EP0542354A1 - Méthode pour le développement de matériaux photographiques sensible aux rayons X - Google Patents
Méthode pour le développement de matériaux photographiques sensible aux rayons X Download PDFInfo
- Publication number
- EP0542354A1 EP0542354A1 EP92203420A EP92203420A EP0542354A1 EP 0542354 A1 EP0542354 A1 EP 0542354A1 EP 92203420 A EP92203420 A EP 92203420A EP 92203420 A EP92203420 A EP 92203420A EP 0542354 A1 EP0542354 A1 EP 0542354A1
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- EP
- European Patent Office
- Prior art keywords
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- grams
- developing
- phenyl
- developing solution
- Prior art date
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- 239000000463 material Substances 0.000 title claims abstract description 29
- 238000000034 method Methods 0.000 title claims description 14
- 238000012545 processing Methods 0.000 claims abstract description 47
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 40
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 claims abstract description 30
- -1 iodide ions Chemical class 0.000 claims abstract description 25
- 150000001875 compounds Chemical class 0.000 claims abstract description 15
- 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 abstract description 13
- ADZWSOLPGZMUMY-UHFFFAOYSA-M silver bromide Chemical compound [Ag]Br ADZWSOLPGZMUMY-UHFFFAOYSA-M 0.000 claims abstract description 9
- ZUNKMNLKJXRCDM-UHFFFAOYSA-N silver bromoiodide Chemical compound [Ag].IBr ZUNKMNLKJXRCDM-UHFFFAOYSA-N 0.000 claims abstract description 9
- NLKNQRATVPKPDG-UHFFFAOYSA-M potassium iodide Chemical compound [K+].[I-] NLKNQRATVPKPDG-UHFFFAOYSA-M 0.000 claims description 33
- 239000000203 mixture Substances 0.000 claims description 14
- 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
- 125000000687 hydroquinonyl group Chemical group C1(O)=C(C=C(O)C=C1)* 0.000 claims 1
- 239000000839 emulsion Substances 0.000 abstract description 16
- 239000000243 solution Substances 0.000 description 42
- 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
- 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
- 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 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
- 159000000000 sodium salts Chemical class 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
- 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
- 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
- GNHQQNHUGNIICU-UHFFFAOYSA-N 4,4-dihydroxy-2-methyl-1-phenylpyrazolidin-3-one Chemical compound C1C(O)(O)C(=O)N(C)N1C1=CC=CC=C1 GNHQQNHUGNIICU-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
- WSGURAYTCUVDQL-UHFFFAOYSA-N 5-nitro-1h-indazole Chemical compound [O-][N+](=O)C1=CC=C2NN=CC2=C1 WSGURAYTCUVDQL-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
- 150000002500 ions 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
- 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 the development of medical X-ray films. More specifically, this invention relates to 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-hydroxy-methyl-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 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 three-part package concentrates for preparing hardener containing developing solutions for rapid processing.
- the above objects are accomplished by using for the processing of exposed silver bromide or silver bromoiodide X-ray materials e.g. in a total processing time of 60 seconds or less 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, and at least one organic antifoggant characterised in that it further contains a compound providing iodide ions.
- 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-hydroxy-methyl-4-hydroxy-1-phenyl-3-pyrazolidinone are added to the alkaline developer part A.
- the one- or three-part package formulation can be 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 of this invention 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 of this invention 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 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. 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 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 less than 5.0 grams per liter, more preferably in an amount between 1.0 and 3.5 grams per liter
- the iodide ion releasing compound e.g.
- potassium iodide is used in an amount to provide at least 4.10 ⁇ 5 equivalents of ions per liter, more preferably in an amount of 8.10 ⁇ 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
- 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.
- Emulsion preparation .
- 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 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 ⁇ m 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.
- 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.
- 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. cross-over 1.5 sec. fixing 6.6 sec. 35°C in fixer I described below cross-over 2.0 sec. rinsing 4.4 sec. 20°C cross-over 4.6 sec. drying 6.7 sec. total 37.6 sec.
