EP0542354B1 - Method of developing x-ray materials - Google Patents
Method of developing x-ray materials Download PDFInfo
- Publication number
- EP0542354B1 EP0542354B1 EP19920203420 EP92203420A EP0542354B1 EP 0542354 B1 EP0542354 B1 EP 0542354B1 EP 19920203420 EP19920203420 EP 19920203420 EP 92203420 A EP92203420 A EP 92203420A EP 0542354 B1 EP0542354 B1 EP 0542354B1
- Authority
- EP
- European Patent Office
- Prior art keywords
- per liter
- grams
- developing
- developing solution
- phenyl
- 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 - Lifetime
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- 239000000463 material Substances 0.000 title claims description 30
- 238000000034 method Methods 0.000 title claims description 23
- 238000012545 processing Methods 0.000 claims description 49
- 239000003795 chemical substances by application Substances 0.000 claims description 38
- NLKNQRATVPKPDG-UHFFFAOYSA-M potassium iodide Chemical compound [K+].[I-] NLKNQRATVPKPDG-UHFFFAOYSA-M 0.000 claims description 32
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 claims description 30
- -1 iodide ions Chemical class 0.000 claims description 24
- 150000001875 compounds Chemical class 0.000 claims description 14
- 239000000203 mixture Substances 0.000 claims description 14
- DSVIHYOAKPVFEH-UHFFFAOYSA-N 4-(hydroxymethyl)-4-methyl-1-phenylpyrazolidin-3-one Chemical compound N1C(=O)C(C)(CO)CN1C1=CC=CC=C1 DSVIHYOAKPVFEH-UHFFFAOYSA-N 0.000 claims description 11
- ADZWSOLPGZMUMY-UHFFFAOYSA-M silver bromide Chemical compound [Ag]Br ADZWSOLPGZMUMY-UHFFFAOYSA-M 0.000 claims description 8
- ZUNKMNLKJXRCDM-UHFFFAOYSA-N silver bromoiodide Chemical compound [Ag].IBr ZUNKMNLKJXRCDM-UHFFFAOYSA-N 0.000 claims description 8
- 238000011161 development Methods 0.000 claims description 7
- GGZHVNZHFYCSEV-UHFFFAOYSA-N 1-Phenyl-5-mercaptotetrazole Chemical compound SC1=NN=NN1C1=CC=CC=C1 GGZHVNZHFYCSEV-UHFFFAOYSA-N 0.000 claims description 5
- LRUDIIUSNGCQKF-UHFFFAOYSA-N 5-methyl-1H-benzotriazole Chemical compound C1=C(C)C=CC2=NNN=C21 LRUDIIUSNGCQKF-UHFFFAOYSA-N 0.000 claims description 5
- 239000004285 Potassium sulphite Substances 0.000 claims description 4
- XMBWDFGMSWQBCA-UHFFFAOYSA-M iodide Chemical compound [I-] XMBWDFGMSWQBCA-UHFFFAOYSA-M 0.000 claims description 4
- 229940006461 iodide ion Drugs 0.000 claims description 4
- BHZRJJOHZFYXTO-UHFFFAOYSA-L potassium sulfite Chemical compound [K+].[K+].[O-]S([O-])=O BHZRJJOHZFYXTO-UHFFFAOYSA-L 0.000 claims description 4
- 235000019252 potassium sulphite Nutrition 0.000 claims description 4
- 150000002500 ions Chemical class 0.000 claims description 2
- 239000000243 solution Substances 0.000 description 44
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 18
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 18
- 239000000839 emulsion Substances 0.000 description 15
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 12
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 12
- 239000004332 silver Substances 0.000 description 10
- 229910052709 silver Inorganic materials 0.000 description 10
- IOLCXVTUBQKXJR-UHFFFAOYSA-M potassium bromide Chemical compound [K+].[Br-] IOLCXVTUBQKXJR-UHFFFAOYSA-M 0.000 description 8
- 238000001035 drying Methods 0.000 description 7
- CMCWWLVWPDLCRM-UHFFFAOYSA-N phenidone Chemical compound N1C(=O)CCN1C1=CC=CC=C1 CMCWWLVWPDLCRM-UHFFFAOYSA-N 0.000 description 6
- 239000004848 polyfunctional curative Substances 0.000 description 6
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 6
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 description 6
- 239000012895 dilution Substances 0.000 description 5
- 238000010790 dilution Methods 0.000 description 5
- 235000010339 sodium tetraborate Nutrition 0.000 description 5
- 239000000654 additive Substances 0.000 description 4
- 229910021538 borax Inorganic materials 0.000 description 4
- UQGFMSUEHSUPRD-UHFFFAOYSA-N disodium;3,7-dioxido-2,4,6,8,9-pentaoxa-1,3,5,7-tetraborabicyclo[3.3.1]nonane Chemical compound [Na+].[Na+].O1B([O-])OB2OB([O-])OB1O2 UQGFMSUEHSUPRD-UHFFFAOYSA-N 0.000 description 4
- 239000003755 preservative agent Substances 0.000 description 4
- 230000035945 sensitivity Effects 0.000 description 4
- GEHJYWRUCIMESM-UHFFFAOYSA-L sodium sulfite Chemical compound [Na+].[Na+].[O-]S([O-])=O GEHJYWRUCIMESM-UHFFFAOYSA-L 0.000 description 4
- 239000004328 sodium tetraborate Substances 0.000 description 4
- GZPBVLUEICLBOA-UHFFFAOYSA-N 4-(dimethylamino)-3,5-dimethylphenol Chemical compound CN(C)C1=C(C)C=C(O)C=C1C GZPBVLUEICLBOA-UHFFFAOYSA-N 0.000 description 3
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 239000012670 alkaline solution Substances 0.000 description 3
- 239000011248 coating agent Substances 0.000 description 3
- 238000000576 coating method Methods 0.000 description 3
- 239000012141 concentrate Substances 0.000 description 3
- 238000009472 formulation Methods 0.000 description 3
- 239000004615 ingredient Substances 0.000 description 3
- 238000004806 packaging method and process Methods 0.000 description 3
- 229910000027 potassium carbonate Inorganic materials 0.000 description 3
- 230000002335 preservative effect Effects 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- BDKLKNJTMLIAFE-UHFFFAOYSA-N 2-(3-fluorophenyl)-1,3-oxazole-4-carbaldehyde Chemical compound FC1=CC=CC(C=2OC=C(C=O)N=2)=C1 BDKLKNJTMLIAFE-UHFFFAOYSA-N 0.000 description 2
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 description 2
- 108010010803 Gelatin Proteins 0.000 description 2
- SXRSQZLOMIGNAQ-UHFFFAOYSA-N Glutaraldehyde Chemical compound O=CCCCC=O SXRSQZLOMIGNAQ-UHFFFAOYSA-N 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- LSNNMFCWUKXFEE-UHFFFAOYSA-N Sulfurous acid Chemical class OS(O)=O LSNNMFCWUKXFEE-UHFFFAOYSA-N 0.000 description 2
- 230000002378 acidificating effect Effects 0.000 description 2
- XYXNTHIYBIDHGM-UHFFFAOYSA-N ammonium thiosulfate Chemical compound [NH4+].[NH4+].[O-]S([O-])(=O)=S XYXNTHIYBIDHGM-UHFFFAOYSA-N 0.000 description 2
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 description 2
- 239000004327 boric acid Substances 0.000 description 2
- 150000004691 decahydrates Chemical class 0.000 description 2
- 230000003247 decreasing effect Effects 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 229920000159 gelatin Polymers 0.000 description 2
- 239000008273 gelatin Substances 0.000 description 2
- 235000019322 gelatine Nutrition 0.000 description 2
- 235000011852 gelatine desserts Nutrition 0.000 description 2
- 230000000977 initiatory effect Effects 0.000 description 2
- 230000001788 irregular Effects 0.000 description 2
- 239000010410 layer Substances 0.000 description 2
- 238000011068 loading method Methods 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 239000011241 protective layer Substances 0.000 description 2
