EP1516227A1 - Entwicklerkonzentrat für schwarz-weiss entwicklung photographischer materialien - Google Patents
Entwicklerkonzentrat für schwarz-weiss entwicklung photographischer materialienInfo
- Publication number
- EP1516227A1 EP1516227A1 EP03732552A EP03732552A EP1516227A1 EP 1516227 A1 EP1516227 A1 EP 1516227A1 EP 03732552 A EP03732552 A EP 03732552A EP 03732552 A EP03732552 A EP 03732552A EP 1516227 A1 EP1516227 A1 EP 1516227A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- developer
- pyrazolidone
- phenyl
- methyl
- hydroxymethyl
- 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.)
- Withdrawn
Links
- 239000012141 concentrate Substances 0.000 title claims abstract description 51
- 239000000463 material Substances 0.000 title claims abstract description 10
- 239000000203 mixture Substances 0.000 claims abstract description 27
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 claims abstract description 26
- NDGRWYRVNANFNB-UHFFFAOYSA-N pyrazolidin-3-one Chemical class O=C1CCNN1 NDGRWYRVNANFNB-UHFFFAOYSA-N 0.000 claims abstract description 25
- 150000003839 salts Chemical class 0.000 claims abstract description 10
- IKQCSJBQLWJEPU-UHFFFAOYSA-N 2,5-dihydroxybenzenesulfonic acid Chemical compound OC1=CC=C(O)C(S(O)(=O)=O)=C1 IKQCSJBQLWJEPU-UHFFFAOYSA-N 0.000 claims abstract description 9
- -1 silver halide Chemical class 0.000 claims abstract description 7
- 229910052709 silver Inorganic materials 0.000 claims abstract description 5
- 239000004332 silver Substances 0.000 claims abstract description 5
- 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 36
- 239000000243 solution Substances 0.000 claims description 35
- 125000000217 alkyl group Chemical group 0.000 claims description 13
- 125000003118 aryl group Chemical group 0.000 claims description 8
- 239000001257 hydrogen Substances 0.000 claims description 8
- 229910052739 hydrogen Inorganic materials 0.000 claims description 8
- 238000000034 method Methods 0.000 claims description 7
- 229910006069 SO3H Inorganic materials 0.000 claims description 6
- VKDSBABHIXQFKH-UHFFFAOYSA-M potassium;4-hydroxy-3-sulfophenolate Chemical group [K+].OC1=CC=C(O)C(S([O-])(=O)=O)=C1 VKDSBABHIXQFKH-UHFFFAOYSA-M 0.000 claims description 6
- 230000003381 solubilizing effect Effects 0.000 claims description 6
- 238000010790 dilution Methods 0.000 claims description 5
- 239000012895 dilution Substances 0.000 claims description 5
- 125000000020 sulfo group Chemical group O=S(=O)([*])O[H] 0.000 claims description 4
- 125000003545 alkoxy group Chemical group 0.000 claims description 2
- 125000004104 aryloxy group Chemical group 0.000 claims description 2
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 2
- 125000004435 hydrogen atom Chemical class [H]* 0.000 claims 3
- 101000957333 Homo sapiens Muscleblind-like protein 3 Proteins 0.000 claims 1
- 102100038751 Muscleblind-like protein 3 Human genes 0.000 claims 1
- 229910006074 SO2NH2 Inorganic materials 0.000 claims 1
- 125000004397 aminosulfonyl group Chemical group NS(=O)(=O)* 0.000 claims 1
- 238000001556 precipitation Methods 0.000 abstract description 7
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 27
- 150000001875 compounds Chemical class 0.000 description 21
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 14
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 11
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 10
- 239000007787 solid Substances 0.000 description 9
- 239000003795 chemical substances by application Substances 0.000 description 8
- 238000003756 stirring Methods 0.000 description 8
- 230000000694 effects Effects 0.000 description 7
- 229910052757 nitrogen Inorganic materials 0.000 description 7
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 description 6
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 6
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 5
