyl, propyl, isopropyl, butyl, octyl, dodecyl, octadecyl, 2-hydroxyethyl, 2-cyanoethyl, and trifluoromethyl), aryl groups or substituted aryl groups (e.g., phenyl, 1-naphthyl, 2-naphthyl, 3-carboxyphenyl, and 4- biphenylyl), aralkyl groups (e.g., benzyl and phenethyl), alkoxy groups (e.g., methoxy, ethoxy, and isopropoxy), aryloxy groups (e.g., phenoxy and 1-naphthoxy), alkylthio groups (e.g., methylthio and ethylthio), arylthio groups (e.g, phenylthio, p-tolylthio, and 2-naphthylthio), methylenedioxy, cyano, 2-thienyl, styryl, amino or substituted amino groups (e.g., anilino, dimethylamino, diethylamino, and morpholino), acyl groups, (e.g, formyl, acetyl, benzoyl, and benzenesulfonyl);
- Q' represents the elements needed to complete a cyclic nucleus derived from basic heterocyclic nitrogen compounds such as pyrrole, pyrazole, indazole, and pyrrolopyridine;
- R represents alkyl groups, aryl groups, alkenyl groups, or aralkyl groups, with or without substituents, (e.g., carboxy, hydroxy, sulfo, alkoxy, sulfato, thiosulfato, phosphono, chloro, and bromo substituents);
- L is in each occurrence independently selected to represent a substituted or unsubstituted methine group―e.g., -CR8 = groups, where R8 represents hydrogen when the methine group is unsubstituted and most commonly represents alkyl of from 1 to 4 carbon atoms or phenyl when the methine group is substituted; and q is 0 or 1.
- Merocyanine dyes link one of the basic heterocyclic nuclei described above to an acidic keto methylene nucleus through a methine linkage, where the methine groups can take the form -CR8 = described above. The greater the number of the methine groups linking nuclei in the polymethine dyes in general and the merocyanine dyes in particular the longer the absorption wavelengths of the dyes.
-
- G1 represents an alkyl group or substituted alkyl group, an aryl or substituted aryl group, an aralkyl group, an alkoxy group, an aryloxy group, a hydroxy group, an amino group, or a substituted amino group, wherein exemplary substituents can take the various forms noted in connection with Formulae VI and VII;
- G2 can represent any one of the groups listed for Gi and in addition can represent a cyano group, an alkyl, or arylsulfonyl group, or a group represented by
- can represent the elements needed to complete a cyclic acidic nucleus such as those derived from 2,4-oxazolidinone (e.g., 3-ethyl-2,4-oxazolidindione), 2,4-thiazolidindione (e.g., 3-methyl-2,4-thiazolidindione), 2-thio-2,4-oxazolidindione (e.g., 3-phenyl-2-thio-2,4-oxazolidindione), rhodanine, such as 3-ethyl- rhodanine, 3-phenylrhodanine, 3-(3-dimethylaminopropyl)rhodanine, and 3-carboxymethylrhodanine, hy- dantoin (e.g., 1,3-diethylhydantoin and 3-ethyl-1-phenylhydantoin), 2-thiohydantoin (e.g., 1-ethyl-3-phenyl-2-thiohydantoin, 3-heptyl-1-phenyl-2-thiohydantoin, and arylsulfonyl-2-thiohydantoin), 2-pyrazolin-5-one, such as 3-methyl-1-phenyl-2-pyrazolin-5-one and 3-methyl-1-(4-carboxyphenyl)-2-pyrazolin-5- one, 2-isoxazolin-5-one (e.g., 3-phenyl-2-isoxazolin-5-one), 3,5-pyrazolidindione (e.g., 1,2-diethyl-3,5-pyrazolidindione and 1,2-diphenyl-3,5-pyrazolidindione), 1,3-indandione, 1,3-dioxane-4,6-dione, 1,3-cyclohexanedione, barbituric acid (e.g., 1-ethylbarbituric acid and 1,3-diethylbarbituric acid), and 2-thiobarbituric acid (e.g., 1,3-diethyl-2-thiobarbituric acid and 1,3-bis(2-methoxyethyl)-2-thiobarbituric acid).
