US2688549A - Photographic developer composition - Google Patents
Photographic developer composition Download PDFInfo
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- US2688549A US2688549A US372169A US37216953A US2688549A US 2688549 A US2688549 A US 2688549A US 372169 A US372169 A US 372169A US 37216953 A US37216953 A US 37216953A US 2688549 A US2688549 A US 2688549A
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- US
- United States
- Prior art keywords
- pyrazolidone
- developer
- acid
- compounds
- developer composition
- Prior art date
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- 239000000203 mixture Substances 0.000 title claims description 65
- -1 3-PYRAZOLIDONE SILVER HALIDE Chemical class 0.000 claims description 32
- 150000001875 compounds Chemical class 0.000 claims description 20
- 239000003795 chemical substances by application Substances 0.000 claims description 18
- 239000000463 material Substances 0.000 claims description 4
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Natural products OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 description 34
- NDGRWYRVNANFNB-UHFFFAOYSA-N pyrazolidin-3-one Chemical group O=C1CCNN1 NDGRWYRVNANFNB-UHFFFAOYSA-N 0.000 description 21
- 239000002253 acid Substances 0.000 description 18
- 229910052709 silver Inorganic materials 0.000 description 17
- 239000004332 silver Substances 0.000 description 17
- 229960005070 ascorbic acid Drugs 0.000 description 16
- 235000010323 ascorbic acid Nutrition 0.000 description 13
- 239000012670 alkaline solution Substances 0.000 description 12
- 239000011668 ascorbic acid Substances 0.000 description 12
- 239000000243 solution Substances 0.000 description 10
- 230000000694 effects Effects 0.000 description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 9
- 150000000996 L-ascorbic acids Chemical class 0.000 description 8
- IOLCXVTUBQKXJR-UHFFFAOYSA-M potassium bromide Chemical compound [K+].[Br-] IOLCXVTUBQKXJR-UHFFFAOYSA-M 0.000 description 8
- GEHJYWRUCIMESM-UHFFFAOYSA-L sodium sulfite Chemical compound [Na+].[Na+].[O-]S([O-])=O GEHJYWRUCIMESM-UHFFFAOYSA-L 0.000 description 8
- CMCWWLVWPDLCRM-UHFFFAOYSA-N phenidone Chemical compound N1C(=O)CCN1C1=CC=CC=C1 CMCWWLVWPDLCRM-UHFFFAOYSA-N 0.000 description 7
- 239000003755 preservative agent Substances 0.000 description 7
- 230000002335 preservative effect Effects 0.000 description 7
- 239000002904 solvent Substances 0.000 description 7
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 description 6
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 6
- NLKNQRATVPKPDG-UHFFFAOYSA-M potassium iodide Chemical compound [K+].[I-] NLKNQRATVPKPDG-UHFFFAOYSA-M 0.000 description 6
- LSNNMFCWUKXFEE-UHFFFAOYSA-N Sulfurous acid Chemical compound OS(O)=O LSNNMFCWUKXFEE-UHFFFAOYSA-N 0.000 description 5
- CIWBSHSKHKDKBQ-DUZGATOHSA-N D-isoascorbic acid Chemical compound OC[C@@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-DUZGATOHSA-N 0.000 description 4
- 239000002211 L-ascorbic acid Substances 0.000 description 4
- 235000000069 L-ascorbic acid Nutrition 0.000 description 4
- 125000003118 aryl group Chemical group 0.000 description 4
- 235000010350 erythorbic acid Nutrition 0.000 description 4
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 4
- 229940026239 isoascorbic acid Drugs 0.000 description 4
- 238000000034 method Methods 0.000 description 4
- 229940001482 sodium sulfite Drugs 0.000 description 4
- 235000010265 sodium sulphite Nutrition 0.000 description 4
- QXANLIDBXRRPBF-RXSVEWSESA-N (2R)-2-[(1S)-1,2-dihydroxyethyl]-3,4-dihydroxy-2H-furan-5-one pyrazolidin-3-one Chemical compound O=C1C(O)=C(O)[C@H](O1)[C@@H](O)CO.N1NC(CC1)=O QXANLIDBXRRPBF-RXSVEWSESA-N 0.000 description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical group C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- 125000000217 alkyl group Chemical group 0.000 description 3
- MQRJBSHKWOFOGF-UHFFFAOYSA-L disodium;carbonate;hydrate Chemical compound O.[Na+].[Na+].[O-]C([O-])=O MQRJBSHKWOFOGF-UHFFFAOYSA-L 0.000 description 3
- 150000002083 enediols Chemical class 0.000 description 3
- 229940001593 sodium carbonate Drugs 0.000 description 3