- GHMLBKRAJCXXBS-UHFFFAOYSA-N resorcinol Chemical compound OC1=CC=CC(O)=C1 GHMLBKRAJCXXBS-UHFFFAOYSA-N 0.000 description 2
- 235000017281 sodium acetate Nutrition 0.000 description 2
- 229940087562 sodium acetate trihydrate Drugs 0.000 description 2
- 235000010265 sodium sulphite Nutrition 0.000 description 2
- HLWRUJAIJJEZDL-UHFFFAOYSA-M sodium;2-[2-[bis(carboxymethyl)amino]ethyl-(carboxymethyl)amino]acetate Chemical compound [Na+].OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC([O-])=O HLWRUJAIJJEZDL-UHFFFAOYSA-M 0.000 description 2
- 239000007858 starting material Substances 0.000 description 2
- LSNNMFCWUKXFEE-UHFFFAOYSA-L sulfite Chemical compound [O-]S([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-L 0.000 description 2
- 150000004684 trihydrates Chemical class 0.000 description 2
- CARFETJZUQORNQ-UHFFFAOYSA-N 1h-pyrrole-2-thiol Chemical class SC1=CC=CN1 CARFETJZUQORNQ-UHFFFAOYSA-N 0.000 description 1
- VZSRBBMJRBPUNF-UHFFFAOYSA-N 2-(2,3-dihydro-1H-inden-2-ylamino)-N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]pyrimidine-5-carboxamide Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)C(=O)NCCC(N1CC2=C(CC1)NN=N2)=O VZSRBBMJRBPUNF-UHFFFAOYSA-N 0.000 description 1
- NYZOFSCKOSTMCQ-UHFFFAOYSA-N 4-hydroxy-4-(hydroxymethyl)-1-phenylpyrazolidin-3-one Chemical compound N1C(=O)C(CO)(O)CN1C1=CC=CC=C1 NYZOFSCKOSTMCQ-UHFFFAOYSA-N 0.000 description 1
- ZZEYCGJAYIHIAZ-UHFFFAOYSA-N 4-methyl-1-phenylpyrazolidin-3-one Chemical compound N1C(=O)C(C)CN1C1=CC=CC=C1 ZZEYCGJAYIHIAZ-UHFFFAOYSA-N 0.000 description 1
- INVVMIXYILXINW-UHFFFAOYSA-N 5-methyl-1h-[1,2,4]triazolo[1,5-a]pyrimidin-7-one Chemical compound CC1=CC(=O)N2NC=NC2=N1 INVVMIXYILXINW-UHFFFAOYSA-N 0.000 description 1
- WSGURAYTCUVDQL-UHFFFAOYSA-N 5-nitro-1h-indazole Chemical compound [O-][N+](=O)C1=CC=C2NN=CC2=C1 WSGURAYTCUVDQL-UHFFFAOYSA-N 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical class [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- FBPFZTCFMRRESA-FSIIMWSLSA-N D-Glucitol Natural products OC[C@H](O)[C@H](O)[C@@H](O)[C@H](O)CO FBPFZTCFMRRESA-FSIIMWSLSA-N 0.000 description 1
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 description 1
- AVXURJPOCDRRFD-UHFFFAOYSA-N Hydroxylamine Chemical compound ON AVXURJPOCDRRFD-UHFFFAOYSA-N 0.000 description 1
- NPYPAHLBTDXSSS-UHFFFAOYSA-N Potassium ion Chemical compound [K+] NPYPAHLBTDXSSS-UHFFFAOYSA-N 0.000 description 1
- 206010070834 Sensitisation Diseases 0.000 description 1
- 239000004133 Sodium thiosulphate Substances 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 1
- 239000012190 activator Substances 0.000 description 1
- 150000001299 aldehydes Chemical class 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 229910001513 alkali metal bromide Inorganic materials 0.000 description 1
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 1
- 239000001164 aluminium sulphate Substances 0.000 description 1
- 235000011128 aluminium sulphate Nutrition 0.000 description 1
- 235000010323 ascorbic acid Nutrition 0.000 description 1
- 229960005070 ascorbic acid Drugs 0.000 description 1
- 239000011668 ascorbic acid Substances 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- YOALFLHFSFEMLP-UHFFFAOYSA-N azane;2,2,3,3,4,4,5,5,6,6,7,7,8,8,8-pentadecafluorooctanoic acid Chemical compound [NH4+].[O-]C(=O)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)F YOALFLHFSFEMLP-UHFFFAOYSA-N 0.000 description 1
- QRUDEWIWKLJBPS-UHFFFAOYSA-N benzotriazole Chemical compound C1=CC=C2N[N][N]C2=C1 QRUDEWIWKLJBPS-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 150000001642 boronic acid derivatives Chemical class 0.000 description 1
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 1
- 125000001309 chloro group Chemical group Cl* 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 238000000326 densiometry Methods 0.000 description 1
- 230000001627 detrimental effect Effects 0.000 description 1
- BUACSMWVFUNQET-UHFFFAOYSA-H dialuminum;trisulfate;hydrate Chemical compound O.[Al+3].[Al+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O BUACSMWVFUNQET-UHFFFAOYSA-H 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 230000006870 function Effects 0.000 description 1
- 229960000587 glutaral Drugs 0.000 description 1
- 229910021505 gold(III) hydroxide Inorganic materials 0.000 description 1
- 150000004820 halides Chemical class 0.000 description 1
- XMBWDFGMSWQBCA-UHFFFAOYSA-N hydrogen iodide Chemical class I XMBWDFGMSWQBCA-UHFFFAOYSA-N 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 150000004679 hydroxides Chemical class 0.000 description 1
- 238000010348 incorporation Methods 0.000 description 1
- 238000007603 infrared drying Methods 0.000 description 1
- 150000002484 inorganic compounds Chemical class 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 229920003229 poly(methyl methacrylate) Polymers 0.000 description 1
- 229920000120 polyethyl acrylate Polymers 0.000 description 1
- 229920000139 polyethylene terephthalate Polymers 0.000 description 1
- 239000005020 polyethylene terephthalate Substances 0.000 description 1
- 239000004926 polymethyl methacrylate Substances 0.000 description 1
- 229910001414 potassium ion Inorganic materials 0.000 description 1
- RWPGFSMJFRPDDP-UHFFFAOYSA-L potassium metabisulfite Chemical compound [K+].[K+].[O-]S(=O)S([O-])(=O)=O RWPGFSMJFRPDDP-UHFFFAOYSA-L 0.000 description 1
- 239000004297 potassium metabisulphite Substances 0.000 description 1
- 235000010263 potassium metabisulphite Nutrition 0.000 description 1
- ZNNZYHKDIALBAK-UHFFFAOYSA-M potassium thiocyanate Chemical compound [K+].[S-]C#N ZNNZYHKDIALBAK-UHFFFAOYSA-M 0.000 description 1
- 229940116357 potassium thiocyanate Drugs 0.000 description 1
- 238000004321 preservation Methods 0.000 description 1
- NDGRWYRVNANFNB-UHFFFAOYSA-N pyrazolidin-3-one Chemical compound O=C1CCNN1 NDGRWYRVNANFNB-UHFFFAOYSA-N 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 239000000837 restrainer Substances 0.000 description 1
- 230000008313 sensitization Effects 0.000 description 1
- 239000003352 sequestering agent Substances 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 159000000000 sodium salts Chemical class 0.000 description 1
- AKHNMLFCWUSKQB-UHFFFAOYSA-L sodium thiosulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=S AKHNMLFCWUSKQB-UHFFFAOYSA-L 0.000 description 1
- 235000019345 sodium thiosulphate Nutrition 0.000 description 1
- 239000000600 sorbitol Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- PXQLVRUNWNTZOS-UHFFFAOYSA-N sulfanyl Chemical class [SH] PXQLVRUNWNTZOS-UHFFFAOYSA-N 0.000 description 1
- 239000001117 sulphuric acid Substances 0.000 description 1
- 235000011149 sulphuric acid Nutrition 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 150000003567 thiocyanates Chemical class 0.000 description 1