- 150000008064 anhydrides Chemical class 0.000 description 5
- 239000002904 solvent Substances 0.000 description 5
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 4
- 239000002253 acid Substances 0.000 description 4
- 238000007792 addition Methods 0.000 description 4
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 4
- 239000000843 powder Substances 0.000 description 4
- 239000002244 precipitate Substances 0.000 description 4
- FYSNRJHAOHDILO-UHFFFAOYSA-N thionyl chloride Chemical compound ClS(Cl)=O FYSNRJHAOHDILO-UHFFFAOYSA-N 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- 239000003963 antioxidant agent Substances 0.000 description 3
- 230000003078 antioxidant effect Effects 0.000 description 3
- 235000006708 antioxidants Nutrition 0.000 description 3
- 235000010323 ascorbic acid Nutrition 0.000 description 3
- 229960005070 ascorbic acid Drugs 0.000 description 3
- 239000011668 ascorbic acid Substances 0.000 description 3
- 239000012043 crude product Substances 0.000 description 3
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 3
- 150000002431 hydrogen Chemical class 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 238000004806 packaging method and process Methods 0.000 description 3
- CMCWWLVWPDLCRM-UHFFFAOYSA-N phenidone Chemical compound N1C(=O)CCN1C1=CC=CC=C1 CMCWWLVWPDLCRM-UHFFFAOYSA-N 0.000 description 3
- 238000000967 suction filtration Methods 0.000 description 3
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 3
- DLYUQMMRRRQYAE-UHFFFAOYSA-N tetraphosphorus decaoxide Chemical compound O1P(O2)(=O)OP3(=O)OP1(=O)OP2(=O)O3 DLYUQMMRRRQYAE-UHFFFAOYSA-N 0.000 description 3
- CDAWCLOXVUBKRW-UHFFFAOYSA-N 2-aminophenol Chemical class NC1=CC=CC=C1O CDAWCLOXVUBKRW-UHFFFAOYSA-N 0.000 description 2
- 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 2
- KMVPXBDOWDXXEN-UHFFFAOYSA-N 4-nitrophenylhydrazine Chemical compound NNC1=CC=C([N+]([O-])=O)C=C1 KMVPXBDOWDXXEN-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 2
- LSNNMFCWUKXFEE-UHFFFAOYSA-N Sulfurous acid Chemical compound OS(O)=O LSNNMFCWUKXFEE-UHFFFAOYSA-N 0.000 description 2
- YDONNITUKPKTIG-UHFFFAOYSA-N [Nitrilotris(methylene)]trisphosphonic acid Chemical compound OP(O)(=O)CN(CP(O)(O)=O)CP(O)(O)=O YDONNITUKPKTIG-UHFFFAOYSA-N 0.000 description 2
- 150000007513 acids Chemical class 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 239000006172 buffering agent Substances 0.000 description 2
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 238000004587 chromatography analysis Methods 0.000 description 2
- UKVIEHSSVKSQBA-UHFFFAOYSA-N methane;palladium Chemical compound C.[Pd] UKVIEHSSVKSQBA-UHFFFAOYSA-N 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 229910052763 palladium Inorganic materials 0.000 description 2
- KDLHZDBZIXYQEI-UHFFFAOYSA-N palladium Substances [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 2
- 238000010992 reflux Methods 0.000 description 2
- 239000003352 sequestering agent Substances 0.000 description 2
- GEHJYWRUCIMESM-UHFFFAOYSA-L sodium sulfite Chemical compound [Na+].[Na+].[O-]S([O-])=O GEHJYWRUCIMESM-UHFFFAOYSA-L 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 239000006228 supernatant Substances 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- PTBDIHRZYDMNKB-UHFFFAOYSA-N 2,2-Bis(hydroxymethyl)propionic acid Chemical compound OCC(C)(CO)C(O)=O PTBDIHRZYDMNKB-UHFFFAOYSA-N 0.000 description 1
- ZMPRRFPMMJQXPP-UHFFFAOYSA-N 2-sulfobenzoic acid Chemical compound OC(=O)C1=CC=CC=C1S(O)(=O)=O ZMPRRFPMMJQXPP-UHFFFAOYSA-N 0.000 description 1
- SJSJAWHHGDPBOC-UHFFFAOYSA-N 4,4-dimethyl-1-phenylpyrazolidin-3-one Chemical compound N1C(=O)C(C)(C)CN1C1=CC=CC=C1 SJSJAWHHGDPBOC-UHFFFAOYSA-N 0.000 description 1
- ZVNPWFOVUDMGRP-UHFFFAOYSA-N 4-methylaminophenol sulfate Chemical compound OS(O)(=O)=O.CNC1=CC=C(O)C=C1.CNC1=CC=C(O)C=C1 ZVNPWFOVUDMGRP-UHFFFAOYSA-N 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical class N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- 150000000996 L-ascorbic acids Chemical class 0.000 description 1