- 229910000029 sodium carbonate Inorganic materials 0.000 description 3
- NATRVBHPDXDFPY-XAHCXIQSSA-N (2R)-2-[(1S,2R)-1,2,3-trihydroxypropyl]-2H-furan-5-one Chemical compound OC[C@@H](O)[C@H](O)[C@@H]1OC(=O)C=C1 NATRVBHPDXDFPY-XAHCXIQSSA-N 0.000 description 2
- ILBBPBRROBHKQL-SFCRRXBPSA-N (2R)-3,4-dihydroxy-2-[(1S,2S)-1,2,3-trihydroxypropyl]-2H-furan-5-one Chemical compound OC[C@H](O)[C@H](O)[C@H]1OC(=O)C(O)=C1O ILBBPBRROBHKQL-SFCRRXBPSA-N 0.000 description 2
- SVJPLZNMCJQWPJ-UHFFFAOYSA-N 1-(4-methylphenyl)pyrazolidin-3-one Chemical compound C1=CC(C)=CC=C1N1NC(=O)CC1 SVJPLZNMCJQWPJ-UHFFFAOYSA-N 0.000 description 2
- FJWJYHHBUMICTP-UHFFFAOYSA-N 4,4-dimethylpyrazolidin-3-one Chemical compound CC1(C)CNNC1=O FJWJYHHBUMICTP-UHFFFAOYSA-N 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical class [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 2
- LAABTJXWUKMZIV-UHFFFAOYSA-N benzene-1,4-diol;4-(methylamino)phenol Chemical compound OC1=CC=C(O)C=C1.CNC1=CC=C(O)C=C1 LAABTJXWUKMZIV-UHFFFAOYSA-N 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- YCIMNLLNPGFGHC-UHFFFAOYSA-N catechol Chemical compound OC1=CC=CC=C1O YCIMNLLNPGFGHC-UHFFFAOYSA-N 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 229940076133 sodium carbonate monohydrate Drugs 0.000 description 2
- GCLGEJMYGQKIIW-UHFFFAOYSA-H sodium hexametaphosphate Chemical compound [Na]OP1(=O)OP(=O)(O[Na])OP(=O)(O[Na])OP(=O)(O[Na])OP(=O)(O[Na])OP(=O)(O[Na])O1 GCLGEJMYGQKIIW-UHFFFAOYSA-H 0.000 description 2
- 235000019982 sodium hexametaphosphate Nutrition 0.000 description 2
- AKHNMLFCWUSKQB-UHFFFAOYSA-L sodium thiosulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=S AKHNMLFCWUSKQB-UHFFFAOYSA-L 0.000 description 2
- 235000019345 sodium thiosulphate Nutrition 0.000 description 2
- 125000001424 substituent group Chemical group 0.000 description 2
- 239000001577 tetrasodium phosphonato phosphate Substances 0.000 description 2
- ZMMZCADSCOTBGA-SFCRRXBPSA-N (2r)-2-[(1s,2s)-1,2-dihydroxypropyl]-3,4-dihydroxy-2h-furan-5-one Chemical compound C[C@H](O)[C@H](O)[C@H]1OC(=O)C(O)=C1O ZMMZCADSCOTBGA-SFCRRXBPSA-N 0.000 description 1
- ILBBPBRROBHKQL-SAMGZKJBSA-N (2s)-3,4-dihydroxy-2-[(1r,2r)-1,2,3-trihydroxypropyl]-2h-furan-5-one Chemical compound OC[C@@H](O)[C@@H](O)[C@@H]1OC(=O)C(O)=C1O ILBBPBRROBHKQL-SAMGZKJBSA-N 0.000 description 1
- BWVQIBKUGHYXLO-UHFFFAOYSA-N 1-(3-methylphenyl)pyrazolidin-3-one Chemical compound CC1=CC=CC(N2NC(=O)CC2)=C1 BWVQIBKUGHYXLO-UHFFFAOYSA-N 0.000 description 1
- YDSYTVIOMNCGSN-UHFFFAOYSA-N 1-(4-methylphenyl)-5-phenylpyrazolidin-3-one Chemical compound C1=CC(C)=CC=C1N1C(C=2C=CC=CC=2)CC(=O)N1 YDSYTVIOMNCGSN-UHFFFAOYSA-N 0.000 description 1
- GGZHVNZHFYCSEV-UHFFFAOYSA-N 1-Phenyl-5-mercaptotetrazole Chemical compound SC1=NN=NN1C1=CC=CC=C1 GGZHVNZHFYCSEV-UHFFFAOYSA-N 0.000 description 1
- XWKAZXKJYHZGAI-UHFFFAOYSA-N 2-acetyl-4,4-dimethyl-1-phenylpyrazolidin-3-one Chemical compound C1C(C)(C)C(=O)N(C(=O)C)N1C1=CC=CC=C1 XWKAZXKJYHZGAI-UHFFFAOYSA-N 0.000 description 1
- JUAGNSFMKLTCCT-UHFFFAOYSA-N 2-aminoacetic acid;carbonic acid Chemical compound OC(O)=O.NCC(O)=O JUAGNSFMKLTCCT-UHFFFAOYSA-N 0.000 description 1
- 125000004182 2-chlorophenyl group Chemical group [H]C1=C([H])C(Cl)=C(*)C([H])=C1[H] 0.000 description 1
- NTQWDHUWWWXZKN-UHFFFAOYSA-N 2-hydroxy-4,4-dimethyl-1-phenylpyrazolidin-3-one Chemical compound ON1C(=O)C(C)(C)CN1C1=CC=CC=C1 NTQWDHUWWWXZKN-UHFFFAOYSA-N 0.000 description 1
- 125000004172 4-methoxyphenyl group Chemical group [H]C1=C([H])C(OC([H])([H])[H])=C([H])C([H])=C1* 0.000 description 1
- ZFIQGRISGKSVAG-UHFFFAOYSA-N 4-methylaminophenol Chemical compound CNC1=CC=C(O)C=C1 ZFIQGRISGKSVAG-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
- WYVJDRGXWOXCCH-UHFFFAOYSA-N 5-methylpyrazolidin-3-one Chemical compound CC1CC(=O)NN1 WYVJDRGXWOXCCH-UHFFFAOYSA-N 0.000 description 1
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 description 1
- CIWBSHSKHKDKBQ-MVHIGOERSA-N D-ascorbic acid Chemical compound OC[C@@H](O)[C@@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-MVHIGOERSA-N 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- CIWBSHSKHKDKBQ-VHUNDSFISA-N L-isoascorbic acid Chemical compound OC[C@H](O)[C@@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-VHUNDSFISA-N 0.000 description 1
