US2688548A - Photographic developer composition - Google Patents
Photographic developer composition Download PDFInfo
- Publication number
- US2688548A US2688548A US372166A US37216653A US2688548A US 2688548 A US2688548 A US 2688548A US 372166 A US372166 A US 372166A US 37216653 A US37216653 A US 37216653A US 2688548 A US2688548 A US 2688548A
- Authority
- US
- United States
- Prior art keywords
- pyrazolidone
- acid
- imino
- compounds
- developer
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Lifetime
Links
- 239000000203 mixture Substances 0.000 title claims description 62
- -1 3-PYRAZOLIDONE SILVER HALIDE Chemical class 0.000 claims description 45
- 150000001875 compounds Chemical class 0.000 claims description 22
- 239000003795 chemical substances by application Substances 0.000 claims description 19
- 239000000463 material Substances 0.000 claims description 4
- NDGRWYRVNANFNB-UHFFFAOYSA-N pyrazolidin-3-one Chemical group O=C1CCNN1 NDGRWYRVNANFNB-UHFFFAOYSA-N 0.000 description 21
- 229910052709 silver Inorganic materials 0.000 description 18
- 239000004332 silver Substances 0.000 description 18
- 239000012670 alkaline solution Substances 0.000 description 13
- 239000002253 acid Substances 0.000 description 10
- GEHJYWRUCIMESM-UHFFFAOYSA-L sodium sulfite Chemical compound [Na+].[Na+].[O-]S([O-])=O GEHJYWRUCIMESM-UHFFFAOYSA-L 0.000 description 10
- 230000000694 effects Effects 0.000 description 8
- 239000002904 solvent Substances 0.000 description 8
- 239000003755 preservative agent Substances 0.000 description 7
- 230000002335 preservative effect Effects 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
- 229960005070 ascorbic acid Drugs 0.000 description 6
- NLKNQRATVPKPDG-UHFFFAOYSA-M potassium iodide Chemical compound [K+].[I-] NLKNQRATVPKPDG-UHFFFAOYSA-M 0.000 description 6
- 239000000243 solution Substances 0.000 description 6
- FSLFAZMYMVFKNB-DMTCNVIQSA-N (2r)-2-[(2r)-3,4-dihydroxy-5-oxo-2h-furan-2-yl]-2-hydroxyacetamide Chemical class OC(=N)[C@H](O)[C@H]1OC(=O)C(O)=C1O FSLFAZMYMVFKNB-DMTCNVIQSA-N 0.000 description 5
- 238000000034 method Methods 0.000 description 5
- 235000010265 sodium sulphite Nutrition 0.000 description 5
- FJWJYHHBUMICTP-UHFFFAOYSA-N 4,4-dimethylpyrazolidin-3-one Chemical compound CC1(C)CNNC1=O FJWJYHHBUMICTP-UHFFFAOYSA-N 0.000 description 4
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 4
- LSNNMFCWUKXFEE-UHFFFAOYSA-N Sulfurous acid Chemical compound OS(O)=O LSNNMFCWUKXFEE-UHFFFAOYSA-N 0.000 description 4
- 125000003118 aryl group Chemical group 0.000 description 4
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 4
- 125000001841 imino group Chemical group [H]N=* 0.000 description 4
- IOLCXVTUBQKXJR-UHFFFAOYSA-M potassium bromide Chemical compound [K+].[Br-] IOLCXVTUBQKXJR-UHFFFAOYSA-M 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- 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
- NVXLIZQNSVLKPO-UHFFFAOYSA-N Glucosereductone Chemical compound O=CC(O)C=O NVXLIZQNSVLKPO-UHFFFAOYSA-N 0.000 description 3
- 239000002211 L-ascorbic acid Substances 0.000 description 3
- 125000000217 alkyl group Chemical group 0.000 description 3
- 239000011668 ascorbic acid Substances 0.000 description 3
- 235000010323 ascorbic acid Nutrition 0.000 description 3
- 150000002083 enediols Chemical class 0.000 description 3