- JLVVSXFLKOJNIY-UHFFFAOYSA-N Magnesium ion Chemical compound [Mg+2] JLVVSXFLKOJNIY-UHFFFAOYSA-N 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- DWAQJAXMDSEUJJ-UHFFFAOYSA-M Sodium bisulfite Chemical compound [Na+].OS([O-])=O DWAQJAXMDSEUJJ-UHFFFAOYSA-M 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- SRSXLGNVWSONIS-UHFFFAOYSA-N benzenesulfonic acid Chemical compound OS(=O)(=O)C1=CC=CC=C1 SRSXLGNVWSONIS-UHFFFAOYSA-N 0.000 description 1
- 229940092714 benzenesulfonic acid Drugs 0.000 description 1
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical class OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 description 1
- ICLJVKBSYXENIB-UHFFFAOYSA-N boric acid;carbonic acid Chemical compound OB(O)O.OC(O)=O ICLJVKBSYXENIB-UHFFFAOYSA-N 0.000 description 1
- 239000012267 brine Substances 0.000 description 1
- 150000003842 bromide salts Chemical class 0.000 description 1
- 230000005587 bubbling Effects 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 229910001424 calcium ion Inorganic materials 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- WBZKQQHYRPRKNJ-UHFFFAOYSA-L disulfite Chemical compound [O-]S(=O)S([O-])(=O)=O WBZKQQHYRPRKNJ-UHFFFAOYSA-L 0.000 description 1
- PCAXGMRPPOMODZ-UHFFFAOYSA-N disulfurous acid, diammonium salt Chemical compound [NH4+].[NH4+].[O-]S(=O)S([O-])(=O)=O PCAXGMRPPOMODZ-UHFFFAOYSA-N 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 150000004820 halides Chemical class 0.000 description 1
- XMBWDFGMSWQBCA-UHFFFAOYSA-N hydrogen iodide Chemical compound I XMBWDFGMSWQBCA-UHFFFAOYSA-N 0.000 description 1
- 229910001425 magnesium ion Inorganic materials 0.000 description 1
- 229910052943 magnesium sulfate Inorganic materials 0.000 description 1
- 235000019341 magnesium sulphate Nutrition 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- QRERGXFPTQGIGU-UHFFFAOYSA-N n,n-diethylethanamine;2-[[4-[4-(hydroxymethyl)-4-methyl-3-oxopyrazolidin-1-yl]phenyl]carbamoyl]benzenesulfonic acid Chemical compound CCN(CC)CC.N1C(=O)C(C)(CO)CN1C(C=C1)=CC=C1NC(=O)C1=CC=CC=C1S(O)(=O)=O QRERGXFPTQGIGU-UHFFFAOYSA-N 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 229920000151 polyglycol Polymers 0.000 description 1
- 239000010695 polyglycol Substances 0.000 description 1
- 150000008442 polyphenolic compounds Chemical class 0.000 description 1
- 235000013824 polyphenols Nutrition 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 235000007686 potassium Nutrition 0.000 description 1
- XAEFZNCEHLXOMS-UHFFFAOYSA-M potassium benzoate Chemical compound [K+].[O-]C(=O)C1=CC=CC=C1 XAEFZNCEHLXOMS-UHFFFAOYSA-M 0.000 description 1
- DJEHXEMURTVAOE-UHFFFAOYSA-M potassium bisulfite Chemical compound [K+].OS([O-])=O DJEHXEMURTVAOE-UHFFFAOYSA-M 0.000 description 1
- 229940099427 potassium bisulfite Drugs 0.000 description 1
- 235000010259 potassium hydrogen sulphite Nutrition 0.000 description 1
- BHZRJJOHZFYXTO-UHFFFAOYSA-L potassium sulfite Chemical compound [K+].[K+].[O-]S([O-])=O BHZRJJOHZFYXTO-UHFFFAOYSA-L 0.000 description 1
- 235000019252 potassium sulphite Nutrition 0.000 description 1
- LPNYRYFBWFDTMA-UHFFFAOYSA-N potassium tert-butoxide Chemical compound [K+].CC(C)(C)[O-] LPNYRYFBWFDTMA-UHFFFAOYSA-N 0.000 description 1
- ABHHITAVUODQNA-UHFFFAOYSA-M potassium;benzenesulfonate Chemical compound [K+].[O-]S(=O)(=O)C1=CC=CC=C1 ABHHITAVUODQNA-UHFFFAOYSA-M 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 239000010802 sludge Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 235000015424 sodium Nutrition 0.000 description 1
- 235000010267 sodium hydrogen sulphite Nutrition 0.000 description 1
- 235000010265 sodium sulphite Nutrition 0.000 description 1
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical compound O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 description 1