-
- G3 and G4 may be the same or different and may represent alkyl, substituted alkyl, aryl, substituted aryl, or aralkyl, as illustrated for R ring substituents in Formula I or G3 and G4 taken together complete a ring system derived from a cyclic secondary amine, such as pyrrolidine, 3-pyrroline, piperidine, piperazine (e.g., 4-methylpiperazine and 4-phenylpiperazine), morpholine, 1,2,3,4-tetrahydroquinoline, decahydro- quinoline, 3-azabicyclo[3,2,2]nonane, indoline, azetidine, and hexahydroazepine.
- Exemplary oxonol dyes exhibit two keto methylene nuclei as shown in Formula III joined through one or higher uneven number of methine groups.
-
-
- R1 and R2 each independently represent alkyl of from 1 to 5 carbon atoms.
-
-
- A represents a substituted or unsubstituted acidic nucleus having a carboxyphenyl substituent selected from the group consisting of 2-pyrazolin-5-ones free of any substituent bonded thereto through a carboxyl group, rhodanines; hydantoins; 2-thiohydan toins; 4-thiohydantions; 2,4-oxazolidindiones; 2-thio-2,4-oxazolidindiones; isoxazolinones; barbiturics; 2-thiobarbiturics and indandiones;
- R represents hydrogen, alkyl of 1 to 4 carbon atoms or benzyl;
- R1 and R2, each independently, represents alkyl or aryl; or taken together with R5, R6, N, and the carbon atoms to which they are attached represent the atoms needed to complete a julolidene ring; R3 represents H, alkyl or aryl;
- R5 and R6, each independently, represents H or R5 taken together with R1; or R6 taken together with R2 each may represent the atoms necessary to complete a 5 or 6 membered ring; and m is 0 or 1.
-
- As indicated above, it is specifically contemplated to employ a UV absorber, either blended with the dye in each of
crossover reducing layers 111 and 113 or confined to one crossover reducing layer with the dye being confined to the other crossover reducing layer. Any conventional UV absorber can be employed for this purpose. Illustrative useful UV absorbers are those disclosed in Research Disclosure, Item 18431, cited above, Section V, or Research Disclosure, Item 17643, cited above, Section Vl-ILC. Preferred UV absorbers are those which either exhibit minimal absorption in the visible portion of the spectrum or are decolorized on processing similarly as the crossover reducing dyes. - Apart from the
crossover reducing layers 111 and 113 described above, the remaining features of the dual coated radiographic elements can take any convenient conventional form. Such conventional radiographic element features are illustrated, for example, in Research Disclosure, Item 18431, cited above. Other conventional features common to both silver halide radiographic elements and photographic elements are disclosed in Research Disclosure, Item 17643, cited above. - Radiographic elements according to this invention having highly desirable imaging characteristics are those which employ one or more tabular grain silver halide emulsions.
- Preferred radiographic elements according to the present invention are those which employ one or more high aspect ratio tabular grain emulsions or thin, intermediate aspect ratio tabular grain emulsions. Preferred tabular grain emulsions for use in the radiographic elements of this invention are those in which tabular silver halide grains having a thickness of less than 0.5 µm (preferably less than 0.3 11m and optimally less than 0.2 11m) have an average aspect ratio of greater than 5:1 (preferably greater than 8:1 and optimally at least 12:1) and account for greater than 50 percent (preferably greater than 70 percent and optimally greater than 90 percent) of the total projected area of the silver halide grains present in the emulsion. Preferred blue and minus blue spectral sensitizing dyes as well as optimum chemical and spectral sensitizations of tabular silver halide grains are disclosed by Kofron et al U.S. Patent 4,439,520.