- CMCWWLVWPDLCRM-UHFFFAOYSA-N phenidone Chemical compound N1C(=O)CCN1C1=CC=CC=C1 CMCWWLVWPDLCRM-UHFFFAOYSA-N 0.000 description 3
- VQAMXXXBDNKODW-UHFFFAOYSA-N 1-(2-methylphenyl)pyrazolidin-3-one Chemical compound CC1=CC=CC=C1N1NC(=O)CC1 VQAMXXXBDNKODW-UHFFFAOYSA-N 0.000 description 2
- GGZHVNZHFYCSEV-UHFFFAOYSA-N 1-Phenyl-5-mercaptotetrazole Chemical compound SC1=NN=NN1C1=CC=CC=C1 GGZHVNZHFYCSEV-UHFFFAOYSA-N 0.000 description 2
- IONPWNMJZIUKJZ-UHFFFAOYSA-N 4,4-dimethyl-1-(4-methylphenyl)pyrazolidin-3-one Chemical compound C1=CC(C)=CC=C1N1NC(=O)C(C)(C)C1 IONPWNMJZIUKJZ-UHFFFAOYSA-N 0.000 description 2
- HVBSAKJJOYLTQU-UHFFFAOYSA-N 4-aminobenzenesulfonic acid Chemical compound NC1=CC=C(S(O)(=O)=O)C=C1 HVBSAKJJOYLTQU-UHFFFAOYSA-N 0.000 description 2
- ALYNCZNDIQEVRV-UHFFFAOYSA-N 4-aminobenzoic acid Chemical compound NC1=CC=C(C(O)=O)C=C1 ALYNCZNDIQEVRV-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
- 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
- MQRJBSHKWOFOGF-UHFFFAOYSA-L disodium;carbonate;hydrate Chemical compound O.[Na+].[Na+].[O-]C([O-])=O MQRJBSHKWOFOGF-UHFFFAOYSA-L 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
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- WQGWDDDVZFFDIG-UHFFFAOYSA-N pyrogallol Chemical compound OC1=CC=CC(O)=C1O WQGWDDDVZFFDIG-UHFFFAOYSA-N 0.000 description 2
- 229940001593 sodium carbonate Drugs 0.000 description 2
- 229910000029 sodium carbonate Inorganic materials 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
- 125000001424 substituent group Chemical group 0.000 description 2
- 235000000346 sugar Nutrition 0.000 description 2
- 239000001577 tetrasodium phosphonato phosphate Substances 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 1
- OWEGMIWEEQEYGQ-UHFFFAOYSA-N 100676-05-9 Natural products OC1C(O)C(O)C(CO)OC1OCC1C(O)C(O)C(O)C(OC2C(OC(O)C(O)C2O)CO)O1 OWEGMIWEEQEYGQ-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
- WUBBRNOQWQTFEX-UHFFFAOYSA-N 4-aminosalicylic acid Chemical compound NC1=CC=C(C(O)=O)C(O)=C1 WUBBRNOQWQTFEX-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
- GUBGYTABKSRVRQ-XLOQQCSPSA-N Alpha-Lactose Chemical compound O[C@@H]1[C@@H](O)[C@@H](O)[C@@H](CO)O[C@H]1O[C@@H]1[C@@H](CO)O[C@H](O)[C@H](O)[C@H]1O GUBGYTABKSRVRQ-XLOQQCSPSA-N 0.000 description 1
- YTBSYETUWUMLBZ-UHFFFAOYSA-N D-Erythrose Natural products OCC(O)C(O)C=O YTBSYETUWUMLBZ-UHFFFAOYSA-N 0.000 description 1
- YTBSYETUWUMLBZ-IUYQGCFVSA-N D-erythrose Chemical compound OC[C@@H](O)[C@@H](O)C=O YTBSYETUWUMLBZ-IUYQGCFVSA-N 0.000 description 1
- WQZGKKKJIJFFOK-QTVWNMPRSA-N D-mannopyranose Chemical compound OC[C@H]1OC(O)[C@@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-QTVWNMPRSA-N 0.000 description 1
- 206010056474 Erythrosis Diseases 0.000 description 1
- 101001001462 Homo sapiens Importin subunit alpha-5 Proteins 0.000 description 1
- 102100036186 Importin subunit alpha-5 Human genes 0.000 description 1
- LKDRXBCSQODPBY-AMVSKUEXSA-N L-(-)-Sorbose Chemical compound OCC1(O)OC[C@H](O)[C@@H](O)[C@@H]1O LKDRXBCSQODPBY-AMVSKUEXSA-N 0.000 description 1
- 150000000996 L-ascorbic acids Chemical class 0.000 description 1
- GUBGYTABKSRVRQ-QKKXKWKRSA-N Lactose Natural products OC[C@H]1O[C@@H](O[C@H]2[C@H](O)[C@@H](O)C(O)O[C@@H]2CO)[C@H](O)[C@@H](O)[C@H]1O GUBGYTABKSRVRQ-QKKXKWKRSA-N 0.000 description 1
- GUBGYTABKSRVRQ-PICCSMPSSA-N Maltose Natural products O[C@@H]1[C@@H](O)[C@H](O)[C@@H](CO)O[C@@H]1O[C@@H]1[C@@H](CO)OC(O)[C@H](O)[C@H]1O GUBGYTABKSRVRQ-PICCSMPSSA-N 0.000 description 1