- 125000000547 substituted alkyl group Chemical group 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-L sulfite Chemical compound [O-]S([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-L 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 150000003567 thiocyanates Chemical class 0.000 description 1
- 238000005292 vacuum distillation Methods 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
- G03C5/26—Processes using silver-salt-containing photosensitive materials or agents therefor
- G03C5/264—Supplying of photographic processing chemicals; Preparation or packaging thereof
- G03C5/266—Supplying of photographic processing chemicals; Preparation or packaging thereof of solutions or concentrates
-
- 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
- G03C5/30—Developers
-
- 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
- G03C5/30—Developers
- G03C5/3028—Heterocyclic compounds
- G03C5/3035—Heterocyclic compounds containing a diazole ring
Definitions
- the present invention relates to a new aqueous developer concentrate for the black and white development of silver halide photographic materials.
- a developer can comprise different developing agents. Such developing agents are described in Chimie et Physique photographiques, P. Glafkides Chapter LX, pages 152-170, firm edition.
- a main developing agent is used in combination with an auxiliary developing agent.
- auxiliary developer i.e. the combined activity of the mixture of these two agents is greater than the sum of the activities of each of these agents used separately in the same solution. This phenomena called “super-additivity” is explained by Mason in “Photographic Processing Chemistry", Focal Press, London, 1975.
- Polyphenols for example hydroquinone, and reductones, for example compounds of the ascorbic acid type, are the main developers most used in practice in black and white developing solutions.
- aminophenols like Elon® (memyl-p-aminophenol sulfate), l-phenyl-3-pyrazolidones or Phenidones, such as Phenidone-A (l-phenyl-3 pyrazolidone), Phenidone-B (1- phenyl-4 methyl-3 -pyrazolidone), Dimezone (l-phenyl-4,4'-dimethyl-3- pyrazolidone), Dimezone-S (l-phenyl-4-methyl-4'-hydroxymethyl-3- pyrazolidone).
- Photographic developers can be sold as working strength diluted solutions or also be packaged as powders to be dissolved in water or concentrated liquids to be diluted before use.
- the packaging of a developer depends on the solubility and stability of its various components and the user's preferences. The current trend is to reduce the number of components in kits and the volume of the packaging to reduce costs.
- One solution consists in the use of very concentrated developers, but these must then have great stability during storage.
- Conventional 3 -pyrazolidone type co-developers have the disadvantage of having insufficient solubility in water.
- a two-component developer as a powder has the disadvantage of multiplying the packaging, increasing costs and reducing the ease of use.
- Hydroquinone can also be replaced by hydroquinonesulfonic acid or one of its salts.
- GB-A-2,329,973 describes a ready-to-use developer, containing hydroquinonesulfonic acid as main developer and a co-developer that can be 4- methyl-4-hydroxvmethyl-l-phenyl-3 -pyrazolidone.
- a development accelerator that is a polyglycol with average molecular weight between 200 g/mol and 600 g/mol.
- the present invention proposes an aqueous developer concentrate provided as a single part that remains stable and does not have a precipitation problem during storage, and that enables a working strength developer to be obtained keeping a super-additivity effect similar to existing developers and enabling sensitometric results to be obtained comparable to those obtained with hydroquinone type developers for the same processing time without the need to use a development accelerator.