- The preferred radiographic elements of this invention are those which employ one or more of the crossover reducing layers described above in combination with tabular grain latent image forming emulsions. Preferred radiographic element and tabular grain silver halide emulsion features are disclosed in Abbott et al U.S. Patents 4,425,425 and 4,425,426 and Dickerson U.S. Patent 4,414,304. Radiographic elements can be constructed according to this invention in which tabular grain silver halide emulsion layers are coated nearer the support than nontabular grain silver halide emulsion layers to reduce crossover, as illustrated by Sugimoto European Patent Application 0,084,637. By employing tabular grain emulsions, which in themselves reduce crossover in combination with the crossover reducing layers provided by this invention radiographic elements exhibiting extremely low crossover levels can be achieved while also achieving high photographic speed, low levels of granularity, high silver covering power, and rapid processing capabilities deemed highly desirable in radiography.
- The invention is further illustrated by the following examples.
- The following examples compare the performance of double coated radiographic elements exposed using blue emitting thulium activating lanthanum oxybromide phosphor intensifying screens. The radiographic elements were identical, except for the choice of the crossover reducing materials employed between the emulsion layer and the support on each major surface.
- The dye satisfying the requirements of the invention was
Dye 1/A shown above in Table II. The dye was employed in a particulate form, the mean diameter of the dye particles being 0.08 11m. - Tartrazine Yellow (C.I. Acid Yellow 23-C.I. 13.065), hereinafter referred to as C-1, was selected as a control exemplary of dyes which are water soluble and nonbleachable taught by the art to be used as a crossover reducing dye in a double coated radiographic element. To reduce wandering of the dye a cationic mordant poly(1-methyl-2-vinylpyridinium p-toluene sulfonate (hereinafter referred to as M-1) was used with the dye in a weight ratio of 5 parts of mordant per part of dye.
- Carey Lea Silver, hereinafter referred to as CLS, was selected as a control exemplary of a particulate material which is neither water soluble nor bleachable under conditions compatible with silver imaging.
- A series of double coated radiographic elements identical, except for the choice and concentration of crossover reducing material listed below in Table IV, were prepared as follows:
- Onto each side of a blue-tinted polyester film support was coated a gelatin hydrophilic colloid layer containing the crossover reducing material. The gelatin coating coverage was 0.11 g/m2.
- One control element was constructed with the same hydrophilic colloid layers, but without a crossover reducing material being present. This element is referred to as C-0.
- An emulsion layer was coated over each hydrophilic colloid layer. The blue recording silver bromide emulsion layer was coated at a coverage of 2.2 g/m2 silver and 2.2 g/m2 gelatin.
- Over each emulsion layer was coated a gelatin overcoat at a coverage of 0.91 g/m2.
- The hydrophilic colloid layers (including the emulsion layers) were hardened with bis(vinylsulfonylmethyl) ether at 1.0% of the gelatin weight.
- To permit crossover determinations, samples of the dual coated radiographic elements were exposed with a single intensifying screen placed in contact with one emulsion layer. Black paper was placed against the other emulsion side of the sample. The X-radiation source was a Picker VTX653 3-phase X-ray machine, with a Dunlee High-Speed PX1431-CQ-150 kVp 0.7/1.4mm focus tube.
- Exposure was made at 70 kVp, 32mAs, at a distance of 1.40 m. Filtration was with 3 mm AI equivalent (1.25 inherent + 1.75 al); Half Value Layer (HVL) - 2.6 mm Al. A 26 step AI wedge was used, differing in thickness by 2 mm per step.
-
- The film was in contact with the developer in each instance for less than 90 seconds.
- The density of the silver developed in each of the silver halide emulsion layers, the emulsion layer adjacent the intensifying screen and the nonadjacent emulsion layer separated from the intensifying screen by the film support. By plotting density produced by each emulsion layer versus the steps of the step-wedge (a measure of exposure), a sensitometric curve was generated for each emulsion layer. A higher density was produced for a given exposure in the emulsion nearest the intensifying screen. Thus, the two sensitometric curves were offset in speed. At three different density levels in the relatively straight line portions of the sensitometric curves between their toe and shoulders the difference in speed (A log E) between the two sensitometric curves was measured. These differences were then averaged and used in the following equation to calculate percent crossover:
-
- All of the crossover reducing materials of Table IV were shown capable of reducing crossover below 10 percent.