- 230000001133 acceleration Effects 0.000 description 1
- 238000013019 agitation Methods 0.000 description 1
- GZCGUPFRVQAUEE-SLPGGIOYSA-N aldehydo-D-glucose Chemical compound OC[C@@H](O)[C@@H](O)[C@H](O)[C@@H](O)C=O GZCGUPFRVQAUEE-SLPGGIOYSA-N 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 229940060532 allent Drugs 0.000 description 1
- 229960004050 aminobenzoic acid Drugs 0.000 description 1
- 229960004909 aminosalicylic acid Drugs 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- GUBGYTABKSRVRQ-QUYVBRFLSA-N beta-maltose Chemical compound OC[C@H]1O[C@H](O[C@H]2[C@H](O)[C@@H](O)[C@H](O)O[C@@H]2CO)[C@H](O)[C@@H](O)[C@@H]1O GUBGYTABKSRVRQ-QUYVBRFLSA-N 0.000 description 1
- SRGKFVAASLQVBO-BTJKTKAUSA-N brompheniramine maleate Chemical compound OC(=O)\C=C/C(O)=O.C=1C=CC=NC=1C(CCN(C)C)C1=CC=C(Br)C=C1 SRGKFVAASLQVBO-BTJKTKAUSA-N 0.000 description 1
- 150000001720 carbohydrates Chemical class 0.000 description 1
- 235000014633 carbohydrates Nutrition 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
- 125000001242 enediol group Chemical group 0.000 description 1
- 125000000623 heterocyclic group Chemical group 0.000 description 1
- 229940026239 isoascorbic acid Drugs 0.000 description 1
- 239000008101 lactose 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
- 229940079877 pyrogallol Drugs 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000010802 sludge Substances 0.000 description 1
- NVIFVTYDZMXWGX-UHFFFAOYSA-N sodium metaborate Chemical compound [Na+].[O-]B=O NVIFVTYDZMXWGX-UHFFFAOYSA-N 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
- 150000008163 sugars Chemical class 0.000 description 1
- 229950000244 sulfanilic acid Drugs 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
- G03C1/00—Photosensitive materials
- G03C1/005—Silver halide emulsions; Preparation thereof; Physical treatment thereof; Incorporation of additives therein
- G03C1/06—Silver halide emulsions; Preparation thereof; Physical treatment thereof; Incorporation of additives therein with non-macromolecular additives
- G03C1/08—Sensitivity-increasing substances
- G03C1/10—Organic substances
-
- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03C—PHOTOSENSITIVE MATERIALS FOR PHOTOGRAPHIC PURPOSES; PHOTOGRAPHIC PROCESSES, e.g. CINE, X-RAY, COLOUR, STEREO-PHOTOGRAPHIC PROCESSES; AUXILIARY PROCESSES IN PHOTOGRAPHY
- G03C1/00—Photosensitive materials
- G03C1/005—Silver halide emulsions; Preparation thereof; Physical treatment thereof; Incorporation of additives therein
- G03C1/06—Silver halide emulsions; Preparation thereof; Physical treatment thereof; Incorporation of additives therein with non-macromolecular additives
- G03C1/34—Fog-inhibitors; Stabilisers; Agents inhibiting latent image regression
-
- 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
- imino-sorboascorbic acid imino-w-lactoascorbic acid, imino-maltoascorbic acid, imino-l-araboascorbic acid, imino-d-glucoascorbic acid, imino-d-galactoascorbic acid, imino-l-guloascorbic acid, and imino-l-alloascorbic acid.
- the above compounds difier principally in the structure of the terminal group R-CH2-(CHOH)n iand in some cases the compounds are stereoisomers.
- the compounds are described in particular by Pigman and Wolfrom, Advances in Carbohydrate Chemistry, Academic Press, New York, 1946, pp. 80-82.
