US3627531A - Stabilizing developed silver halide emulsions with heterocyclic thiol compounds - Google Patents
Stabilizing developed silver halide emulsions with heterocyclic thiol compounds Download PDFInfo
- Publication number
- US3627531A US3627531A US753699A US3627531DA US3627531A US 3627531 A US3627531 A US 3627531A US 753699 A US753699 A US 753699A US 3627531D A US3627531D A US 3627531DA US 3627531 A US3627531 A US 3627531A
- Authority
- US
- United States
- Prior art keywords
- solution
- stabilizing
- mercapto
- silver
- thiol compound
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Lifetime
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- -1 silver halide Chemical class 0.000 title abstract description 60
- 230000000087 stabilizing effect Effects 0.000 title abstract description 48
- 229910052709 silver Inorganic materials 0.000 title abstract description 36
- 239000004332 silver Substances 0.000 title abstract description 36
- 239000000839 emulsion Substances 0.000 title abstract description 14
- 239000003795 chemical substances by application Substances 0.000 abstract description 28
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 abstract description 26
- 230000007423 decrease Effects 0.000 abstract description 17
- 238000004321 preservation Methods 0.000 abstract description 3
- OXFSTTJBVAAALW-UHFFFAOYSA-N 1,3-dihydroimidazole-2-thione Chemical compound SC1=NC=CN1 OXFSTTJBVAAALW-UHFFFAOYSA-N 0.000 abstract description 2
- 238000002845 discoloration Methods 0.000 abstract description 2
- 239000000243 solution Substances 0.000 description 81
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 25
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 15
- 229910021607 Silver chloride Inorganic materials 0.000 description 14
- HKZLPVFGJNLROG-UHFFFAOYSA-M silver monochloride Chemical compound [Cl-].[Ag+] HKZLPVFGJNLROG-UHFFFAOYSA-M 0.000 description 14
- 230000001476 alcoholic effect Effects 0.000 description 13
- SOIFLUNRINLCBN-UHFFFAOYSA-N ammonium thiocyanate Chemical compound [NH4+].[S-]C#N SOIFLUNRINLCBN-UHFFFAOYSA-N 0.000 description 13
- 239000000203 mixture Substances 0.000 description 13
- 239000003381 stabilizer Substances 0.000 description 11
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 10
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 10
- 229910052700 potassium Inorganic materials 0.000 description 10
- 239000011591 potassium Substances 0.000 description 10
- 229910052783 alkali metal Inorganic materials 0.000 description 9
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 description 8
- ZMZDMBWJUHKJPS-UHFFFAOYSA-N hydrogen thiocyanate Natural products SC#N ZMZDMBWJUHKJPS-UHFFFAOYSA-N 0.000 description 8
- 150000003839 salts Chemical class 0.000 description 7
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- 239000007864 aqueous solution Substances 0.000 description 6
- 238000000034 method Methods 0.000 description 6
- 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 5
- 239000000463 material Substances 0.000 description 5
- 229910052708 sodium Inorganic materials 0.000 description 5
- 239000011734 sodium Substances 0.000 description 5
- YHMYGUUIMTVXNW-UHFFFAOYSA-N 1,3-dihydrobenzimidazole-2-thione Chemical compound C1=CC=C2NC(S)=NC2=C1 YHMYGUUIMTVXNW-UHFFFAOYSA-N 0.000 description 4
- HWGBHCRJGXAGEU-UHFFFAOYSA-N Methylthiouracil Chemical compound CC1=CC(=O)NC(=S)N1 HWGBHCRJGXAGEU-UHFFFAOYSA-N 0.000 description 4
- IOLCXVTUBQKXJR-UHFFFAOYSA-M potassium bromide Chemical compound [K+].[Br-] IOLCXVTUBQKXJR-UHFFFAOYSA-M 0.000 description 4
- 230000006641 stabilisation Effects 0.000 description 4
- 238000011105 stabilization Methods 0.000 description 4
- 238000005406 washing Methods 0.000 description 4
- FHTDDANQIMVWKZ-UHFFFAOYSA-N 1h-pyridine-4-thione Chemical compound SC1=CC=NC=C1 FHTDDANQIMVWKZ-UHFFFAOYSA-N 0.000 description 3
- JRFUIXXCQSIOEB-UHFFFAOYSA-N 3-phenyl-1,3,4-thiadiazolidine-2,5-dithione Chemical compound S=C1SC(S)=NN1C1=CC=CC=C1 JRFUIXXCQSIOEB-UHFFFAOYSA-N 0.000 description 3
- YXIWHUQXZSMYRE-UHFFFAOYSA-N 1,3-benzothiazole-2-thiol Chemical compound C1=CC=C2SC(S)=NC2=C1 YXIWHUQXZSMYRE-UHFFFAOYSA-N 0.000 description 2