- The mordanted water soluble dye C-1 and the CLS both gave unacceptable results, since in neither instance did bleaching occur on processing. Further, the dye C-1 by reason of its wandering characteristic reduced photographic speed significantly, even though it was incorporated with a mordant to prevent wandering.
- The
dye 1/A.was entirely decolorized during processing. From Figure 2 it can be seen that the density of the element after processing was essentially similar to the element lacking a crossover reducing material. At the same time the capability of crossover reduction below 10 percent was demonstrated. Some loss of photographic speed was observed, but it is to be noted that, since the purpose of a crossover reducing agent is to prevent a portion of the light emitted by the screens from exposing the emulsion layers, some reduction in photographic speed is inherent in crossover reduction. - This example demonstrates the satisfactory performance of a bleachable particulate dye to reduce crossover without producing dye stain in the processed radiographic element and with only minimal impact on imaging speed. The control crossover reducing materials were unacceptable because of their high dye stain, and the control dye was unacceptable in producing an increased loss in imaging speed. Further, the control dye required the further incorporation of a mordant, which added to the drying load on the processor. Without the mordant being present the imaging speed loss would have been significantly higher.
- The procedure of Examples 1 through 6 was repeated, except that magenta dyes were substituted for testing, green sensitized radiographic emulsions were employed, and green emitting intensifying screens, Kodak Lanex Regular@ screens, were employed.
- The dye satisfying the requirements of the invention was
Dye 4/A shown above the Table II. The dye was employed in a particulate form, the mean diameter of the dye particles being 0.2 µm. - Acid Magenta (C.I. Acid Violet 19-C.I. 42,685), hereinafter referred to as C-2, was selected as a control exemplary of dyes which are water soluble and bleachable taught by the art to be used as a crossover reducing dye in a double coated radiographic element. To reduce wandering of the dye the cationic mordant M-1 was employed in a 5 parts mordant to 1 part dye weight ratio.
- 1,3-Bis[i-(4-sulfonylphenyl)-3-carboxy-2-pyrazolin-5-one-4] trimethine oxonol, disodium salt, hereinafter referred to as C-3, was selected as a control exemplary of magenta dyes which are water soluble and nonbleachable. Dye C-3 differed from
dye 10 disclosed on page 5 of U.K. Pat. Spec. 1,414,456 only in that the nuclei were joined by 3 methine groups instead of 5 (to shift absorption into the desired green spectral region). To reduce wandering of the dye cationic mordant M-1 was again employed in a 5 parts mordant to 1 part dye weight ratio. -
- From Table V it is apparent that the control crossover reducing dyes were inferior, both in terms of relatively lower crossover reduction and in terms of relatively greater speed loss imparted. The
dyes 4/A and C-2 exhibited essentially similar bleaching characteristics. The dye C-3 produced a significantly higher dye stain. - 1-(p-Carboxyphenyl)-3-methylpyrazolone (21.8 g), ethanol (100 ml), and triethylamine (14.6 g or 20 ml) were combined and boiled under reflux for 30 minutes. The mixture was chilled and then combined with 200 ml methanol, then 40 ml concentrated hydrochloric acid. A red precipitate formed immediately. The mixture was stirred at room temperature for 15 minutes and filtered. The precipitate was washed with 300 ml ethanol, 1000 ml methanol, 1000 ml ether, and then air dried to yield a dry weight of 12.4 g.