- 150000004764 thiosulfuric acid derivatives Chemical class 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- NRZWQKGABZFFKE-UHFFFAOYSA-N trimethylsulfonium Chemical compound C[S+](C)C NRZWQKGABZFFKE-UHFFFAOYSA-N 0.000 description 1
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
- G03C5/00—Photographic processes or agents therefor; Regeneration of such processing agents
- G03C5/26—Processes using silver-salt-containing photosensitive materials or agents therefor
- G03C5/29—Development processes or agents therefor
- G03C5/305—Additives other than developers
Definitions
- This invention relates to a method of processing, more particularly to a method of development of medical X-ray films. More specifically, this invention relates to application in the said method of an improved aqueous alkaline photographic developing solution that is especially adapted for the use in the development of X-ray films.
- developing solutions for use with X-ray film have typically been formulated using hydroquinone as the primary developing agent, 1-phenyl-3-pyrazolidinone as a super-additive auxiliary developing agent and glutaric aldehyd as a hardening agent.
- These developing solutions have been packaged as three-part formulations.
- the need for the added cost and complexity of three-part packaging has been dictated by the fact that glutaric aldehyd tends to react with 1-phenyl-3-pyrazolidinone, that 1-phenyl-3-pyrazolidinone tends to oxidize in alkaline solution and that glutaric aldehyde tends to polymerize in alkaline solution.
- the hydroquinone has been packaged in a first part which is alkaline
- the 1-phenyl-3-pyrazolidinone has been packaged in a second part which is acidic
- the glutaric aldehyd has been packaged in a third part which is acidic.
- the three parts Prior to use the three parts are blended together and diluted with water to give the appropriate concentration and alkaline pH for use as working developing solution.
- These developing solutions are used in the standard 90 seconds processing of commercial medical X-ray materials having a film support and on one or both sides thereof silver bromide or silver bromoiodide emulsion layers.
- EP Application 428,455 the accelerated processing of forehardened X-ray films has been described leading to sensitometric results comparable to those obtained with standard 90 seconds processing with aldehyde containing developers of conventional X-ray materials.
- fore-hardened X-ray films are developed with a developing solution having a pH in the range of 9 to 12, being substantially free of both aldehydic hardening agents and silver halide solvents and comprising dihydroxybenzene developing agent, a superadditive developing agent, an alkaline agent, an organic anti-foggant and a preservative, the super-additive auxiliary developing agent being present in a concentration of at least 3.5 grams per liter of said developing solution and being a 4,4'-disubstituted-1-aryl-3-pyrazolidinone in particular 4-methyl-4-hydroxymethyl-1-phenyl-3-pyrazolidinone.
- the use of the latter auxiliary developing agent in this context is also known from USP 4,957,
- the developing solution becomes quite expensive due to the high amounts of expensive auxiliary developing agents.
- the degree of concentration is limited by the crystallization tendency of the auxiliary developing agent.
- auxiliary developer 1-phenyl-3-pyrazolidinone is not preferred due to its tendency to crystallize into the solution as its solubility is low, due to its insufficient stability so that it decomposes and due to the resulting fog increase that is sensitometrically unacceptable.
- 4-methyl-1-phenyl-3-pyrazolidinone doesn't satisfy either as the preservation stability is rather poor. More substituted compounds are more stable in alkaline solutions but the cost is increasing to unacceptable levels. 4-hydroxymethyl-4-methyl-1-phenyl-3-pyrazolidinone is very effective although the cost remains high.
- a further object of the present invention is to provide a method for processing which may make use of a one-part package hardener-free concentrate for preparing developing solutions for rapid processing of fore-hardened X-ray materials, in particular X-ray materials with tabular silver halide emulsions as well as a method for processing which may make use of three-part package concentrates for preparing hardener containing developing solutions for rapid processing.
- the above objects are accomplished by providing a method of processing of exposed silver bromide or silver bromoiodide X-ray film materials which may be processed in a total processing time of 60 seconds or less in an aqueous alkaline photographic developing solution, having a pH in the range of 9 to 12, comprising a dihydroxybenzene developing agent, 4-hydroxymethyl-4-methyl-1-phenyl-3-pyrazolidinone as an auxiliary developing agent, in an amount of from 1.0 g to less than 3.5 g per liter of said developing solution , and at least one organic antifoggant characterised in that it further contains a compound providing iodide ions in an amount between 4 10 -5 and 8 10 -4 valents of ions per liter.
- the iodide ions providing compound which is preferably potassium iodide
- an amount of less than 3.5 g of said auxiliary developing agent it is possible to achieve a very short process time while meeting all sensitometric requirements that are important for X-ray film development provided that a iodide ion releasing compound is present.
- iodide ions for part of the auxiliary developing agent in the developing solution, the cost of the developer can be reduced.
- auxiliary developing agent reduces the tendency of said agent to crystallize, so that a more concentrated one-part developing solution can be offered to the customer. So it is possible e.g. to deliver very concentrated developer solutions, the customer has to dilute "1+3", "1" standing for the volume of concentrated developer solution and "3" for the volume of water, instead of e.g. "1+1.5" indicating that the developer solution is less concentrated, allowing less water to be added to make it ready for use.
- iodide ions providing compound or compounds in an adapted amount to one of the three parts.
- iodide ions providing compounds and the 4-hydroxymethyl-4-hydroxy-1-phenyl-3-pyrazolidinone are added to the alkaline developer part A.
- one- or three-part package formulation can be used to prepare the developing solution used for rapidly processing silver bromide or silver bromoiodide X-ray films within a total cycle including developing, fixing, rinsing and drying of less than 60 seconds.
- a developing time of 9.3 (respectively 14) seconds for a 38 (respectively 45) seconds processing cycle can be attained. Even for longer processing times of 90 seconds specific advantages are encountered.