- YQQSRZSUGBETRS-UHFFFAOYSA-N 1h-pyridazine-6-thione Chemical compound SC1=CC=CN=N1 YQQSRZSUGBETRS-UHFFFAOYSA-N 0.000 description 2
- GDGIVSREGUOIJZ-UHFFFAOYSA-N 5-amino-3h-1,3,4-thiadiazole-2-thione Chemical compound NC1=NN=C(S)S1 GDGIVSREGUOIJZ-UHFFFAOYSA-N 0.000 description 2
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- 239000001828 Gelatine Substances 0.000 description 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- ZMZDMBWJUHKJPS-UHFFFAOYSA-M Thiocyanate anion Chemical compound [S-]C#N ZMZDMBWJUHKJPS-UHFFFAOYSA-M 0.000 description 2
- 239000012190 activator Substances 0.000 description 2
- 239000012670 alkaline solution Substances 0.000 description 2
- 238000005282 brightening Methods 0.000 description 2
- 125000004432 carbon atom Chemical group C* 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 238000011109 contamination Methods 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000005562 fading Methods 0.000 description 2
- 229920000159 gelatin Polymers 0.000 description 2
- 235000019322 gelatine Nutrition 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- RWPGFSMJFRPDDP-UHFFFAOYSA-L potassium metabisulfite Chemical compound [K+].[K+].[O-]S(=O)S([O-])(=O)=O RWPGFSMJFRPDDP-UHFFFAOYSA-L 0.000 description 2
- 229940043349 potassium metabisulfite Drugs 0.000 description 2
- 235000010263 potassium metabisulphite Nutrition 0.000 description 2
- ADZWSOLPGZMUMY-UHFFFAOYSA-M silver bromide Chemical compound [Ag]Br ADZWSOLPGZMUMY-UHFFFAOYSA-M 0.000 description 2
- GEHJYWRUCIMESM-UHFFFAOYSA-L sodium sulfite Chemical compound [Na+].[Na+].[O-]S([O-])=O GEHJYWRUCIMESM-UHFFFAOYSA-L 0.000 description 2
- DNIAPMSPPWPWGF-GSVOUGTGSA-N (R)-(-)-Propylene glycol Chemical compound C[C@@H](O)CO DNIAPMSPPWPWGF-GSVOUGTGSA-N 0.000 description 1
- FKASFBLJDCHBNZ-UHFFFAOYSA-N 1,3,4-oxadiazole Chemical compound C1=NN=CO1 FKASFBLJDCHBNZ-UHFFFAOYSA-N 0.000 description 1
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 1
- FLFWJIBUZQARMD-UHFFFAOYSA-N 2-mercapto-1,3-benzoxazole Chemical compound C1=CC=C2OC(S)=NC2=C1 FLFWJIBUZQARMD-UHFFFAOYSA-N 0.000 description 1
- GZEYLLPOQRZUDF-UHFFFAOYSA-N 7-(dimethylamino)-4-methylchromen-2-one Chemical compound CC1=CC(=O)OC2=CC(N(C)C)=CC=C21 GZEYLLPOQRZUDF-UHFFFAOYSA-N 0.000 description 1
- 229920002134 Carboxymethyl cellulose Polymers 0.000 description 1
- QXNVGIXVLWOKEQ-UHFFFAOYSA-N Disodium Chemical compound [Na][Na] QXNVGIXVLWOKEQ-UHFFFAOYSA-N 0.000 description 1
- 125000000066 S-methyl group Chemical group [H]C([H])([H])S* 0.000 description 1
- KEAYESYHFKHZAL-UHFFFAOYSA-N Sodium Chemical compound [Na] KEAYESYHFKHZAL-UHFFFAOYSA-N 0.000 description 1
- 235000010724 Wisteria floribunda Nutrition 0.000 description 1
- SJOOOZPMQAWAOP-UHFFFAOYSA-N [Ag].BrCl Chemical compound [Ag].BrCl SJOOOZPMQAWAOP-UHFFFAOYSA-N 0.000 description 1
- 239000003929 acidic solution Substances 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 150000001491 aromatic compounds Chemical group 0.000 description 1
- 125000003785 benzimidazolyl group Chemical group N1=C(NC2=C1C=CC=C2)* 0.000 description 1
- 125000001164 benzothiazolyl group Chemical group S1C(=NC2=C1C=CC=C2)* 0.000 description 1
- 125000004541 benzoxazolyl group Chemical group O1C(=NC2=C1C=CC=C2)* 0.000 description 1
- ZEUDGVUWMXAXEF-UHFFFAOYSA-L bromo(chloro)silver Chemical compound Cl[Ag]Br ZEUDGVUWMXAXEF-UHFFFAOYSA-L 0.000 description 1
- 229910052793 cadmium Inorganic materials 0.000 description 1
- 239000001768 carboxy methyl cellulose Substances 0.000 description 1
- 235000010948 carboxy methyl cellulose Nutrition 0.000 description 1
- 239000008112 carboxymethyl-cellulose Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000002950 deficient Effects 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 125000005843 halogen group Chemical group 0.000 description 1
- 229910001385 heavy metal Inorganic materials 0.000 description 1
- 150000002391 heterocyclic compounds Chemical group 0.000 description 1
- 125000002883 imidazolyl group Chemical group 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 125000001715 oxadiazolyl group Chemical group 0.000 description 1