- 230000001133 acceleration Effects 0.000 description 1
- 238000013019 agitation Methods 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 229940101006 anhydrous sodium sulfite Drugs 0.000 description 1
- 150000001491 aromatic compounds Chemical class 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 150000001720 carbohydrates Chemical class 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 239000003518 caustics Substances 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 230000000295 complement effect Effects 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 238000002845 discoloration Methods 0.000 description 1
- 239000000839 emulsion Substances 0.000 description 1
- 125000001242 enediol group Chemical group 0.000 description 1
- 125000000623 heterocyclic group Chemical group 0.000 description 1
- 125000001841 imino group Chemical group [H]N=* 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 125000001624 naphthyl group Chemical group 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- WQGWDDDVZFFDIG-UHFFFAOYSA-N pyrogallol Chemical compound OC1=CC=CC(O)=C1O WQGWDDDVZFFDIG-UHFFFAOYSA-N 0.000 description 1
- 150000003839 salts Chemical class 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
- 235000010352 sodium erythorbate Nutrition 0.000 description 1
- NVIFVTYDZMXWGX-UHFFFAOYSA-N sodium metaborate Chemical compound [Na+].[O-]B=O NVIFVTYDZMXWGX-UHFFFAOYSA-N 0.000 description 1
- 229960001922 sodium perborate Drugs 0.000 description 1
- YKLJGMBLPUQQOI-UHFFFAOYSA-M sodium;oxidooxy(oxo)borane Chemical compound [Na+].[O-]OB=O YKLJGMBLPUQQOI-UHFFFAOYSA-M 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
- G03C5/29—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
- G03C5/264—Supplying of photographic processing chemicals; Preparation or packaging thereof
- G03C5/265—Supplying of photographic processing chemicals; Preparation or packaging thereof of powders, granulates, tablets
Definitions
- R represents a hydroxy group when n represents a positive integer from 1 to 4 and.
- R represents a hydrogen atom when n represents a positive integer of from 2 to 4.
- CHzOH d-glucoheptoascorbic acid Other compounds contemplated by the invention which have the above general structure are dand l-ascorbic acids, isoascorbic acid and other ascorbic acid analogs, e. g., sorboascorbic acid, w-lactoascorbic acid, maltoascorbic acid, 1- araboascorbic acid, l-glucoascorbic acid, d-galactoascorbic acid, l-guloascorbic acid, and. l-alloascorbic acid.
- the compounds are non-aromatic and contain the characteristic mononuclear heterocyclic ene-diol group and are not to be confused with the polyhydric aromatic compounds such as catechol or pyrogallic acid which show serious disadvantages such as strong tendency to form colored oxidation products in the development reaction or on contact with the oxygen in the air, which products discolor solutions and stain photographic materials.
- ene-diol-pyrazolidone developer compositions Another advantageous characteristic of the ene-diol-pyrazolidone developer compositions is that the developers show little tendency for the formation of silver sludge or for the formation of dichroic stain on silver images.
- a further advantage is that since the ene-diol compounds are very effective preservatives for the pyrazolidone developing agents and are highly soluble in water, it is possible to prepare concentrated developer compositions more readily than in the case where a less soluble preservative such as sodium sulfite is used.
- a further characteristic of the ene-diol-pyrazolidone developer compositions of the invention resides in the fact that the compositions behave as strong surface latent image developers as opposed to internal latent image developers, as long as they are free of silver halide solvents such as sodium sulfite.
- silver halide solvents such as sodium sulfite.
- taining 3-pyrazolidone compounds have been described in the literature but invariably they have been compounded so as to contain a silver halide solvent such as sodium sulfite as a preservative.
- the 3-pyrazolidone developers free of preservative are very unstable.