- a more consumer-friendly low temperature processing is accessible: temperatures lower than 35°C being allowed instead of the normally used 35°C, is accessible. Economical and environmental advantages are thus offered without loss of sensitometric characteristics.
- the developing solution may be free, or at least substantially free, of aldehydic hardening agents such as glutaric aldehyd.
- aldehydic hardening agents such as glutaric aldehyd.
- the developing solution is preferably free, or is at least substantially free, of silver halide solvents, such as thiosulphates or thiocyanates, these solvents being detrimental to its performance in development of fore-hardened X-ray films, providing an unacceptable sensitometry.
- silver halide solvents such as thiosulphates or thiocyanates
- dihydroxybenzene developing agents employed in the aqueous alkaline developing solutions used in the method of this invention are well known and widely used in photographic processing, hydroquinone being a preferred developing agent of this class.
- Other useful dihydroxybenzene developing agents have been described in EP Application 428,455. A combination of two or more of these developing agents is also possible.
- the developing solution must include 4-hydroxymethyl-4-methyl-1-phenyl-3-pyrazolidinone functioning as an auxiliary super-additive developing agent.
- iodide ions in black and white developers, as e.g. US Patent 5,037,727 where iodide ions are used in an alkaline activator to control the image tone, the combination with foresaid auxiliary developing agent or agents to meet the desired sensitometric requirements was not described untill now.
- a preferred iodide ion providing compound is potassium iodide, although other alkaline or alkaline earth metal salts of iodide are principally usable as well as other inorganic or organic compounds providing iodide ions. So it has been proved that the replacement in equimolar amounts of the potassium ion by e.g. trimethylsulphonium-, tetraphenylphosphonium- and/or tetraethylammonium-ions is offering the same sensitometric results.
- Suitable alkaline agents which can be included in the developing solution to maintain the desired alkaline pH include hydroxides such as sodium hydroxide, carbonates such as sodium carbonate and borates such as sodium tetraborate.
- organic antifoggants particularly suitable are benztriazole antifoggants.
- Further preferred classes of organic antifoggants include mercapto azoles and mercapto azines.
- a combination in adjusted amounts of two or more of said organic antifoggants which have been described in detail in EP Application 428,455 is also possible.
- organic antifoggant inorganic restrainers or antifoggants can be utilized, such as alkali metal bromides, preferably potassium bromide.
- a sulphite preservative can be added in such an amount as to protect the developing agents against this disadvantageous effect, thereby providing sufficiently good stability characteristics.
- Useful sulphite preservatives include sulphites, bisulphites, metabisulphites and carbonyl bisulphite adducts present as alkaline metal ion or ammonium ion salts.
- Alternatives like hydroxylamine and ascorbic acid can be used alone or in combination with one another or with said sulphites.
- Additional optional additives include sequestering agents, surfactants and organic solvents. Examples of these ingredients are given in EP Application 428,455.
- aqueous alkaline developing solutions used in accordance with the method of this invention can vary widely with regard to the concentration of the various ingredients included therein.
- the dihydroxybenzene developing agent e.g. hydroquinone
- the 4-hydroxymethyl-4-methyl-1-phenyl-3-pyrazolidinone is used in an amount of 1.0 g to less than 3.5 grams per liter
- the iodide ion releasing compound e.g.
- potassium iodide is used in an amount of 4.10 -5 to 8.10 -4 equivalents per liter
- 5-methyl-benzotriazole is used in an amount of about 8.10 -5 to about 8.10 -4 moles per liter
- 1-phenyl-5-mercaptotetrazole is used in an amount of about 0 to 3.10 -4 moles.
- the preservative e.g. potassium sulphite
- Auxiliary agents present in the developer are sodium tetraborate in an amount of 0 to 25 grams per liter, potassium carbonate in an amount of 5 to 20 grams per liter, potassium bromide in an amount of 1 to 5 grams per liter, diethylene glycol in an amount of 10 to 50 grams per liter, ethylenediaminetetraacetic acid (sodium salt) in an amount of 1 to 5 grams per liter.
- the pH of the developing solution is in the range from 9 to 12 and more preferably in the range from 9.5 to 11.
- the developing process is typically carried out at a temperature of about 25°C to about 50°C.
- very short developing times such as 10 seconds or less, are feasable, with total processing times of less than 45 seconds, preferably 38 seconds, being contemplated.
- a typical 38 seconds cycle has development, fixing , rinsing and drying times of 9.3 seconds at 35°C, 6.6 seconds at 35°C, 4.4 seconds at 20°C and 6.7 seconds at 46°C respectively, time for film transport to be added to reach 38 seconds altogether.
- the drying temperature of 46°C is referring to an infrared drying system, whereas with a conventional drying system the temperature is about 55°C.
- the invention is directed to the development of medical X-ray materials. These materials contain emulsions based on silver bromide or silver bromoiodide grains, preferably-containing at most 2.5 mole % of iodide ions.
- the silver halide grains of the photographic emulsions used according to the present invention may have a regular crystalline form such as a cubic or octahedral form or they may have a transition form. They may also have an irregular crystalline form such as a spherical form or a tabular form, or may otherwise have a composite crystal form comprising a mixture of said regular and irregular crystalline forms.
- the silver halide grains may have a multilayered grain structure. According to a simple embodiment the grains may comprise a core and a shell, which may have different halide compositions and/or may have undergone different modifications such as the addition of dopes. Besides having a differently composed core and shell the silver halide grains may also comprise different phases inbetween.
- Two or more types of silver halide emulsions that have been prepared differently can be mixed for forming a photographic emulsion for use in accordance with the present invention.
- the average size of the silver halide grains may range from 0.1 to 1.00 ⁇ m, preferably from 0.3 to 0.7 ⁇ m.
- the size distribution of the silver halide particles of the photographic emulsions to be used according to the present invention can be homodisperse or heterodisperse, a homodisperse size distribution being obtained when 95% of the grains have a size that does not deviate more than 30% from the average grain size.
- the thus obtained tabular grain emulsion, containing 75 grams of gelatin pro mole of AgNO 3 had the following characteristics:
- This emulsion was chemically sensitised in the presence of dye 1 (anhydro-5,5'-dichloro-3,3'-bis(n.sulfobutyl)-9-ethyloxacarbocyanine hydroxide), chloro auric acid, sodium thiosulphate and potassium thiocyanate.
- dye 1 anhydro-5,5'-dichloro-3,3'-bis(n.sulfobutyl)-9-ethyloxacarbocyanine hydroxide
- chloro auric acid sodium thiosulphate
- sodium thiosulphate sodium thiosulphate
- potassium thiocyanate potassium thiocyanate
- the coating weight is expressed in grams per square meter per side gelatin 1.10 polymethylmethacrylate (average particle diameter : 3.5 ⁇ m) 0.023 ammoniumperfluorocaprylate 0.0075 C 17 H 15 -CO-NH-(CH 2 -CH 2 -O-) 17 -H 0.0188 formaldehyde 0.1
- Both emulsion layer and protective layer were simultaneously coated on both sides of a polyethylene terephthalate film support of 175 ⁇ m thickness.
- the resulting photographic material contained 3.5 grams of AgNO 3 per m 2 per side.
- This material is the commercially available medical X-ray material CURIX ORTHO STA manufactured by Agfa-Gevaert N.V., Belgium, which is a double coated film suitable for use with green light emitting X-ray sensitive screens.