- 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 pH adjusted with acetic acid to 5.30 at 25°C
- ammonium thiosulfate 78% solution
- boric acid 25 grams sodium acetate-trihydrate
- acetic acid 40 grams water to make 1 liter pH adjusted with acetic acid to 5.30 at 25°C
- a pH of 5.25 was measured at 25°C.
- 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):
- -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
- glutaric dialdehyde 50% solution
- potassiummetabisulphite 17.8 grams water to make 100ml
- 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):
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- Physics & Mathematics (AREA)
- General Physics & Mathematics (AREA)
- Silver Salt Photography Or Processing Solution Therefor (AREA)
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
EP19920203420 EP0542354B1 (fr) | 1991-11-14 | 1992-11-09 | Méthode pour le développement de matériaux photographiques sensible aux rayons X |
Applications Claiming Priority (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
EP91202953 | 1991-11-14 | ||
EP91202953 | 1991-11-14 | ||
EP19920203420 EP0542354B1 (fr) | 1991-11-14 | 1992-11-09 | Méthode pour le développement de matériaux photographiques sensible aux rayons X |
Publications (2)
Publication Number | Publication Date |
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EP0542354A1 true EP0542354A1 (fr) | 1993-05-19 |
EP0542354B1 EP0542354B1 (fr) | 2002-05-29 |
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Application Number | Title | Priority Date | Filing Date |
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EP19920203420 Expired - Lifetime EP0542354B1 (fr) | 1991-11-14 | 1992-11-09 | Méthode pour le développement de matériaux photographiques sensible aux rayons X |
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EP (1) | EP0542354B1 (fr) |
Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP0651284A1 (fr) * | 1993-10-29 | 1995-05-03 | Agfa-Gevaert N.V. | Précipitation de cristaux à l'halogénure d'argent comprenant de l'iodure |
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 |
Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US2553498A (en) * | 1947-11-18 | 1951-05-15 | Gen Aniline & Film Corp | First developer for multilayer color film of the reversal type |
US3826654A (en) * | 1971-06-01 | 1974-07-30 | Eastman Kodak Co | Developer for surface-and internalimage silver halide photographic materials |
US4436805A (en) * | 1981-10-26 | 1984-03-13 | Mitsubishi Paper Mills, Ltd. | Silver complex diffusion transfer process using two toning agents |
EP0428455A2 (fr) * | 1989-11-13 | 1991-05-22 | Eastman Kodak Company | Solution de développement photographique à utiliser avec des films prétannés pour radiographie |
-
1992
- 1992-11-09 EP EP19920203420 patent/EP0542354B1/fr not_active Expired - Lifetime
Patent Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US2553498A (en) * | 1947-11-18 | 1951-05-15 | Gen Aniline & Film Corp | First developer for multilayer color film of the reversal type |
US3826654A (en) * | 1971-06-01 | 1974-07-30 | Eastman Kodak Co | Developer for surface-and internalimage silver halide photographic materials |
US4436805A (en) * | 1981-10-26 | 1984-03-13 | Mitsubishi Paper Mills, Ltd. | Silver complex diffusion transfer process using two toning agents |
EP0428455A2 (fr) * | 1989-11-13 | 1991-05-22 | Eastman Kodak Company | Solution de développement photographique à utiliser avec des films prétannés pour radiographie |
Non-Patent Citations (2)
Title |
---|
PATENT ABSTRACTS OF JAPAN vol. 13, no. 271 (P-889)(3619) 22 June 1989 & JP-A-1 063 959 ( KONICA CORPORATION ) 9 March 1989 * |
T.H.JAMES ED 'the theory of the photographic process forth edition' 1977 , MACMILLAN PUBLISHING CO. INC. , NEW YORK USA * |
Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP0651284A1 (fr) * | 1993-10-29 | 1995-05-03 | Agfa-Gevaert N.V. | Précipitation de cristaux à l'halogénure d'argent comprenant de l'iodure |
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 |
Also Published As
Publication number | Publication date |
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EP0542354B1 (fr) | 2002-05-29 |
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