- The precipitate containing the dye was then purified through a number of washing and dissolu- tion/recrystallization steps. The precipitate was first slurried in 500 ml refluxing glacial acetic acid, cooled to room temperature, filtered, washed with 250 ml acetic acid, 250 ml H20, 250 ml methanol, and then dried. It was then dissolved in 100 ml hot dimethylsulfoxide and cooled to 40°C. 300 ml methanol was added, upon which a red precipitate formed, which was filtered, washed with methanol, acetone, and ligroin, and dried. This precipitate was dissolved in 200 ml methanol and 6 ml (4.38 g) triethylamine and heated to reflux. 4.8 ml of concentrated hydrochloric acid was added and a fine red precipitate was formed. The solution was filtered while hot and the precipitate was washed with methanol and acetone and dried. The precipitate was then dissolved in a refluxing mixture of 200 ml ethanol and 6.0 ml (4.38 g) triethylamine. 9.0 g of sodium iodide dissolved in 50 ml methanol was added. Upon cooling to room temperature, a red precipitate formed. The mixture was chilled in ice for one hour, then filtered. The precipitate was washed with ethanol, ligroin and dried to yield the sodium salt of the dye.
- The sodium salt of the dye was dissolved in 200 ml water with rapid stirring. 6.0 ml concentrated hydrochloric acid was added and a fluffy red precipitate formed. The mixture was filtered and the precipitate was washed with water, methanol, acetone, and ligroin, and dried to yield
Dye 1/0. - A solution of sodium nitrate (35.8 gm, 0.52 mol) in water (75 ml) was added to a slurry of 5-aminoisophthalic acid (90.6 gm, 0.50 mol) in 4.8 molar HCI (500 ml) at 0°C over 15 minutes with stirring. Stirring was continued for one hour at 0-5°C and the slurry was then added to a solution of sodium sulfite (270 gm, 2.2 mol) in water (1.21) all at one time, with stirring, at 2°C. The resulting homogeneous solution was heated at 50-60°C for 45 minutes. Concentrated HCI (60 ml) was added and the reaction mixture was heated further at 90°C for one hour. After cooling to RT another portion of concentrated HCI (500 ml) was added. The solid was isolated by filtration and washed on a funnel with acidified water, EtOH and ligroin in succession. The off-white solid was dissolved in a solution of NaOH (76 gm, 1.85 mol in 600 ml water). This solution was subsequently acidified with glacial acetic acid (166 ml, 3.0 mol) to yield a thick slurry. This was isolated by filtration, washed on the funnel with water, EtOH and ligroin in succession, and thoroughly dried in a vacuum oven at 80°C, and 10 mm Hg. The mp was above 300°C. The NMR and IR spectra were consistent with the structure for 5-hydrazino-1,3-benzenedicarboxylic acid. The product gave a positive test for hydrazine with Tollens' reagent.
- A slurry composed of the product 5-hydrazino-1,3-benzenedicarboxylic acid (64.7 gm, 0.33 mol), ethylacetoacetate (50.7 gm, 0.39 mol) and glacial acetic acid (250 ml) was stirred and refluxed for 22 hours. The mixture was cooled to RT and the product which had precipitated was isolated by filtration, washed with water, EtOH, Et20, and ligroin in succession and thoroughly dried in a vacuum oven at 80°C and 10 mm Hg. The mp of the solid was above 310°C. The NMR and IR spectra were consistent with the assigned structure. The product gave a negative test with Tollens' reagent. The C, H and N elemental analyses were in agreement with those calculated for the empirical formula for 1-(3,5-dicarboxyphenyl)-3-methyl-2-pyrazoline-5-one.
- A slurry composed of 1-(3,5-dicarboxyphenyl)-3-methyl-2-pyrazoline-5-one (44.6 grams, 0.17 mol), 4-dimethylaminobenzaldehyde (26.9 grams, 0.18 mol) and EtOH (500 mL) was heated at reflux for three hours. The reaction mixture was chilled in ice and the resulting crude orange product was isolated by filtration and washing with EtOH (200 mL). The product was purified by three repetitive slurries of the solid in acetone (1.4 I) at a reflux and filtering to recover the dye. The mp of the product was above 310°C. The NMR and IR spectra were consistent with the structure assigned. The C, H and N elemental analyses were in agreement with those calculated for the empirical formula for the dye.