- the ene-diol compounds are incorporated into the 3-pyrazolidone developer compositions, the enediol compounds supply the required preservative effect and the surface latent image developer characteristics are maintained.
- An additional unexpected feature of the developers containing the 3-pyrazolidone and ascorbic acid compounds resides in the fact that similar developer compositions can be prepared, in which the pyrazolidone is replaced by a conventional developing agent, for example, a mixture of N-methyl-p-aminophenol and ascorbic acid, which compositions do not exhibit the mentioned development acceleration effect to anything like the same effect.
- a conventional developing agent for example, a mixture of N-methyl-p-aminophenol and ascorbic acid
- the 3-pyrazolidone developer compositions of the invention containing the above ene-diol compounds can be readily converted to internal latent image developer compositions by merely adding a silver halide solvent such as sodium thiosulfate thereto.
- the resultant internal latent image developer composition by virtue of the presence of one of the mentioned ene-diol compounds, likewise possesses excellent keeping properties even in the absence of the usual sulfite preservative.
- the 3-pyrazolidone silver halide developing agents employed in the developer compositions together with ascorbic acid and its analogs have the general structure in which the R groups each represent various substituents such as hydrogen, alkyl or aryl groups, for example, R1 can be hydrogen or a group such as alkyl preferably containing from 1 to 4 carbon atoms, or an aryl group of the benzene or naphthalene series substituted or not, and R2, R3, R4 and R5 can be hydrogen atoms or alkyl as above or aryl such as phenyl.
- R1 can be hydrogen or a group such as alkyl preferably containing from 1 to 4 carbon atoms, or an aryl group of the benzene or naphthalene series substituted or not
- R2, R3, R4 and R5 can be hydrogen atoms or alkyl as above or aryl such as phenyl.
- l-phenyl-4,4-dimethyl-3-pyrazolidone 15. 1 m aminophenyl 4 methyl 4 propyl 3 pyrazolidone 16. l o chlorophenyl 4 methyl 4 ethyl 3 pyrazolidone 1'7. 1 m acetamidophenyl 4,4 diethyl 3 pyrazolidone 18. l (p ⁇ 3 hydroxyethylphenyl) 4,4 dimethyl 3 pyrazolidone 19. 1 p hydroxyphenyl 4,4 dimethyl 3 pyrazolidone 20. 1 p methoxyphenyl 4,4 diethyl 3 pyrazolidone 21.
- the 4,4-dialkyl-3-pyrazolidone compounds 13 to 23 and 26 above are particularly eflicacious for use in the developer compositions of our in-' vention inasmuch as they are more active developing agents than are compounds 1 to 12 which contain a single substituent or only hydrogen atoms in the 4-position of the pyrazolidone nucleus.
- the 4,4 dialkyl 3 pyrazolidone compounds are described and claimed in the Allen et a1.
- the w-hydroxyalkyl- 3-pyrazolidones are also especially useful in concentrated formulas, in replenishers and in the presence of high salt concentrations where their increased solubility enables obtaining and holding adequate amounts of the pyrazolidone compound in solution.
- the compounds are described and claimed in the Allen et a1.
- the Reynolds U. S. Patent application Serial No. 372,166 filed concurrently describes and claims developer compositions containing mixtures of the indicated ascorbic acid and ascorbic acid analogs containing an imino group, such as iminoglucoascorbic acid, in combination with the indicated 3-pyrazolidones.
- Example 1 A solution of the following ingredients in 900 cc. water was prepared:
- Example 2 Development of an exposed positive film was carried out using the 3-pyrazolidone-ascorbic acid developer of Example 1, the pH of which had been raised to 9.8. After 12 minutes development, the sensitometric curve of the film was found to be identical to that obtained in Example 1 by development for 24 minutes. The developer showed no signs of internal latent image development under these conditions.
- Example 3 A pyrazolidone-ascorbic acid developer was developed in the N-methyl-p-aminophenol hydroquinone developer 3 of Example 1 for 12 minutes. As a result, the hydroquinone developer produced a slightly higher contrast image. When the development time was increased to 60 minutes, very little change in density or fog occurred with the developer of the invention.
- Example 1 The presence of internal latent image development was tested as in Example 1 but was found to be similarly absent with the pyrazolidoneascorbic acid developer and present with the N- methyl-p-aminophenol-hydroquinone developer. However, when 3 grams of sodium thiosulfate per liter were added to the pyrazolidone developer composition (pH 9.8 and containing 3.6 grams of bromide per liter), a stronger internal image development took place than when the same amount of hypo was added to the hydroquinone developer.
- Example 4 A developing solution containing 1 gram of 1-phenyl-3-pyrazolidone and 10 grams of dascorbic acid per liter was prepared and adjusted to pH 10.0 with sodium carbonate solution. This developer was used for the development of a fast positive film and was found to give much faster development than the pyrazolidone-ascorbic acid developer compositions of the previous examples and there was no indication of internal latent image.
- Example 5 The striking superadditivity obtained by combining the pyrazolidones and ene-diols, is shown in the following table. It is seen that the individual agents develop only weakly, but that when combined, they develop vigorously, producing images of high density.