- Samples of the photographic materials 1 and 2 were illuminated using a continuous wedge with green light of 540nm during 0.02 seconds and were processed under the circumstances described further; material 1 being processed in accordance with the present invention in 38 sec. whereas material 2 being processed for comparison purposes in the known 90 sec. commercial processing cycle.
- the density as a function of the light dose was measured and therefrom were determined : fog level (with an accuracy of 0.001 density point), the relative speed S at a density of 1 above fog (reference was set to a speed of 100), maximum density DMAX, the gradient AG between 0.25 above fog and 2.0 above fog, the gradient AGTOE between 0.1 and 1.0 above fog and the gradient AGBACK between 1.0 and 2.5 above fog.
- Samples of the commercial CURIX ORTHO STA were exposed as described in example 1 and processed on the one hand in a commercial 90 sec. processing cycle as referred to in example 1 and on the other hand in a 38 seconds processing with hardener containing developer.
- composition of the developing and fixing solutions that were applied for the 38 sec. processing are as follows:
- composition of developer II (containing a hardener):
- the three parts were mixed in the following ratio : 250 ml of part A, 700 ml of water, 25 ml of part B and 25 ml of part C. No starter solution was added. A pH of 10.40 at 25°C was measured.
- Composition fixer II (containing a hardener):
- the fixer ready for use was then made by mixing concentrated part A, water and concentrated part B in the following ratio: respectively 250 ml, 687.5 ml and 62.5 ml. A pH of this mixture of 4.25 at 25°C was measured.
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Description
- This invention relates to a method of processing, more particularly to a method of development of medical X-ray films. More specifically, this invention relates to application in the said method of an improved aqueous alkaline photographic developing solution that is especially adapted for the use in the development of X-ray films.
- Heretofore, developing solutions for use with X-ray film have typically been formulated using hydroquinone as the primary developing agent, 1-phenyl-3-pyrazolidinone as a super-additive auxiliary developing agent and glutaric aldehyd as a hardening agent. These developing solutions have been packaged as three-part formulations. The need for the added cost and complexity of three-part packaging has been dictated by the fact that glutaric aldehyd tends to react with 1-phenyl-3-pyrazolidinone, that 1-phenyl-3-pyrazolidinone tends to oxidize in alkaline solution and that glutaric aldehyde tends to polymerize in alkaline solution. To avoid these problems, the hydroquinone has been packaged in a first part which is alkaline, the 1-phenyl-3-pyrazolidinone has been packaged in a second part which is acidic and the glutaric aldehyd has been packaged in a third part which is acidic. Prior to use the three parts are blended together and diluted with water to give the appropriate concentration and alkaline pH for use as working developing solution.
- These developing solutions are used in the standard 90 seconds processing of commercial medical X-ray materials having a film support and on one or both sides thereof silver bromide or silver bromoiodide emulsion layers.
- There is a tendency of further decreasing the total processing time of X-ray materials in particular to less than 60 seconds e.g. 45 seconds processing and even 38 seconds processing. The requirement is that the sensitometry obtained with such short processing times should match the sensitometry of conventional radiographic materials now processed in 90 seconds as referred to above.
- Decreasing processing time is possible when using X-ray materials that have been adequately fore-hardened so that they absorb less water and lend themselves to accelerated processing and drying. However increasing the level of fore-hardening usually results in a decrease of the covering power so that not all materials can be adequately fore-hardened. Tabular grain emulsions lend themselves to increased levels of fore-hardening because they are less sensitive to a decrease in covering power.
- In EP Application 428,455 the accelerated processing of forehardened X-ray films has been described leading to sensitometric results comparable to those obtained with standard 90 seconds processing with aldehyde containing developers of conventional X-ray materials. In said EP Application 428,455 fore-hardened X-ray films are developed with a developing solution having a pH in the range of 9 to 12, being substantially free of both aldehydic hardening agents and silver halide solvents and comprising dihydroxybenzene developing agent, a superadditive developing agent, an alkaline agent, an organic anti-foggant and a preservative, the super-additive auxiliary developing agent being present in a concentration of at least 3.5 grams per liter of said developing solution and being a 4,4'-disubstituted-1-aryl-3-pyrazolidinone in particular 4-methyl-4-hydroxymethyl-1-phenyl-3-pyrazolidinone. The use of the latter auxiliary developing agent in this context is also known from USP 4,957,856.
- Although sensitometric responses similar to those achieved with conventional aldehydic developers in very short processing times are claimed, the developing solution becomes quite expensive due to the high amounts of expensive auxiliary developing agents. Moreover although one-part packaging of the developing solution is possible the degree of concentration is limited by the crystallization tendency of the auxiliary developing agent. Where it was possible to concentrate the three-part package for the 90 seconds processing so that for a developing solution ready for use up to three volumes of water could be added to part A, the one-part package of EP Application 428,455 can be concentrated only to a degree that maximum dilution is up to two times.
- In rapid processing cycles of less than 90 seconds the aim is to maintain unchanged sensitometric characteristics according to the previously formulated requirements. Losses in sensitivity or gradation can be compensated e.g. by reducing the amount of antifoggant or increasing pH of the developer. As a more alkali containing developer is more sensitive to oxidation phenomena this way should not be followed. This can also be stated for a decrease of the amount of antifogging agent, leading to a tremendous fog increase and a gradation decrease. Looking for a suitable auxiliary developer 1-phenyl-3-pyrazolidinone is not preferred due to its tendency to crystallize into the solution as its solubility is low, due to its insufficient stability so that it decomposes and due to the resulting fog increase that is sensitometrically unacceptable. As another auxiliary developing compound 4-methyl-1-phenyl-3-pyrazolidinone doesn't satisfy either as the preservation stability is rather poor. More substituted compounds are more stable in alkaline solutions but the cost is increasing to unacceptable levels. 4-hydroxymethyl-4-methyl-1-phenyl-3-pyrazolidinone is very effective although the cost remains high.
- It is an object of the present invention to provide a method of processing wherein a developing solution suitable for rapid processing of medical X-ray films, materials, is applied, said materials containing silver bromide or silver bromoiodide emulsions, preferably in an overall processing time of 60 seconds or less with sensitometric results matching those with standard 90 seconds processing.
- It is another object of the present invention to provide a method of developing a silver bromide or silver bromoiodide material with a hydroquinone/4-hydroxymethyl-1-phenyl-3-pyrazolidinone developing solution with a reduced amount of the said 3-pyrazolidinone thus making the developing solution less expensive.
- A further object of the present invention is to provide a method for processing which may make use of a one-part package hardener-free concentrate for preparing developing solutions for rapid processing of fore-hardened X-ray materials, in particular X-ray materials with tabular silver halide emulsions as well as a method for processing which may make use of three-part package concentrates for preparing hardener containing developing solutions for rapid processing.
- Further objects will become apparent from the description hereinafter.
- The above objects are accomplished by providing a method of processing of exposed silver bromide or silver bromoiodide X-ray film materials which may be processed in a total processing time of 60 seconds or less in an aqueous alkaline photographic developing solution, having a pH in the range of 9 to 12, comprising a dihydroxybenzene developing agent, 4-hydroxymethyl-4-methyl-1-phenyl-3-pyrazolidinone as an auxiliary developing agent, in an amount of from 1.0 g to less than 3.5 g per liter of said developing solution, and at least one organic antifoggant characterised in that it further contains a compound providing iodide ions in an amount between 4 10-5 and 8 10-4 valents of ions per liter.