- A slurry composed of 1-(4-carboxyphenyl)-3-methyl-2-pyrazolin-5-one (21.8 gm, 0.10 mol), 4- dimethylaminobenzaldehyde (14.9 gm, 0.10 mol) and EtOH (250 ml) was heated at reflux for two hours. The reaction mixture was cooled to RT resulting in a crude orange product which was isolated by filtration. The product was then washed with ether and dried. The product was purified further by making a slurry of the solid in EtOH (700 ml) at refluxing temperature and filtering the slurry to recover the dye. The treatment was repeated. The mp of the product was above 310°C. The NMR and IR spectra were consistent with the structure assigned. The C,H, and N elemental analyses were in agreement with those calculated for the empirical formula.
- 1-(4-Carboxyphenyl)-3-methyl-2-pyrazolin-5-one (2.18 gm 0.010 mol), 4-dimethylaminocinnamaldehyde (1.75 gm, 0.010 mol) and glacial acetic acid (10 ml) were mixed together to form a slurry. It was heated to reflux with stirring, held at reflux for five minutes and then cooled for RT. EtOH (20 ml) was added to the reaction mixture which was heated again to reflux, and held there for five minutes and cooled to RT. The product was isolated by filtration, washed in succession with ethanol and ligroin, and dried. The reaction was repeated twice on the same scale and the products obtained were all combined. They were treated further by first slurrying in refluxing EtOH (150 ml), isolating the solid by filtration while hot, and then slurrying in refluxing MeOH (200 ml) and isolating it again, while hot, by filtration. The mp was 282-284°C. The NMR and IR spectra were consistent for the structure assigned. The C, H and N elemental analyses were in agreement with those calculated for the empirical formula of the dye.
Claims (10)
Applications Claiming Priority (4)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US94563486A | 1986-12-23 | 1986-12-23 | |
US945634 | 1986-12-23 | ||
US07/073,256 US4803150A (en) | 1986-12-23 | 1987-07-13 | Radiographic element exhibiting reduced crossover |
US73256 | 1987-07-13 |
Publications (2)
Publication Number | Publication Date |
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EP0276566A1 EP0276566A1 (en) | 1988-08-03 |
EP0276566B1 true EP0276566B1 (en) | 1990-10-24 |
Family
ID=26754291
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
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EP19870311289 Expired EP0276566B1 (en) | 1986-12-23 | 1987-12-22 | Radiographic element exhibiting reduced crossover |
Country Status (4)
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EP (1) | EP0276566B1 (en) |
JP (1) | JP2567434B2 (en) |
CA (1) | CA1299424C (en) |
DE (1) | DE3765770D1 (en) |
Families Citing this family (21)
Publication number | Priority date | Publication date | Assignee | Title |
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US4997750A (en) * | 1989-02-23 | 1991-03-05 | Eastman Kodak Company | Radiographic elements with selected speed relationships |
EP0384634A3 (en) * | 1989-02-23 | 1990-11-07 | Eastman Kodak Company | Radiographic screen/film assemblies with improved detection quantum efficiencies |
CA2008456A1 (en) * | 1989-02-23 | 1990-08-23 | Robert E. Dickerson | Radiographic elements with selected contrast relationships |
JPH02264936A (en) * | 1989-04-06 | 1990-10-29 | Fuji Photo Film Co Ltd | Silver halide photographic sensitive material for x-ray photography |
DE69029676T2 (en) * | 1989-04-06 | 1997-05-07 | Fuji Photo Film Co Ltd | Silver halide photographic material and processing method therefor |