- the formulas compare the activity of the enediol ascorbic acid alone at an 0.02 molar concentration (3.5 grams per liter), of the pyrazolidone by itself, at 0.0025 molar concentration (0.4 to 0.5 gram per liter), and combinations of the 7 agents in these concentrations. Th activity was tested with a fine grain positive film given a step wedge exposure and developed for a series of times at 68 F. and with high agitation.
- Example 6 done such as 1- (p-fi-hydroxyethylphenyl) -4,4-
- developer compositions are of particular use as negative developers for color films:
- the developers of this example can be used in any of the well-known processes of color development where a black-and-white developer is required.
- the developers are especially useful in mixed grain color processes employing films such as disclosed in Marines et al. U. S. Patent 2,388,856 or in the Carroll et al. U. S. Patent 2,614,925, October 21, 1952, wherein, for example, is shown a two-layer film, one layer containing blue-sensitive silver halide, the other containing a mixture of green and red-sensitive silver halide grains.
- developer compositions either containing or free of silver halide solvents, are prepared from mixtures of at least one of the indicated B-pyrasolidone compounds and at least one of the indicated ascorbic acids or ascorbic acid analogs.
- Particularly valuable developer compositions in addition to those exemplified above are those containing l-, isoor dimethyl-ZZ-pyrazolidone, or a l-(p-w-hydroxyalkylphenyD-3-pyrazolidone such as l-(p-p-hydroxyethylphenyl) -3-pyrazolidone.
- a photographic developer composition comprising an alkaline material, a 3-pyrazolidone silver halide developing agent and a compound having the general structure wherein R represents a hydroxyl group when n represents a positive integer from 1 to 4 and R represents a hydrogen atom when n represents a positive integer from 2 to 4.
- a photographic developer composition comprising an aqueous alkaline solution containing a mixture of a S-pyrazolidone silver halide developing agent and a compound having the general structure HOH 4.
- a photographic developer composition comprising an aqueous alkaline solution containing a mixture of a 3-pyrazolidone silver halide developing agent and a compound having the structure 6.
- a photographic developer composition comprising an aqueous alkaline solution contain ing a mixture of a 3-pyrazolidone silver halide developing agent and a compound having the structure 7.
- a photographic developer composition comprising an aqueous alkaline solution containing a mixture of a 3-pyrazolidone silver halide developing agent and ascorbic acid.
- a photographic developer composition comprising an aqueous alkaline solution containing a mixture of a l-tolyl-3-pyrazolidone and ascorbic acid.
- a photographic developer composition comprising an aqueous alkaline solution contain- 1o ing a mixture of 1-p-toly1-4A-dimethyl-3- pyrazolidone and ascorbic acid.
- a photographic developer composition com prising an aqueous alkaline solution containing a mixture of 1-phenyl-4,4-dimethyl-B-pyrazolidone and ascorbic acid.
- a photographic developer composition comprising an aqueous alkaline solution containing a mixture of l-p-(/3-hydroxyethylpheny1) -3- pyrazolidone and ascorbic acid.
- a photographic developer composition comprising an aqueous alkaline solution containing a mixture of 1-phenyl-3-pyrazolidone and ascorbic acid.
- a photographic developer composition comprising an aqueous alkaline solution containing a mixture of 1-p-tolyl-3-pyrazolidone and ascorbic acid.
- a photographic developer composition comprising an aqueous alkaline solution containing a mixture of a B-pyrazolidone silver halide developing agent and a compound of the class consisting of isoascorbic acid, l-ascorbic acid, (1- ascorbic acid, fi-desoxy-l-ascorbic acid, l-erythroascorbic acid, l-gluco-ascorbic acid, d-glucoascorbic acid, d-galactoascorbic acid, l-guloascorbic acid, l-alloascorbic acid, d-glucoheptoascorbic acid, l-rhamnoascorbic acid, l-fucoascorbic acid, l-araboascorbic acid, sorboascorbic acid, w-lactoascorbic acid and maltoascorbic acid.
- the developer composition designated in claim 1 which has been adapted to the development of the internal latent image of exposed silver halide by the addition of a silver halide solvent.