- It has been found that the iodide ions providing compound, which is preferably potassium iodide, can partly replace the 4-hydroxymethyl-4 methyl-1-phenyl-3-pyrazolidinone auxiliary developing agent with maintenance of sensitometric results. With an amount of less than 3.5 g of said auxiliary developing agent it is possible to achieve a very short process time while meeting all sensitometric requirements that are important for X-ray film development provided that a iodide ion releasing compound is present. Obviously by substituting iodide ions for part of the auxiliary developing agent in the developing solution, the cost of the developer can be reduced. Moreover the use in a reduced amount of auxiliary developing agent reduces the tendency of said agent to crystallize, so that a more concentrated one-part developing solution can be offered to the customer. So it is possible e.g. to deliver very concentrated developer solutions, the customer has to dilute "1+3", "1" standing for the volume of concentrated developer solution and "3" for the volume of water, instead of e.g. "1+1.5" indicating that the developer solution is less concentrated, allowing less water to be added to make it ready for use.
- Also for three-part formulations it is possible to add the iodide ions providing compound or compounds in an adapted amount to one of the three parts. Preferably said iodide ions providing compounds and the 4-hydroxymethyl-4-hydroxy-1-phenyl-3-pyrazolidinone are added to the alkaline developer part A.
- Thus one- or three-part package formulation can be used to prepare the developing solution used for rapidly processing silver bromide or silver bromoiodide X-ray films within a total cycle including developing, fixing, rinsing and drying of less than 60 seconds. A developing time of 9.3 (respectively 14) seconds for a 38 (respectively 45) seconds processing cycle can be attained. Even for longer processing times of 90 seconds specific advantages are encountered. A more consumer-friendly low temperature processing is accessible: temperatures lower than 35°C being allowed instead of the normally used 35°C, is accessible. Economical and environmental advantages are thus offered without loss of sensitometric characteristics.
- The developing solution may be free, or at least substantially free, of aldehydic hardening agents such as glutaric aldehyd. When the developing solution is intended for use with x-ray films that have been adequately fore-hardened the incorporation of hardening agents in the developing solution is not necessary.
- The developing solution is preferably free, or is at least substantially free, of silver halide solvents, such as thiosulphates or thiocyanates, these solvents being detrimental to its performance in development of fore-hardened X-ray films, providing an unacceptable sensitometry.
- The dihydroxybenzene developing agents employed in the aqueous alkaline developing solutions used in the method of this invention are well known and widely used in photographic processing, hydroquinone being a preferred developing agent of this class. Other useful dihydroxybenzene developing agents have been described in EP Application 428,455. A combination of two or more of these developing agents is also possible.
- In addition to the dihydroxybenzene developing agent, the developing solution must include 4-hydroxymethyl-4-methyl-1-phenyl-3-pyrazolidinone functioning as an auxiliary super-additive developing agent.
- This compound is well-known from Ciba-Geigy's "Irgaform 1266" trademarked black and white photographic developer, disclosed in April 1986 in its "Product Information Bulletin", where the advantages concerning solubility, storage stability and economised packaging costs in X-ray and graphic arts developer applications are mentioned.
- Although it is common knowledge to use iodide ions in black and white developers, as e.g. US Patent 5,037,727 where iodide ions are used in an alkaline activator to control the image tone, the combination with foresaid auxiliary developing agent or agents to meet the desired sensitometric requirements was not described untill now. A preferred iodide ion providing compound is potassium iodide, although other alkaline or alkaline earth metal salts of iodide are principally usable as well as other inorganic or organic compounds providing iodide ions. So it has been proved that the replacement in equimolar amounts of the potassium ion by e.g. trimethylsulphonium-, tetraphenylphosphonium- and/or tetraethylammonium-ions is offering the same sensitometric results.
- Suitable alkaline agents which can be included in the developing solution to maintain the desired alkaline pH include hydroxides such as sodium hydroxide, carbonates such as sodium carbonate and borates such as sodium tetraborate.
- Problems of fog formation are reduced by adding an effective amount of one or more organic antifoggants to the developer. Particularly suitable are benztriazole antifoggants. Further preferred classes of organic antifoggants include mercapto azoles and mercapto azines. A combination in adjusted amounts of two or more of said organic antifoggants which have been described in detail in EP Application 428,455 is also possible. Besides in conjunction with the use of one or more organic antifoggant inorganic restrainers or antifoggants can be utilized, such as alkali metal bromides, preferably potassium bromide.
- As the aqueous alkaline photographic developing solutions used in the method of this invention are sensitive to aerial oxidation a sulphite preservative can be added in such an amount as to protect the developing agents against this disadvantageous effect, thereby providing sufficiently good stability characteristics. Useful sulphite preservatives include sulphites, bisulphites, metabisulphites and carbonyl bisulphite adducts present as alkaline metal ion or ammonium ion salts. Alternatives like hydroxylamine and ascorbic acid can be used alone or in combination with one another or with said sulphites.
- Additional optional additives include sequestering agents, surfactants and organic solvents. Examples of these ingredients are given in EP Application 428,455.
- The aqueous alkaline developing solutions used in accordance with the method of this invention can vary widely with regard to the concentration of the various ingredients included therein. Preferably the dihydroxybenzene developing agent (e.g. hydroquinone) is used in an amount of from about 20 to about 40 grams per liter. The 4-hydroxymethyl-4-methyl-1-phenyl-3-pyrazolidinone is used in an amount of 1.0 g to less than 3.5 grams per liter, the iodide ion releasing compound (e.g. potassium iodide) is used in an amount of 4.10-5 to 8.10-4 equivalents per liter, 5-methyl-benzotriazole is used in an amount of about 8.10-5 to about 8.10-4 moles per liter and 1-phenyl-5-mercaptotetrazole is used in an amount of about 0 to 3.10-4 moles. The preservative (e.g. potassium sulphite) is used in an amount of about 20 to 100 grams per liter. Auxiliary agents present in the developer are sodium tetraborate in an amount of 0 to 25 grams per liter, potassium carbonate in an amount of 5 to 20 grams per liter, potassium bromide in an amount of 1 to 5 grams per liter, diethylene glycol in an amount of 10 to 50 grams per liter, ethylenediaminetetraacetic acid (sodium salt) in an amount of 1 to 5 grams per liter.
The pH of the developing solution is in the range from 9 to 12 and more preferably in the range from 9.5 to 11. - The developing process is typically carried out at a temperature of about 25°C to about 50°C. With the developing solution of this invention, very short developing times, such as 10 seconds or less, are feasable, with total processing times of less than 45 seconds, preferably 38 seconds, being contemplated. A typical 38 seconds cycle has development, fixing , rinsing and drying times of 9.3 seconds at 35°C, 6.6 seconds at 35°C, 4.4 seconds at 20°C and 6.7 seconds at 46°C respectively, time for film transport to be added to reach 38 seconds altogether. The drying temperature of 46°C is referring to an infrared drying system, whereas with a conventional drying system the temperature is about 55°C.