- the aqueous developer concentrate for black and white development is free of hydroquinone, comprises hydroquinonesulfonic acid or one of its salts as main developer, and is characterized in that a) it comprises as co-developer a mixture comprised of 4-methyl-4- hydroxymethyl-1 -phenyl-3 -pyrazolidone and at least one 3 -pyrazolidone type co-developer of formula (I), b) the concentration of 4-methyl-4-hydroxymethyl- 1 -phenyl-3 -pyrazolidone is lower than the solubility of 4-methyl-4-hydroxymethyl-l -phenyl-3 - pyrazolidone measured at 18°C in a developer with composition similar to said developer concentrate but not comprising a co-developer, and c) the quantity of 3 -pyrazolidone type co-developers of formula (I) is between 2 and 60 mole percent in relation to the total quantity of co- developers, the 3 -pyrazolidone type co-developer of formula (I) being:
- R.1 and R.2 each independently represents hydrogen, a substituted or not substituted alkyl group, or a group having the formula:
- n 0 or 1
- L represents a divalent group selected from among 0 0 o
- (Sol) is a solubilizing group selected from among: CO H, SO 3 H, SO 3 K, NHSO R 10 , SO NH 2 , SO 2 HR 10 , polyhydroxyalkyl,
- RlO is alkyl or aryl
- R * is OH, alkyl or aryl
- R*2 is hydrogen, alkyl or aryl
- R3 to R7 in formula (I) each independently represents hydrogen, an alkyl group, a substituted or unsubstituted alkoxy group, a substituted or unsubstituted aryloxy group, or a group having the formula:
- X represents a divalent group selected from among
- the present invention also relates to a working strength developing solution, obtainable by dilution of the developer concentrate described above.
- the present invention also relates to a process for a black and white photographic development or for the black and white development step of color reversal films and papers comprising contacting an exposed photographic material with a working strength developing solution, obtainable by dilution of the developer concentrate described above.
- the developer concentrate according to the present invention and its working strength solution can be used to develop black and white materials, like graphic arts materials, x-ray materials, black and white photographic films and papers, microfilms or for the black and white development step of color reversal films and papers.
- Figures 1 and 2 represent the sensitometric curves obtained with control developers and with developers according to the present invention used for the black and white development step of color reversal films.
- the aqueous developer concentrate according to the present invention comprises hydroquinonesulfonic acid or one of its salts as main developer of silver halides.
- hydroquinonesulfonic acid or one of its salts as main developer of silver halides.
- potassium hydroquinone-monosulfonate is used.
- the co-developer comprises a mixture of 4-methyl-4- hydroxymethyl- 1 -phenyl-3 -pyrazolidone and a 3 -pyrazolidone type co-developer of formula (I) as defined above.
- These co-developers of formula (I) have solubilizing groups that are generally not directly attached to the phenyl ring or pyrazolidino ring and are described in Patents US-A-5,780,212 and US-A- 5,942,379.
- Examples of 3 -pyrazolidone type compounds of formula (I) useful in the present invention have the following formulas:
- 3 -pyrazolidone type compounds (1) and (17) are especially preferred.
- Other 3 -pyrazolidone type compounds useful in the present invention have the following formulas:
- the concentration of 4-rnethyl ⁇ 4- hydroxymethyl-1 -phenyl-3 -pyrazolidone is lower than the solubility of 4-methyl-4- hydroxymethyl-1 -phenyl-3 -pyrazolidone measured at 18°C in a developer with composition similar to said developer concentrate but not initially comprising a co-developer.
- This solubility was measured by adding 1 gram of 4-methyl-4- hydroxymethyl-1 -phenyl-3 -pyrazolidone to 100 ml of tested developer concentrate. The sample was kept at 18°C and was stirred daily. After one week, the sample was filtered using a 3 ⁇ m filter. The supernatant was analyzed by chromatography.
- the concentration of main developer of hydroquinonesulfonic acid type is between 50 g/1 and 150 g/1, and preferably between 80 g/1 and 120 g/1 and the weight ratio of main developer to 4-methyl-4-hydroxymethyl-l -phenyl-3 -pyrazolidone is preferably greater than 10 to ensure complete efficiency of the working strength developer.
- the quantity of 3 -pyrazolidone type co-developers of formula (I) is between 2 and 60 mole percent in relation to the total quantity of co-developers.
- One or more 3 -pyrazolidone type co-developers of formula (I) can be used in combination with 4-methyl-4-hydroxymethyl-l -phenyl-3 -pyrazolidone.