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- Physics & Mathematics (AREA)
- General Physics & Mathematics (AREA)
- Silver Salt Photography Or Processing Solution Therefor (AREA)
Priority Applications (4)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
BE530885D BE530885A (en, 2012) | 1953-08-03 | ||
US372169A US2688549A (en) | 1953-08-03 | 1953-08-03 | Photographic developer composition |
FR1108865D FR1108865A (fr) | 1953-08-03 | 1954-08-02 | Révélateur photographique |
GB22506/54A GB767700A (en) | 1953-08-03 | 1954-08-03 | Improvements in photographic developer compositions |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US372169A US2688549A (en) | 1953-08-03 | 1953-08-03 | Photographic developer composition |
Publications (1)
Publication Number | Publication Date |
---|---|
US2688549A true US2688549A (en) | 1954-09-07 |
Family
ID=23466983
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
US372169A Expired - Lifetime US2688549A (en) | 1953-08-03 | 1953-08-03 | Photographic developer composition |
Country Status (4)
Country | Link |
---|---|
US (1) | US2688549A (en, 2012) |
BE (1) | BE530885A (en, 2012) |
FR (1) | FR1108865A (en, 2012) |
GB (1) | GB767700A (en, 2012) |
Cited By (38)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US2751300A (en) * | 1954-07-15 | 1956-06-19 | Eastman Kodak Co | Photographic solvent transfer reproduction process |
US2979406A (en) * | 1956-04-11 | 1961-04-11 | Gen Aniline & Film Corp | Single powder photographic developers |
US3022168A (en) * | 1958-06-28 | 1962-02-20 | Pharmacia Ab | Photographic developer |
US3649280A (en) * | 1968-11-29 | 1972-03-14 | Eastman Kodak Co | Photographic elements and compositions |
US3658527A (en) * | 1966-08-30 | 1972-04-25 | Eastman Kodak Co | Oxidation inhibitors for photographic materials |
US3938997A (en) * | 1975-03-28 | 1976-02-17 | Minnesota Mining And Manufacturing Company | Rapid access, air stable, regenerable iron chelate developer solutions |
US3942985A (en) * | 1973-08-24 | 1976-03-09 | Minnesota Mining And Manufacturing Company | High contrast, rapid access, air stable, regenerable iron chelate developer solutions |
US4038080A (en) * | 1972-09-21 | 1977-07-26 | Minnesota Mining And Manufacturing Company | Fix and bleach-fix bath desilvering |
EP0461783A1 (en) * | 1990-06-11 | 1991-12-18 | Audenried W. Knapp | Photographic developer composition |
AU621779B2 (en) * | 1990-01-31 | 1992-03-19 | Audenried W. Knapp | Non-toxic photographic developer composition |
EP0518352A1 (en) | 1991-06-13 | 1992-12-16 | Dainippon Ink And Chemicals, Inc. | Process for forming super high-contrast negative images and silver halide photographic material and developer being used therefor |
US5196298A (en) * | 1991-02-14 | 1993-03-23 | Agfa-Gevaert, N.V. | Photographic developing solution containing an ascorbic acid derivative |
US5217842A (en) * | 1990-09-19 | 1993-06-08 | Dainippon Ink And Chemical, Inc. | Superhigh contrast negative image forming process |
US5236816A (en) * | 1992-04-10 | 1993-08-17 | Eastman Kodak Company | Photographic developing solution and use thereof in the high contrast development of nucleated photographic elements |
US5264323A (en) * | 1992-04-10 | 1993-11-23 | Eastman Kodak Company | Photographic developing solution and use thereof in the high contrast development of nucleated photographic elements |
EP0580041A2 (en) | 1992-07-10 | 1994-01-26 | Fuji Photo Film Co., Ltd. | Method of processing silver halide photographic material and composition for processing |
US5384232A (en) * | 1991-12-02 | 1995-01-24 | E. I. Du Pont De Nemours And Company | Process for rapid access development of silver halide films using pyridinium as development accelerators |
US5384233A (en) * | 1992-06-15 | 1995-01-24 | Konica Corporation | Chemicals kit including a container formed of multilayer film, for processing photographic light-sensitive materials |
EP0649062A3 (en) * | 1993-10-15 | 1995-08-16 | Minnesota Mining & Mfg | Method for reducing the formation of mud in printing plates for the diffusion-transfer process. |
US5457011A (en) * | 1993-12-27 | 1995-10-10 | Eastman Kodak Company | Photographic developing composition containing a sludge inhibiting agent and use thereof in the high contrast development of nucleated photographic elements |
US5503966A (en) * | 1994-07-22 | 1996-04-02 | International Paper Company | Photographic developing compositions and use thereof in the processing of photographic elements |
US5503965A (en) * | 1993-09-27 | 1996-04-02 | Fuji Photo Film Co., Ltd. | Process for development of black-and-white- silver halide photographic material |
US5578433A (en) * | 1994-10-17 | 1996-11-26 | Fuji Photo Film Co., Ltd. | Processing composition and processing method for silver halide photographic materials |
EP0774687A1 (en) * | 1995-10-30 | 1997-05-21 | Konica Corporation | Solid processing composition and method for processing silver halide photographic light-sensitive material |
US5648205A (en) * | 1994-10-13 | 1997-07-15 | Fuji Photo Film Co., Ltd. | Processing method for silver halide photographic material |