- the above iminoascorbic acid analogs are named to denote the particular sugar from which they can be synthesized. It will be observed that the compounds are non-aromatic and contain the characteristic mononuclear heterocyclic ene-diol group.
- the compounds are particularly distinguished from aromatic silver halide developing agents such as catechol or pyro gallol 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.
- 3-pyrazolidone compounds such as 1-phenyl-3-pyrazolidone
- 3-pyrazolidone compounds are highly unstable in alkaline developer compositions free of a preservative and tend to darken and lose development activity quickly particularly through aerial oxidation.
- the 3-pyrazolidone compounds when development is carried out with the 3-pyrazolidone compounds in the presence of the enediol compounds, the latter function as preservatives and the developer is highly resistant to discoloration and loss of activity.
- 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
- a further characteristic of the ene-diolpyrazolidone 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. That is, developer compositions containing 3-pyrazolidone compounds have been described in the literature but invariably they have been compounded so as to con tain 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 ene-diol compounds supply the required preservative effect and the surface latent image developer characteristics are maintained.
- 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 formula 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,
- 1-phenyl-4,4-dimethyl-3-pyrazo1idone 15. 1 m aminophenyl 4 methyl 4 propyl- S-pyrazolidone 16. 1 o chlorophenyl 4 methyl 4 ethyl- S-pyrazolidone 17. 1 m acetamidophenyl 4,4 diethyl 3- pyrazolidone 18. 1 (p 3 hydroxyethylphenyl) 4,4 dimethyl-3-pyrazolidone 19. 1 p hydroxyphenyl 4,4 dimethyl 3- pyrazolidone 2'0. 1 p methoxyphenyl 4,4 diethyl 3- pyrazolidone 21.
- the 4,4-dialkyl-3-pyrazolidone compounds 13 to 23 and 26 above are particularly efiicacious for use in the developer compositions of my invention 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 al. U. S. patent application Serial No. 372,148 filed concurrently herewith.
- w-hydroxyalkyl-3-pyrazolidones for example, compounds iminoreductone derivative such as p-aminobenzoic acid reductone, mand p-aminosalicylic acid reductone and sulfanilic acid reductone are similar in structure to the imino ascorbic acid compounds and their use in developer compositions is disclosed and claimed in the Henn and Reynolds U. S. patent application Serial No. 372,168 filed concurrently herewith.
- Example 1 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 agents in these concentrations.
- the 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.
- the ene-diol compounds imino-d-glucoascorbic acid above obtained from d-glucose is representative of a number of ene-diol compounds containing the iminoascorbic acid group derived from sugars.
- the compound is of particular value in my invention since its development rate is markedly accelerated by the 3-pyrazolidone silver halide developing agents, particularly l-phenyl-3-pyrazolidone.
- the other ene-diol compounds containing the imino group can be prepared by the methods of the reference immediately above from, for example, erythrose, galla-ctose, sorbose, mannose, maltose, and lactose and are likewise useful in the 3-pyrazolidone developer compositions where the latter compounds appreciably accelerate the development rate of the ene-diol compounds.
- Example 2 The following developer compositions are particularly suitable 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 7 mixed grain color processes employing films such as disclosed in Mannes et a1.
- developer compositions containing or free of silver halide solvents, are prepared from mixtures of at least one of the indicated 3-pyrazolidone compounds and at least one of the iminoascorbic acid compounds.
- the enediol-pyrazolidone developer composition of the above example exhibits internal latent image development characteristics particularly by virtue of the presence of the silver halide solvent.
- developer compositions in addition to that exemplified above, are those containing imino-d-glucoascorbic acid and either l-phenyl-B-pyrazolidone or a l-tolyl-3-pyrazolidone such as l-p-tolyl-3-pyrazolidone or l-ptolyl-4A-dimethyl-3-p-yrazolidone or a l-(p-flhydroxyalkylphenyl) 4,4 dialkyl 3 pyrazolidone such as 1-(p-c-hydroxyethylphenyl)- 4,4-dimethyl-3pyrazolidone, or a 1-(p-B-w-hY- droxyalkylphenyl) -3-pyrazolidone' such as 1- (pfl-hydroxyethylphenyl) -3-pyrazolidone.
- l-phenyl-B-pyrazolidone or a l-tolyl-3-pyrazolidone such as l-p-to
- 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 general structure prising an aqueous alkaline solution containing a mixture of a 3-pyrazolidone silver halide developing agent and a compound having the struc- 4.