- the developer concentrate according to the invention can contain numerous conventional additives such as an antioxidant, a sequestering agent, a buffering agent, an antifoggant, a solvent, a surfactant, anti-sludging agents, contrast- promoting agents, halides (such as iodide and bromide salts), a silver metal solvent (such as thiocyanates), and other additives known to those skilled in the art.
- the antioxidant can be sulfite or a compound capable of supplying sulfite ions in aqueous solution.
- the antioxidant can be a sulfite, a bisulfite, or a metabisulfite.
- alkali metal or ammonia salts such as sodium sulfite, potassium sulfite, sodium bisulfite, potassium bisulfite, sodium, potassium or ammonium metabisulfite can be used.
- the buffering agent or a compound capable of controlling the pH can be for example a carbonate, a bicarbonate boric acid or a boric acid salt, or an alkanolamine.
- Sequestering agents especially to trap calcium and magnesium ions, can be polyphosphonic acids and aminopolycarboxylic acids and salts thereof.
- composition of the developer concentrate is capable of numerous variants accessible to those skilled in the art according to the planned application.
- the developer concentrate according to the present invention is diluted with water to obtain a working strength solution, just before its use.
- the developer concentrate according to the invention can be diluted up to 10 times with water. Dilution between 5 and 6 times is preferred.
- the working strength developing solution then preferably comprises between 15 g/1 and 25 g/1 of hydroquinonesulfonic acid or one of its salts as main developer, between 0.5 g/1 and 2 g/1 of 4-methyl-4-hydroxymethyl-l -phenyl-3 -pyrazolidone and between 0.5 g/1 and 2 g/1 of 3 -pyrazolidone type co-developer of formula (I).
- the developer concentrate according to the present invention comprises a quantity of 4-methyl-4-hydroxvmethyl-l -phenyl-3 -pyrazolidone selected to be lower than the solubility of 4-methyl-4-hydroxymethyl-l -phenyl-3 - pyrazolidone in the developer concentrate and to no longer be in supersaturation condition to no longer have a precipitation problem.
- Example 1 Synthesis of the compound [4-[4,4 , -dimethyl-3-oxo-l-pyrazolidinyl]phenyl]amino methanesulfonyl (Compound (1))
- DMSO was degassed by nitrogen bubbling for about 20 minutes.
- potassium t-butoxide (1.8 g, 16 mmol) at ambient temperature, under nitrogen and with stirring.
- the solution was stirred under nitrogen at ambient temperature for 3.5 hours, then added dropwise to tetrahydrofuran (about 800 ml) with rapid stirring.
- a red/brown precipitate was recovered, which was suction washed with THF using a sintered glass funnel. The solid was quickly transferred to a recrystallising dish while it was still damp with THF. Then the solid was dried in a vacuum dryer on phosphorous pentoxide.
- a Kodak Ektachrome 100 ® film was processed according to the Ektachrome E-6® process.
- This process is described in the manual Z-l 19 "Using KODAK Chemicals, Process E-6", Fifth Edition, published by the Eastman Kodak Company.
- This process comprises different successive steps in different baths.
- the first bath corresponds to the first black and white development, this step being performed at 38°C for 6 minutes.
- the control developer (example 3) and the working strength developing solution according to the invention (example 4), both obtained from developer concentrates whose composition is given in table I below, were used respectively.
- the co-developer used in the developer concentrate according to the invention comprised 66.66-mol % of 4-methyl-4-hydroxymethyl-l -phenyl-3 -pyrazolidone and 33.33-mol % of compound (1).
- 190 ml of corresponding developer concentrate were used diluted with the required amount of water.
- the pH of working strength solutions was 9.68.
- Figure 1 gives the sensitometric curves obtained using, for the first black and white development, the control developer and the developing solution respectively corresponding to examples 3 and 4 for 6 minutes of development. It can be seen that when the developer solution obtained from the developer concentrate according to the invention was used, sensitometric results comparable with the control developer were obtained, for the same processing time.
- the combination of 4-methyl-4-hydroxymethyl-l -phenyl-3 -pyrazolidone with the compound (1) as co-developers and potassium hydroquinone- monosulfonate as main developer enabled a working strength developer to be obtained keeping the same super-additivity effect as the known control developer.