EP0785467A1 (en) * | 1996-01-16 | 1997-07-23 | Konica Corporation | Solid processing composition for silver halide photographic light sensitive material |
US5702875A (en) * | 1996-06-28 | 1997-12-30 | Eastman Kodak Company | Weakly alkaline ascorbic acid developing composition, processing kit and method using same |
US5766832A (en) * | 1995-09-28 | 1998-06-16 | Konica Corporation | Solid developer-replenishing composition for processing silver halide photographic light sensitive material |
US5766830A (en) * | 1994-09-09 | 1998-06-16 | Konica Corporation | Photographic processing method for processing a silver halide photographic light-sensitive material |
EP0848287A1 (en) | 1996-12-11 | 1998-06-17 | Imation Corp. | Photographic silver halide developer composition and process for forming photographic silver images |
US5798204A (en) * | 1994-07-26 | 1998-08-25 | Fuji Photo Film Co., Ltd. | Development processing method of ultrahigh-contrast black-and-white silver halide photographic material |
US5866309A (en) * | 1997-10-22 | 1999-02-02 | Fitterman; Alan S. | Method for processing roomlight handleable photographic elements |
US5871890A (en) * | 1997-11-14 | 1999-02-16 | Eastman Kodak Company | Method for processing roomlight handleable radiographic films using two-stage development |
US5932398A (en) * | 1997-11-14 | 1999-08-03 | Eastman Kodak Company | Kit for roomlight processing of black-and-white photographic elements |
US5989773A (en) * | 1994-05-09 | 1999-11-23 | Fuji Photo Film Co., Ltd | Development processing method of silver halide photographic material and image forming method |
US5994040A (en) * | 1996-03-04 | 1999-11-30 | Fuji Photo Film Co., Ltd. | Processing composition for silver halide photographic light-sensitive material, developer and processing method using the same |
EP2042871A1 (en) | 2007-09-28 | 2009-04-01 | Fujifilm Corporation | Method for mixing two or more types of liquids in porous carrier |
EP2065706A2 (en) | 2007-11-29 | 2009-06-03 | Fujifilm Corporation | A measurement kit and an immunochromatography method |
Families Citing this family (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP0588408B1 (en) * | 1992-09-15 | 1998-05-13 | Agfa-Gevaert N.V. | An ascorbic acid type developer with a particular composition |
EP0738400B1 (en) | 1993-06-18 | 2001-02-28 | Fuji Hunt Photographic Chemicals, N.V. | Non-hydroquinone photographic developer composition and processing method |
-
0
- BE BE530885D patent/BE530885A/xx unknown
-
1953
- 1953-08-03 US US372169A patent/US2688549A/en not_active Expired - Lifetime
-
1954
- 1954-08-02 FR FR1108865D patent/FR1108865A/fr not_active Expired
- 1954-08-03 GB GB22506/54A patent/GB767700A/en not_active Expired
Non-Patent Citations (1)
Title |
---|
None * |
Cited By (46)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US2751300A (en) * | 1954-07-15 | 1956-06-19 | Eastman Kodak Co | Photographic solvent transfer reproduction process |
US2979406A (en) * | 1956-04-11 | 1961-04-11 | Gen Aniline & Film Corp | Single powder photographic developers |
US3022168A (en) * | 1958-06-28 | 1962-02-20 | Pharmacia Ab | Photographic developer |
US3658527A (en) * | 1966-08-30 | 1972-04-25 | Eastman Kodak Co | Oxidation inhibitors for photographic materials |
US3649280A (en) * | 1968-11-29 | 1972-03-14 | Eastman Kodak Co | Photographic elements and compositions |
US4038080A (en) * | 1972-09-21 | 1977-07-26 | Minnesota Mining And Manufacturing Company | Fix and bleach-fix bath desilvering |
US3942985A (en) * | 1973-08-24 | 1976-03-09 | Minnesota Mining And Manufacturing Company | High contrast, rapid access, air stable, regenerable iron chelate developer solutions |
US3938997A (en) * | 1975-03-28 | 1976-02-17 | Minnesota Mining And Manufacturing Company | Rapid access, air stable, regenerable iron chelate developer solutions |
US5098819A (en) * | 1990-01-31 | 1992-03-24 | Knapp Audenried W | Non-toxic photographic developer composition |
US5278035A (en) * | 1990-01-31 | 1994-01-11 | Knapp Audenried W | Non-toxic photographic developer composition for processing x-ray films in automatic film processors |
AU621779B2 (en) * | 1990-01-31 | 1992-03-19 | Audenried W. Knapp | Non-toxic photographic developer composition |
EP0461783A1 (en) * | 1990-06-11 | 1991-12-18 | Audenried W. Knapp | Photographic developer composition |
AU622364B2 (en) * | 1990-06-11 | 1992-04-02 | Audenried W. Knapp | Non-toxic photographic developer composition for processing x-ray films in automatic processors |
US5217842A (en) * | 1990-09-19 | 1993-06-08 | Dainippon Ink And Chemical, Inc. | Superhigh contrast negative image forming process |
US5196298A (en) * | 1991-02-14 | 1993-03-23 | Agfa-Gevaert, N.V. | Photographic developing solution containing an ascorbic acid derivative |
EP0518352A1 (en) | 1991-06-13 | 1992-12-16 | Dainippon Ink And Chemicals, Inc. | Process for forming super high-contrast negative images and silver halide photographic material and developer being used therefor |
US5384232A (en) * | 1991-12-02 | 1995-01-24 | E. I. Du Pont De Nemours And Company | Process for rapid access development of silver halide films using pyridinium as development accelerators |