- a photographic developer composition comprising an aqueous alkaline solution containin a mixture of a 3-pyrazolidone silver halide developing agent and a compound having the structure 5.
- 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 containing a mixture of a B-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 imino-d-glucoascorbic acid.
- a photographic developer composition comprising an aqueous alkaline solution containing a mixture of a 1-tolyl-3-pyrazolidone and iminod-glucoascorbic acid.
- a photographic developer composition comprising an aqueous alkaline solution containing a mixture of 1-p-tolyl-4,4-dimethyl-3-pyrazolidone and imino-d-glucoascorbic acid.
- a photographic developer composition comprising an aqueous alkaline solution containing a mixture of 1-phenyl-4A-dimethyl-3-pyrazolidone and. imino-d-glucoascorbic acid.
- a photographic developer composition comprising an aqueous alkaline solution containing a mixture of 1-(p-/3-hydroxyethy1phenyl-3-pyrazolidone and imino-d-glucoascorbic acid.
- a photographic developer composition comprising an aqueous alkaline solution containing a mixture of 1-(p-B-hydroxyethylphenyl)-4,4-dimethyl 3 pyrazolidone and imino d glucoascorbic acid.
- a photographic developer composition comprising an aqueous alkaline solution containing a mixture of 1-phenyl-3-pyrazolidone and iminod-glucoascorbic acid.
- a photographic developer composition comprising an aqueous alkaline solution containing a mixture of 1-p-tolyl-3-pyrazolidone and iminod-glucoascorbic acid.
- a photographic developer composition comprising an aqueous alkaline solution containing a mixture of a 3-pyrazolidone silver halide developing agent and a compound of the class consisting of imino-l-ascorbic acid, imino-d-ascorbic acid, imino-l-erythroascorbic acid, imino-l-glucoascorbic acid, imino-d-glucoascorbic acid, iminod gelactoascorbic acid, imino l guloascorbic acid, imino-l-alloascorbic acid, imino-d-glucoheptoascorbic acid, imino 1 rhamnoascorbic acid, imino-l-fucoascorbic acid, imino-l-araboascorbic acid, imino-sorboascorbic acid, iminoisoascorbic acid, imino-fi-desoxy-l-ascorbie acid,
Landscapes
- Physics & Mathematics (AREA)
- Chemical & Material Sciences (AREA)
- General Physics & Mathematics (AREA)
- Spectroscopy & Molecular Physics (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Silver Salt Photography Or Processing Solution Therefor (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Plural Heterocyclic Compounds (AREA)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US372166A US2688548A (en) | 1953-08-03 | 1953-08-03 | Photographic developer composition |
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US371948A US2751297A (en) | 1953-08-03 | 1953-08-03 | Photographic emulsion layer containing a 3-pyrazolidone |
| US372166A US2688548A (en) | 1953-08-03 | 1953-08-03 | Photographic developer composition |
| US372168A US2691589A (en) | 1953-08-03 | 1953-08-03 | Photographic developer compositions |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| US2688548A true US2688548A (en) | 1954-09-07 |
Family
ID=27005592
Family Applications (3)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| US372166A Expired - Lifetime US2688548A (en) | 1953-08-03 | 1953-08-03 | Photographic developer composition |
| US371948A Expired - Lifetime US2751297A (en) | 1953-08-03 | 1953-08-03 | Photographic emulsion layer containing a 3-pyrazolidone |
| US372168A Expired - Lifetime US2691589A (en) | 1953-08-03 | 1953-08-03 | Photographic developer compositions |
Family Applications After (2)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| US371948A Expired - Lifetime US2751297A (en) | 1953-08-03 | 1953-08-03 | Photographic emulsion layer containing a 3-pyrazolidone |
| US372168A Expired - Lifetime US2691589A (en) | 1953-08-03 | 1953-08-03 | Photographic developer compositions |
Country Status (4)
| Country | Link |
|---|---|
| US (3) | US2688548A (enEXAMPLES) |
| BE (2) | BE530883A (enEXAMPLES) |
| FR (3) | FR1106144A (enEXAMPLES) |
| GB (2) | GB767699A (enEXAMPLES) |
Cited By (20)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2875048A (en) * | 1957-09-30 | 1959-02-24 | Eastman Kodak Co | Combined photographic developing and stabilizing solution |