DE69024409T2 (en) * | 1989-06-05 | 1996-11-07 | Fuji Photo Film Co Ltd | X-ray photographic material |
USH1105H (en) * | 1990-03-29 | 1992-09-01 | Eastman Kodak Company | Asymmetrical radiographic elements, assemblies and packages |
JPH0414033A (en) * | 1990-05-08 | 1992-01-20 | Fuji Photo Film Co Ltd | Silver halide photographic sensitive material |
JP2835638B2 (en) * | 1990-05-08 | 1998-12-14 | 富士写真フイルム株式会社 | Silver halide photographic material |
US5041364A (en) * | 1990-10-01 | 1991-08-20 | Eastman Kodak Company | Diagnostic photographic elements exhibiting reduced glare following rapid access processing |
DE69318438T2 (en) * | 1992-02-14 | 1998-11-26 | Agfa Gevaert Nv | Photographic silver halide X-ray material with matching image tone and surface gloss |
EP0587229B1 (en) * | 1992-09-11 | 2002-05-08 | Agfa-Gevaert | Photographic element containing a filter dye for rapid processing applications |
EP0586749A1 (en) * | 1992-09-11 | 1994-03-16 | Agfa-Gevaert N.V. | Dyes absorbing light in the extended red and infrared region of the wavelength spectrum |
EP0587230B1 (en) * | 1992-09-11 | 2003-11-26 | Agfa-Gevaert | Photographic element containing a filter dye for rapid processing applications |
EP0586748A1 (en) * | 1992-09-11 | 1994-03-16 | Agfa-Gevaert N.V. | Filter dyes for rapid processing applications |
US5576156A (en) * | 1995-05-22 | 1996-11-19 | Eastman Kodak Company | Low crossover radiographic elements capable of being rapidly processed |
JPH09230540A (en) * | 1996-02-26 | 1997-09-05 | Fuji Photo Film Co Ltd | Silver halide photographic sensitive material and image forming method using that |
JP2000267227A (en) * | 1999-03-18 | 2000-09-29 | Fuji Photo Film Co Ltd | Silver halide color photographic sensitive material and image forming method |
US7579139B2 (en) | 2005-12-26 | 2009-08-25 | Fujifilm Corporation | Silver halide color photographic light-sensitive material |
ATE466311T1 (en) | 2006-03-10 | 2010-05-15 | Fujifilm Corp | FLAT PLATE PRECURSORS AND STACKS THEREOF |
JP2007264031A (en) | 2006-03-27 | 2007-10-11 | Fujifilm Corp | Silver halide color photographic sensitive material |
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Publication number | Priority date | Publication date | Assignee | Title |
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DE2119718C3 (en) * | 1970-04-24 | 1980-08-28 | Minnesota Mining And Manufacturing Co., Saint Paul, Minn. (V.St.A.) | Photosensitive recording material for radiographic purposes |
GB1414456A (en) * | 1971-11-05 | 1975-11-19 | Agfa Gevaert | Combination of photosensitive element suited for use in radiography |
JPS4868623A (en) * | 1971-12-21 | 1973-09-19 | ||
US4294916A (en) * | 1979-05-22 | 1981-10-13 | Ciba-Geigy Ag | Photographic silver halide material containing a dye filter or a dye anti-halation layer |
CA1148788A (en) * | 1979-06-29 | 1983-06-28 | Raymond G. Lemahieu | Photographic silver halide materials containing dispersed light-absorbing merostyryl dyes |
-
1987
- 1987-12-02 CA CA000553296A patent/CA1299424C/en not_active Expired - Fee Related
- 1987-12-22 EP EP19870311289 patent/EP0276566B1/en not_active Expired
- 1987-12-22 DE DE8787311289T patent/DE3765770D1/en not_active Expired - Lifetime
- 1987-12-23 JP JP62324178A patent/JP2567434B2/en not_active Expired - Fee Related
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EP0276566A1 (en) | 1988-08-03 |
JPH01172828A (en) | 1989-07-07 |
CA1299424C (en) | 1992-04-28 |
DE3765770D1 (en) | 1990-11-29 |
JP2567434B2 (en) | 1996-12-25 |
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