US5236816A (en) * | 1992-04-10 | 1993-08-17 | Eastman Kodak Company | Photographic developing solution and use thereof in the high contrast development of nucleated photographic elements |
US5264323A (en) * | 1992-04-10 | 1993-11-23 | Eastman Kodak Company | Photographic developing solution and use thereof in the high contrast development of nucleated photographic elements |
US5384233A (en) * | 1992-06-15 | 1995-01-24 | Konica Corporation | Chemicals kit including a container formed of multilayer film, for processing photographic light-sensitive materials |
EP0580041A2 (en) | 1992-07-10 | 1994-01-26 | Fuji Photo Film Co., Ltd. | Method of processing silver halide photographic material and composition for processing |
US5503965A (en) * | 1993-09-27 | 1996-04-02 | Fuji Photo Film Co., Ltd. | Process for development of black-and-white- silver halide photographic material |
EP0649062A3 (en) * | 1993-10-15 | 1995-08-16 | Minnesota Mining & Mfg | Method for reducing the formation of mud in printing plates for the diffusion-transfer process. |
US5457011A (en) * | 1993-12-27 | 1995-10-10 | Eastman Kodak Company | Photographic developing composition containing a sludge inhibiting agent and use thereof in the high contrast development of nucleated photographic elements |
US5989773A (en) * | 1994-05-09 | 1999-11-23 | Fuji Photo Film Co., Ltd | Development processing method of silver halide photographic material and image forming method |
US5503966A (en) * | 1994-07-22 | 1996-04-02 | International Paper Company | Photographic developing compositions and use thereof in the processing of photographic elements |
US5792598A (en) * | 1994-07-22 | 1998-08-11 | International Paper Company | Photographic developing compositions and use thereof in the processing of photographic elements |
US5798204A (en) * | 1994-07-26 | 1998-08-25 | Fuji Photo Film Co., Ltd. | Development processing method of ultrahigh-contrast black-and-white silver halide photographic material |
US5766830A (en) * | 1994-09-09 | 1998-06-16 | Konica Corporation | Photographic processing method for processing a silver halide photographic light-sensitive material |
US5648205A (en) * | 1994-10-13 | 1997-07-15 | Fuji Photo Film Co., Ltd. | Processing method for silver halide photographic material |
US5578433A (en) * | 1994-10-17 | 1996-11-26 | Fuji Photo Film Co., Ltd. | Processing composition and processing method for silver halide photographic materials |
US5766832A (en) * | 1995-09-28 | 1998-06-16 | Konica Corporation | Solid developer-replenishing composition for processing silver halide photographic light sensitive material |
US5851742A (en) * | 1995-10-30 | 1998-12-22 | Konica Corporation | Solid processing composition and method for processing silver halide photographic light-sensitive material |
EP0774687A1 (en) * | 1995-10-30 | 1997-05-21 | Konica Corporation | Solid processing composition and method for processing silver halide photographic light-sensitive material |
EP0785467A1 (en) * | 1996-01-16 | 1997-07-23 | Konica Corporation | Solid processing composition for silver halide photographic light sensitive material |
US5834171A (en) * | 1996-01-16 | 1998-11-10 | Konica Corporation | Solid processing composition for silver halide photographic light sensitive material |
US5994040A (en) * | 1996-03-04 | 1999-11-30 | Fuji Photo Film Co., Ltd. | Processing composition for silver halide photographic light-sensitive material, developer and processing method using the same |
US5702875A (en) * | 1996-06-28 | 1997-12-30 | Eastman Kodak Company | Weakly alkaline ascorbic acid developing composition, processing kit and method using same |
US5756271A (en) * | 1996-06-28 | 1998-05-26 | Eastman Kodak Company | Weakly alkaline ascorbic acid developing composition, processing kit and method using same |
EP0848287A1 (en) | 1996-12-11 | 1998-06-17 | Imation Corp. | Photographic silver halide developer composition and process for forming photographic silver images |
US5998110A (en) * | 1996-12-11 | 1999-12-07 | Ferrania S.P.A. | Photographic silver halide developer composition and process for forming photographic silver images |
US5866309A (en) * | 1997-10-22 | 1999-02-02 | Fitterman; Alan S. | Method for processing roomlight handleable photographic elements |
US5871890A (en) * | 1997-11-14 | 1999-02-16 | Eastman Kodak Company | Method for processing roomlight handleable radiographic films using two-stage development |
US5932398A (en) * | 1997-11-14 | 1999-08-03 | Eastman Kodak Company | Kit for roomlight processing of black-and-white photographic elements |
EP2042871A1 (en) | 2007-09-28 | 2009-04-01 | Fujifilm Corporation | Method for mixing two or more types of liquids in porous carrier |
EP2065706A2 (en) | 2007-11-29 | 2009-06-03 | Fujifilm Corporation | A measurement kit and an immunochromatography method |
Also Published As
Publication number | Publication date |
---|---|
BE530885A (en, 2012) | |
FR1108865A (fr) | 1956-01-18 |
GB767700A (en) | 1957-02-06 |
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