- The invention is directed to the development of medical X-ray materials. These materials contain emulsions based on silver bromide or silver bromoiodide grains, preferably-containing at most 2.5 mole % of iodide ions. The silver halide grains of the photographic emulsions used according to the present invention may have a regular crystalline form such as a cubic or octahedral form or they may have a transition form. They may also have an irregular crystalline form such as a spherical form or a tabular form, or may otherwise have a composite crystal form comprising a mixture of said regular and irregular crystalline forms.
- The silver halide grains may have a multilayered grain structure. According to a simple embodiment the grains may comprise a core and a shell, which may have different halide compositions and/or may have undergone different modifications such as the addition of dopes. Besides having a differently composed core and shell the silver halide grains may also comprise different phases inbetween.
- Two or more types of silver halide emulsions that have been prepared differently can be mixed for forming a photographic emulsion for use in accordance with the present invention.
- The average size of the silver halide grains may range from 0.1 to 1.00 µm, preferably from 0.3 to 0.7 µm.
- The size distribution of the silver halide particles of the photographic emulsions to be used according to the present invention can be homodisperse or heterodisperse, a homodisperse size distribution being obtained when 95% of the grains have a size that does not deviate more than 30% from the average grain size.
- Further illustrations of the invention will be given in the following examples.
- A tabular silver bromoiodide emulsion, containing 1 mole % of AgI and 99 mole % of AgBr, was precipitated using the double jet technique. The thus obtained tabular grain emulsion, containing 75 grams of gelatin pro mole of AgNO3, had the following characteristics:
- mean diameter of the circle with the same projective surface of the tabular grain: 1.12 +/- 0.23 µm (0.23 being the standard variation s).
- mean thickness of the tabular grains : 0.23 µm.
- aspect-ratio : 5.5.
- percentage of total projective surface covered by the tabular grains: 98%.
- This emulsion was chemically sensitised in the presence of dye 1 (anhydro-5,5'-dichloro-3,3'-bis(n.sulfobutyl)-9-ethyloxacarbocyanine hydroxide), chloro auric acid, sodium thiosulphate and potassium thiocyanate.
- The following ingredients were added per mole of silver halide :
- 4-hydroxy-6-methyl-1,3,3a,7-tetraazaindene: 0.29 grams
- sorbitol 9.10 grams
- polyethylacrylate (MW=1000000) 14.50 grams
- 1,3 dihydroxybenzene 3.05 grams
- dextrane (MW=10000) 31.00 grams
- The coating weight is expressed in grams per square meter per side
gelatin 1.10 polymethylmethacrylate
(average particle diameter : 3.5 µm)0.023 ammoniumperfluorocaprylate 0.0075 C17H15-CO-NH-(CH2-CH2-O-)17-H 0.0188 formaldehyde 0.1 - Both emulsion layer and protective layer were simultaneously coated on both sides of a polyethylene terephthalate film support of 175 µm thickness. The resulting photographic material contained 3.5 grams of AgNO3 per m2 per side.
- This material is the commercially available medical X-ray material CURIX ORTHO STA manufactured by Agfa-Gevaert N.V., Belgium, which is a double coated film suitable for use with green light emitting X-ray sensitive screens.
- Samples of the photographic materials 1 and 2 were illuminated using a continuous wedge with green light of 540nm during 0.02 seconds and were processed under the circumstances described further; material 1 being processed in accordance with the present invention in 38 sec. whereas material 2 being processed for comparison purposes in the known 90 sec. commercial processing cycle. The density as a function of the light dose was measured and therefrom were determined : fog level (with an accuracy of 0.001 density point), the relative speed S at a density of 1 above fog (reference was set to a speed of 100), maximum density DMAX, the gradient AG between 0.25 above fog and 2.0 above fog, the gradient AGTOE between 0.1 and 1.0 above fog and the gradient AGBACK between 1.0 and 2.5 above fog.
-
- processing machine : CURIX 402 (Agfa-Gevaert trademarked name) with the
following time (in seconds) and temperature (in °C) characteristics:
loading 3.4 sec. developing 23.4 sec./ 35°C. in Agfa-Gevaerts commercial G138 developer cross-over 3.8 sec. fixing 15.7 sec./ 35°C. in Agfa-Gevaerts commercial G334 fixer cross-over 3.8 sec. rinsing 15.7 sec./ 20°C. cross-over + drying 32.2 sec. total time 98.0 sec. -
- processing machine : CURIX HT530 (Agfa-Gevaert trademarked name) with the
following time (in seconds) and temperature (in °C) characteristics:
loading 0.2 sec. developing 9.3 sec. 35°C in developer I described below cross-over 1.4 sec. rinsing 0.9 sec. crossover 1.5 sec. fixing 6.6 sec. 35°C in fixer I described below crossover 2.0 sec. rinsing 4.4 sec. 20°C cross-over 4.6 sec. drying 6.7 sec. total 37.6 sec. -
- concentrated part :
water 200 ml potassium bromide 12 grams potassium sulphite (65% solution) 249 grams ethylenediaminetetraacetic acid, sodium salt,trihydrate 9.6 grams hydroquinone 106 grams 5-methylbenzotriazole 0.076 grams 1-phenyl-5-mercaptotetrazole 0.040 grams sodiumtetraborate (decahydrate) 70 grams potassium carbonate 38 grams potassium hydroxide 49 grams diethylene glycol 11 grams potassium iodide: in variable amounts(see Table I: amounts after dilution) 4-hydroxymethyl-4methyl-1phenyl- 3-pyrazolidinone: in variable amounts(see Table I: amounts after dilution) Water to make 1 liter - For initiation of the processing one part of the concentrated developer was mixed with 3 parts of water.
No starter was added.
The pH of this mixture was 10.30 at 25°C. -
- concentrated part :
ammonium thiosulfate (78% solution) 661 grams sodium sulphite 54 grams boric acid 25 grams sodium acetate-trihydrate 70 grams acetic acid 40 grams water to make 1 liter - The effect of KI in a hydroquinone/4-hydroxymethyl-4-methyl-1-phenyl--3-pyrazolidinone (HMMPHEN) developing bath for 38 seconds processing on the sensitometric characteristics of material 1 is given in Table 1 as compared with conventional 90 sec. processing of material 2.
(ref.)= standard 90 s processing of material 2.
(comp.)=comparative 38 s processing of material 1;
(inv.)= 38 s processing of material 1 in accordance with the invention.MAT. KI (g/l) HMMPHEN (g/l) FOG S DMAX AG AGTOE AGBACK 2 ---- - 0.035 100 3.63 3.40 1.90 4.16 (ref.) 1 0 3 0.024 73 3.58 3.55 1.97 4.58(comp.) 1 0.022 3 0.036 100 3.57 3.41 1.97 4.21 (inv.) 1 0 5 0.030 87 3.59 3.51 1.93 4.54(comp.) 1 0.022 5 0.053 120 3.58 3.28 1.87 4.15 (inv.) - The results in Table 1 clearly show that in the presence of potassium iodide in the hardener free developer a higher sensitivity is obtained after 38 s processing so that even with less than 3.5 g of the expensive HMMPHEN the desired sensitometric profile (see reference) is obtained. Combined with HMMPHEN still higher sensitivities may be achieved.
- Samples of the commercial CURIX ORTHO STA were exposed as described in example 1 and processed on the one hand in a commercial 90 sec. processing cycle as referred to in example 1 and on the other hand in a 38 seconds processing with hardener containing developer.