- the solubility of 4-methyl-4-hydroxymethyl-l -phenyl-3 - pyrazolidone in the developer concentrate was measured by adding 1 gram of 4- methyl-4-hydroxymethyl-l -phenyl-3 -pyrazolidone to 100 ml of a developer concentrate with composition similar to example 3 but not initially comprising 4- methyl-4-hydroxymethyl- 1 -phenyl-3 -pyrazolidone.
- the sample was kept at 18°C and was stirred daily. After one week, the sample was filtered using a 3 ⁇ m filter. The supernatant was analyzed by chromatography. For the 4-methyl-4- hydroxymethyl-1 -phenyl-3 -pyrazolidone a solubility of about 5.4 g/1 at 18°C was measured.
- the concentration of 4-methyl-4-hydroxymethyl- 1 -phenyl-3 -pyrazolidone was only 5 g/1, and thus lower than its solubility.
- 4-methyl-4-hydroxymethyl-l-phenyl-3- pyrazolidone in the developer concentrate according to the invention was no longer in supersaturation condition.
- the developer concentrate according to the invention does not have a problem of precipitation of 4-methyl-4- hydroxymethyl- 1 -phenyl-3 -pyrazolidone. Examples 5-6
- a Kodak Ektachrome 100S Professional® film was processed according to the Ektachrome E-6® process, using for the first black and white development working strength developing solutions obtained from the developer concentrates whose composition is given in table II below.
- the co-developer used in the developer concentrate according to the invention comprised 55-mol % of 4-methyl-4-hydroxymethyl-l -phenyl-3 - pyrazolidone and 45-mol % of compound (17).
- 190 ml of corresponding developer concentrate were used diluted with the required amount of water.
- the pH of working strength solutions was 9.83.
- Figure 2 gives the sensitometric curves obtained using, for the first black and white development, the control developer and the developing solution respectively corresponding to examples 5 and 6 for 6 minutes of development. It can be seen that when the developing solution obtained from the developer concentrate according to the invention was used, sensitometric results comparable with the control developer were obtained, for the same processing time.
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- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Physics & Mathematics (AREA)
- General Physics & Mathematics (AREA)
- Silver Salt Photography Or Processing Solution Therefor (AREA)
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| FR0207768A FR2841347B1 (fr) | 2002-06-24 | 2002-06-24 | Concentre de revelateur pour le developpement noir et blanc de produits photographiques |
| FR0207768 | 2002-06-24 | ||
| PCT/EP2003/006007 WO2004001503A1 (en) | 2002-06-24 | 2003-06-07 | Developer concentrate for black and white development of photographic materials |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| EP1516227A1 true EP1516227A1 (de) | 2005-03-23 |
Family
ID=29719979
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| EP03732552A Withdrawn EP1516227A1 (de) | 2002-06-24 | 2003-06-07 | Entwicklerkonzentrat für schwarz-weiss entwicklung photographischer materialien |
Country Status (3)
| Country | Link |
|---|---|
| EP (1) | EP1516227A1 (de) |
| FR (1) | FR2841347B1 (de) |
| WO (1) | WO2004001503A1 (de) |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| FR2743905B1 (fr) * | 1996-01-23 | 1999-03-05 | Kodak Pathe | Composition de revelateur organique-inorganique |
| FR2750225B1 (fr) * | 1996-06-24 | 1999-09-24 | Kodak Pathe | Composition de developpement photographique |
| US5948604A (en) * | 1998-08-11 | 1999-09-07 | Eastman Kodak Company | Single-use processing kit for processing color reversal photographic elements |
-
2002
- 2002-06-24 FR FR0207768A patent/FR2841347B1/fr not_active Expired - Fee Related
-
2003
- 2003-06-07 WO PCT/EP2003/006007 patent/WO2004001503A1/en not_active Ceased
- 2003-06-07 EP EP03732552A patent/EP1516227A1/de not_active Withdrawn
Non-Patent Citations (1)
| Title |
|---|
| See references of WO2004001503A1 * |
Also Published As
| Publication number | Publication date |
|---|---|
| WO2004001503A1 (en) | 2003-12-31 |
| FR2841347A1 (fr) | 2003-12-26 |
| FR2841347B1 (fr) | 2004-11-05 |
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