| US3330661A (en) * | 1962-11-13 | 1967-07-11 | Eastman Kodak Co | Photographic development precursors |
| US3649280A (en) * | 1968-11-29 | 1972-03-14 | Eastman Kodak Co | Photographic elements and compositions |
| 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 |
| EP0508691A1 (en) * | 1991-04-10 | 1992-10-14 | Audenried W. Knapp | Gluconic-acid based developer composition |
| 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 |
| US5273865A (en) * | 1990-04-24 | 1993-12-28 | Minnesota Mining And Manufacturing Company | Photographic color developing composition and method for processing a silver halide color photographic element |
| 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 |
| US5399457A (en) * | 1993-10-15 | 1995-03-21 | Minnesota Mining And Manufacturing Company | Process for reducing sludge in diffusion transfer printing plates |
| US5503965A (en) * | 1993-09-27 | 1996-04-02 | Fuji Photo Film Co., Ltd. | Process for development of black-and-white- silver halide photographic material |
| 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 |
| 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 |
| US5824458A (en) * | 1994-02-28 | 1998-10-20 | Fuji Photo Film Co., Ltd. | Developer and fixing solution for silver halide photographic material and processing method using the same |
Families Citing this family (16)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| NL110284C (enEXAMPLES) * | 1960-10-12 | |||
| US3278307A (en) * | 1961-11-21 | 1966-10-11 | Eastman Kodak Co | Photographic process for producing prints stabilized against print-out |
| GB1054253A (enEXAMPLES) * | 1962-06-15 | 1900-01-01 | ||
| US3300307A (en) * | 1963-01-18 | 1967-01-24 | Eastman Kodak Co | Photographic developer composition |
| US3632340A (en) * | 1968-09-09 | 1972-01-04 | Eastman Kodak Co | Cored direct positive silver halide emulsion developed with polyhydroxybenzene |
| US4365085A (en) * | 1978-02-27 | 1982-12-21 | Polaroid Corporation | Bicyclic reductone developing agents |
| US4154611A (en) * | 1978-02-27 | 1979-05-15 | Polaroid Corporation | Bicyclic reductone developing agents |
| JPS6187148A (ja) * | 1984-10-05 | 1986-05-02 | Konishiroku Photo Ind Co Ltd | ハロゲン化銀写真感光材料 |
| AU590563B2 (en) | 1985-05-16 | 1989-11-09 | Konishiroku Photo Industry Co., Ltd. | Method for color-developing a silver halide color photographic light-sensitive material |
| JPH03215845A (ja) | 1990-01-19 | 1991-09-20 | Fuji Photo Film Co Ltd | 直接ポジ写真感光材料 |
| EP0449340B1 (en) * | 1990-02-26 | 1996-10-16 | Agfa-Gevaert N.V. | Photographic stabilizers containing a developer group |
| JP2873852B2 (ja) | 1990-03-03 | 1999-03-24 | コニカ株式会社 | ハロゲン化銀写真感光材料 |
| EP0528480B1 (en) * | 1991-08-16 | 1997-11-19 | Agfa-Gevaert N.V. | A photographic silver halide material |
| DE69223192T2 (de) * | 1991-08-16 | 1998-06-18 | Agfa Gevaert Nv | Ein photographisches Silberhalogenidmaterial |
| US5427905A (en) * | 1994-07-13 | 1995-06-27 | Polaroid Corporation | Thermally processable image-recording material including reductone developing agent |
| FR2743905B1 (fr) | 1996-01-23 | 1999-03-05 | Kodak Pathe | Composition de revelateur organique-inorganique |
Family Cites Families (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US742405A (en) * | 1901-12-17 | 1903-10-27 | Farbenfabriken Elberfeld Co | Photographic plate and process of making same. |
| US2477462A (en) * | 1946-03-26 | 1949-07-26 | Du Pont | Polymeric color formers from hydroxyl polymers containing reactive ketaldone groups with reactive methylene and amino color formers |
| US2672416A (en) * | 1949-11-16 | 1954-03-16 | Austin N Stanton | Reflex photography utilizing a luminescent light source |
| GB679677A (en) * | 1950-04-06 | 1952-09-24 | Ilford Ltd | Improvements in or relating to pyrazolidones |
| GB679678A (en) * | 1950-04-06 | 1952-09-24 | Ilford Ltd | Improvements in or relating to the production of 3-amino pyrazolines |
-
1953
- 1953-08-03 US US372166A patent/US2688548A/en not_active Expired - Lifetime
- 1953-08-03 US US371948A patent/US2751297A/en not_active Expired - Lifetime