- 125000002971 oxazolyl group Chemical group 0.000 description 1
- 238000006303 photolysis reaction Methods 0.000 description 1
- 230000015843 photosynthesis, light reaction Effects 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
- 230000002265 prevention Effects 0.000 description 1
- 125000002098 pyridazinyl group Chemical group 0.000 description 1
- 125000004076 pyridyl group Chemical group 0.000 description 1
- 125000000714 pyrimidinyl group Chemical group 0.000 description 1
- 230000000717 retained effect Effects 0.000 description 1
- 239000012047 saturated solution Substances 0.000 description 1
- 150000003378 silver Chemical class 0.000 description 1
- RHUVFRWZKMEWNS-UHFFFAOYSA-M silver thiocyanate Chemical compound [Ag+].[S-]C#N RHUVFRWZKMEWNS-UHFFFAOYSA-M 0.000 description 1
- 235000010265 sodium sulphite Nutrition 0.000 description 1
- PXQLVRUNWNTZOS-UHFFFAOYSA-N sulfanyl Chemical class [SH] PXQLVRUNWNTZOS-UHFFFAOYSA-N 0.000 description 1
- 125000003831 tetrazolyl group Chemical group 0.000 description 1
- 125000005305 thiadiazolinyl group Chemical group 0.000 description 1
- 125000001113 thiadiazolyl group Chemical group 0.000 description 1
- 125000000335 thiazolyl group Chemical group 0.000 description 1
- 150000003567 thiocyanates Chemical class 0.000 description 1
- 150000003573 thiols Chemical class 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 229910052725 zinc Inorganic materials 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
- G03C5/38—Fixing; Developing-fixing; Hardening-fixing
- G03C5/39—Stabilising, i.e. fixing without washing out
Definitions
- This invention relates to a process for the production of photographic stable visible images in a photographic silver halide emulsion layer, and more particularly to a method for stabilizing the developed image without necessary fixing and washing.
- Fixing and washing followed thereby are carried out in order to remove silver halide in the non-exposed parts after development.
- the water soluble silverthiosulfate complex formed during fixing is unstable to light, it must be removed by washing with water.
- stabilizers are thiol compounds represented by the general formula RSH Where R is an aliphatic, aromatic or heterocyclic compound with a free SH group. Most thiol compounds are difiicultly soluble in an acidic solution and form yellow silver salts or complex salts. Further, they are usually toxic and have an offensive smell (ref. H. D. Russell: Photographic Engineering, 2(3), 136 (1951)). Thus due to defective properties, a thiol compound alone is of no practical use. Generally, alkali metal thiocyanates and ammonium thiocyanate are used as stabilizers.
- the silver-thiocyanate complex is a transparent crystal and locates at white or transparent parts. Since this salt is stable to light it is unnecessary to remove it by washing with water (ref. British patent specification No. 867,242, French patent specifications No. 1,206,359, No. 1,239,429 and No. 1,258,356). Such treatment for stabilization enables rapid treatment but it is attended by many disadvantages in the quality of the image. In order to secure the stabilization to light, the silver complex forming agent is used in excess of the theoretical amount. Because of the hygroscopic property of the agent, the surface of the 3,627,531 Patented Dec. 14, 1971 processed emulsion layer tends to become sticky.
- the silver complex forming agent gradually oxidizes metallic silver constituting the image, converts it into a silver complex and decreases the density of the image or causes the image to disappear.
- the decrease in density, and the change in color from black to brown to yellow becomes remarkable with the lapse of time, and in an extreme case the image disappears.
- Such fading phenomenon is often observed when the material is preserved under high humidity. If the exposure is effected before the completion of reaction between unexposed silver halide and silver complex forming agent, the photolysis of unstable silver complex salt and unstabilized silver halide occurs and the white part or the transparent part is contaminated.