- The composition of the developing and fixing solutions that were applied for the 38 sec. processing are as follows:
-
- concentrated part A:
water 200 ml potassium bromide 12 grams potassium sulphite (65% solution) 249 grams ethylenediaminetetraacetic acid, sodium salt, trihydrate 9.6 grams hydroquinone 106 grams sodiumtetraborate, decahydrate 70 grams potassium carbonate 38 grams potassium hydroxide 77 grams diethylene glycol 56 grams 1-phenyl-5-mercaptotetrazole 0.10 grams 5-methylbenzotriazole 0.076 grams 4-hydroxymethyl-4methyl-1phenyl-
3-pyrazolidinone: in variable amounts(see Table 2: amounts after dilution)potassium iodide: in variable amounts(see Table 2: amounts after dilution) water to make 1 liter pH adjusted to 11.80 at 25 C with potassium hydroxide. - concentrated part B:
acetic acid 30.1 grams 1-phenyl-3-pyrazolidinone 10.0 grams 5-nitro-indazole 1.15 grams diethylene glycol to make 100ml - concentrated part C:
glutaric dialdehyde (50% solution) 17.8 grams potassiummetabisulphite 26.0 grams water to make 100ml - For initiation of the processing the three parts were mixed in the following ratio : 250 ml of part A, 700 ml of water, 25 ml of part B and 25 ml of part C. No starter solution was added. A pH of 10.40 at 25°C was measured.
-
- concentrated part A :
ammoniumthiosulphate (78% solution) 661 grams sodium sulphite 54 grams boric acid 25 grams sodium acetate trihydrate 70 grams acetic acid 40 grams water to make 1 liter pH adjusted with acetic acid to 5.30 at 25°C - concentrated part B :
water 150 ml acetic acid 10 grams sulphuric acid 13 grams aluminium sulphate (34% solution) 27 grams water to make 250ml - The fixer ready for use was then made by mixing concentrated part A, water and concentrated part B in the following ratio: respectively 250 ml, 687.5 ml and 62.5 ml. A pH of this mixture of 4.25 at 25°C was measured.
- The sensitometric results obtained are set forth in Table 2.
MAT KI (g/l) HMMPHEN (g/l) FOG S DMAX AG AGTOE AGBACK 2 ---- - 0.020 100 3.59 3.25 1.97 3.77 (ref.) 2 0 0 0.027 53 3.63 3.19 1.90 3.89 (comp.) 2 0.050 0 0.030 80 3.62 3.21 1.98 3.78 (comp.) 2 0 4.25 0.026 70 3.66 3.20 1.89 3.96 (comp.) 2 0.050 4.25 0.031 93 3.65 3.17 1.93 3.75 (inv.) - The results in table 2 clearly show that in the presence of potassium iodide in the hardener containing developer a higher sensitivity is obtained after 38 s processing. In the presence of HMMPHEN the same desired sensitometric profile can be obtained as in the 90 s reference cycle. To obtain this reference sensitometric profile with the expensive HMMPHEN alone even higher concentrations than 4.25 grams per liter are necessary.
To make this fixer ready for use one part of this concentrated part was mixed with 4 parts of water. A pH of 5.25 was measured at 25°C.
Claims (8)
- Method of processing an exposed silver bromide or silver bromoiodide medical X-ray film material which comprises development with an aqueous alkaline photographic developing solution having a pH in the range of 9 to 12, comprising a dihydroxybenzene developing agent, 4-hydroxymethyl-4-methyl-1-phenyl-3-pyrazolidinone as an auxiliary developing agent in an amount of from 1.0 g to less than 3.5 g per liter of said developing solution, and at least one organic antifoggant characterised in that the developing solution further contains a compound providing iodide ions in an amount between 4 10-5 and 8 10-4 equivalents of ions per liter.
- Method as claimed in claim 1 wherein said dihydroxybenzene developing agent is hydroquinone.
- Method as claimed in claim 1 or 2 wherein said iodide ion providing compound is potassium iodide.
- Method as claimed in any of claims 1 to 3 wherein said organic antifoggant(s) is (are) 5-methylbenzotriazole and/or 1-phenyl-5-mercaptotetrazole.
- Method as claimed in any of claims 1 to 4 wherein said iodide ions providing compound is potassium iodide and is present in an amount from 0.010 to 0.1 grams per liter of said developing solution.
- Method as claimed in any of claims 1 to 5 wherein the amount of hydroquinone is from 20 to 40 grams per liter of said developing solution.
- Method according to any of claims 2 to 6 wherein said developing solution essentially has the following composition: from 20 to 40 grams per liter of hydroquinone, from 1.0 to 3.5 grams per liter of 4-hydroxymethyl-4-methyl-1-phenyl-3-pyrazolidinone, from 0.010 to 0.1 gram per liter of potassium iodide, from 0.01 to 0.1gram per liter of 5-methyl-benzotriazole, from 0 to 0.050 gram per liter of 1-phenyl-5-mercaptotetrazole and from 20 to 100 grams per liter of potassium sulphite.
- Method according to any of the preceding claims wherein the total processing time is 60 seconds or less.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
EP19920203420 EP0542354B1 (en) | 1991-11-14 | 1992-11-09 | Method of developing x-ray materials |
Applications Claiming Priority (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
EP91202953 | 1991-11-14 | ||
EP91202953 | 1991-11-14 | ||
EP19920203420 EP0542354B1 (en) | 1991-11-14 | 1992-11-09 | Method of developing x-ray materials |
Publications (2)
Publication Number | Publication Date |
---|---|
EP0542354A1 EP0542354A1 (en) | 1993-05-19 |
EP0542354B1 true EP0542354B1 (en) | 2002-05-29 |
Family
ID=26129470
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP19920203420 Expired - Lifetime EP0542354B1 (en) | 1991-11-14 | 1992-11-09 | Method of developing x-ray materials |
Country Status (1)
Country | Link |
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EP (1) | EP0542354B1 (en) |
Families Citing this family (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP0651284A1 (en) * | 1993-10-29 | 1995-05-03 | Agfa-Gevaert N.V. | Precipitation of silver halide crystals comprising iodide |
US6277551B1 (en) * | 1999-02-02 | 2001-08-21 | Agfa-Gevaert | Emulsion, material and screen/film system for radiological image formation |
US6737228B2 (en) * | 2001-05-22 | 2004-05-18 | Agfa-Gevaert | Film material exhibiting a “colder” blue-black image tone and improved preservation characteristics |
Family Cites Families (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
BE484696A (en) * | 1947-11-18 | |||
US3826654A (en) * | 1971-06-01 | 1974-07-30 | Eastman Kodak Co | Developer for surface-and internalimage silver halide photographic materials |
JPS5872143A (en) * | 1981-10-26 | 1983-04-30 | Mitsubishi Paper Mills Ltd | Developer for diffusion transfer of silver complex salt |
CA2026606A1 (en) * | 1989-11-13 | 1991-05-14 | Eastman Kodak Company | Photographic developing solution for use with fore-hardened x-ray films |
-
1992
- 1992-11-09 EP EP19920203420 patent/EP0542354B1/en not_active Expired - Lifetime
Also Published As
Publication number | Publication date |
---|---|
EP0542354A1 (en) | 1993-05-19 |
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