- 1953-08-03 US US372168A patent/US2691589A/en not_active Expired - Lifetime
- 1953-08-03 BE BE530883D patent/BE530883A/xx unknown
-
1954
- 1954-08-02 FR FR1106144D patent/FR1106144A/fr not_active Expired
- 1954-08-02 FR FR1109575D patent/FR1109575A/fr not_active Expired
- 1954-08-02 FR FR1106813D patent/FR1106813A/fr not_active Expired
- 1954-08-03 GB GB22505/54A patent/GB767699A/en not_active Expired
- 1954-08-03 GB GB22510/54A patent/GB767704A/en not_active Expired
- 1954-08-03 BE BE530887D patent/BE530887A/xx unknown
Non-Patent Citations (1)
| Title |
|---|
| None * |
Cited By (24)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2875048A (en) * | 1957-09-30 | 1959-02-24 | Eastman Kodak Co | Combined photographic developing and stabilizing solution |
| US3330661A (en) * | 1962-11-13 | 1967-07-11 | Eastman Kodak Co | Photographic development precursors |
| 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 |
| US5273865A (en) * | 1990-04-24 | 1993-12-28 | Minnesota Mining And Manufacturing Company | Photographic color developing composition and method for processing a silver halide color photographic element |
| EP0508691A1 (en) * | 1991-04-10 | 1992-10-14 | Audenried W. Knapp | Gluconic-acid based developer composition |
| 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 |
| 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. |
| US5399457A (en) * | 1993-10-15 | 1995-03-21 | Minnesota Mining And Manufacturing Company | Process for reducing sludge in diffusion transfer printing plates |
| US5824458A (en) * | 1994-02-28 | 1998-10-20 | Fuji Photo Film Co., Ltd. | Developer and fixing solution for silver halide photographic material and processing method using the same |
| 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 |
| EP0774687A1 (en) * | 1995-10-30 | 1997-05-21 | Konica Corporation | Solid processing composition and method 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 |
| 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 |
| 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 |
Also Published As
| Publication number | Publication date |
|---|---|
| US2691589A (en) | 1954-10-12 |
| FR1106813A (fr) | 1955-12-23 |
| US2751297A (en) | 1956-06-19 |
| GB767699A (en) | 1957-02-06 |
| BE530883A (enEXAMPLES) | 1957-10-25 |
| GB767704A (en) | 1957-02-06 |
| FR1106144A (fr) | 1955-12-12 |
| BE530887A (enEXAMPLES) | 1957-10-25 |
| FR1109575A (fr) | 1956-01-31 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US2688548A (en) | Photographic developer composition | |
| US2688549A (en) | Photographic developer composition | |
| GB1019222A (en) | Improvements in or relating to silver halide photographic materials | |
| US3221023A (en) | (2-hydroxymethyl-3-pyrazolidones) | |
| DE69109653T2 (de) | Verfahren zur photographischen Herstellung von Silberbildern. | |
| US4155764A (en) | Photographic color developer composition | |
| US3650749A (en) | Photographic development | |
| US3782945A (en) | Mercaptotetrazaindene in photographic printing plate development | |
| US2685516A (en) | Photographic developer composition | |
| US2685515A (en) | Photographic developer composition | |
| GB1251558A (enEXAMPLES) | ||
| US3765901A (en) | Spectral sensitization of light-sensitive silver halide emulsions | |
| US4737450A (en) | Method for bleach-fixing of photographic elements | |
| US2271229A (en) | Fog inhibitor for photographic developers | |
| US2981623A (en) | Photographic developers | |
| US2384593A (en) | Antifoggant | |
| US3622339A (en) | Polymeric antifoggant containing at least four triazine rings | |
| US3615509A (en) | Photographic fixer-developer containing compounds with p-aminophenol and dyeforming nuclei | |
| US4717649A (en) | Photographic bleach-fixing compositions | |
| US3276875A (en) | Developing composition with pyrrolidone anti-sludging agent | |
| US3740221A (en) | Development of photographic material | |
| US3043694A (en) | Novel class of 3-indazolinone developing agent | |
| US3532499A (en) | Amino - n - oxides as development accelerators in photography | |
| US3161514A (en) | Nonstaining photographic developers | |
| US3563747A (en) | Photographic developing combinations |