- Alkali metal thiocyanates and ammonium thiocyanate have defects as aforementioned, but these thiocyanates exceed the other stabilizers in solubility, and are nonodorous and easily obtainable, and a colorless silver complex salt can be obtained using them.
- an object of the present invention to provide an improved method of stabilization using alkali metal thiocyanates or ammonium thiocyanate.
- Another object is to prevent decrease in density, change in tone or contamination of the white part or transparent part of the image by light when the photographic image obtained by the stabilizing treatment is preserved in an atmospheric condition.
- Still another object is to modify said stabilizers so that good properties are retained and the defects are removed.
- a latent image formed in a silver halide emulsion layer containing a developing agent in an alkaline solution either stabilizing the layer in an aqueous solution containing a silver complex forming agent, such as an alkali metal thiocyanate or ammonium thiocyanate, and at least 0.01%, based on the weight of the silver complex forming agent, of a thiol compound as below-mentioned, or stabilizing the layer in a first aqueous solution containing the silver complex forming agent, followed by processing the layer with a second aqueous solution containing at least 0.01%, based on the weight of the silver complex forming agent, of the thiol compound when compared on the basis of the same volume. That is, the concentration of the thiol compound in the second solution is at least 0.01% of the concentration of the silver complex forming agent in the first solution.
- the thiol compound used in the process of this invention is represented by the general formula:
- the amount of the thiol compound added to the alkali metal thiocyanate or ammonium thiocyanate is preferably 0.8% by weight at the maximum. Addition of more than 0.8% of the thiol compound leaves much undissolved, and since addition of 0.8% or less is effective, the use of more than 0.8%
- the treating solution of the present invention it is possible to utilize the good properties of an alkali metal thiocyanate or ammonium thiocyanate as stabilizer and to get rid of the unfavourable effects thereof.
- the thiol compound used in the present invention is generally poor in solubility so that its sole use as stabilizer does not produce a solution having a concentration suflicient enough to be a treating solution.
- the thiol compound is not used as stabilizing agent, but as an addition agent in a small amount, so that a poorly soluble thiol compound can be employed without the least inconvenience.
- the thiol compound even in the form of a super-saturated solution is inadequate by itself to function as a stabilizer, since the photosensitive material treated therewith is printed-out and then fades at high temperature and in high humidity. Nevertheless, the joint use of an alkaline metal thiocyanate or ammonium thiocyanate and a small amount of a thiol compound achieves good effects such as prevention of change in tone. Due to this fact, the present invention has accomplished improvements in the stabilization using an alkali metal thiocyanate or ammonium thiocyanate.
- the abovementioned thiol compounds may be used together with salts of heavy metals such as Ni, Co, Cd, Zn and Au, which can form soluble or insoluble complex salts with the stabilizing agent to stabilize the image.
- the treating solution of the present invention may contain a hardening agent, carboxymethyl cellulose or alcohol.
- the thiol compound according to the present invention can also be used in the form of a separate solution, without incorporating it into the stabilizing solution.
- the developed photosensitive material is treated with a stablizing agent such as ammonium thiocyanate and then immersed in a solution containing at least 0.01% and up to about 0.8% based on the weight of the silver complex forming agent, by weight of the thiol compound when compared on the basis of the same volume.
- This aqueous solution may contain a fluorescent brightening agent.
- the time of immersion is about 2 seconds but it is not so limited.
- EXAMPLE 1 An emulsion was prepared by adding 20 grams of hydroquinone to one kilogram of a gelatino silver chloride emulsion (silver chloride 4.3% by weight) and adjusting the pH to 5.0. This emulsion was coated on a paper support.
- the coating was exposed, developed in an activator solution having the following composition:
- the procedure for preparing the solution was as follows: potassium metabisulfite was dissolved in 300 cc. of water and then Formalin was added. The solution after mixing was heated by the heat of reaction. After the temperature of the solution was lowered to room temperature, 0.4% alcohol solution of Z-mercaptoimidazole was added, then water was added until the total amount of the solution was attained to 1000 cm.
- the image stabilized with this solution showed sufficient stability after drying. Even when preserved under a severe condition of high humidity such as RH the decrease in density of image was less than that of an image treated with a solution which contained the agents listed above excepting Z-mercaptoimidazole. That is, the preservation property was better.
- EXAMPLE 2 A photosensitive paper of silver chloride was treated with a stabilizing solution having the following composition in the same way as in Example 1.
- the print was exposed to the light of a fluorescent lamp of 1,000 lux for 24 hours immediately after drying. Con tamination of white parts was apparently less than the case when a stabilizing solution without Z-mercaptobenzimidazole was employed.
- EXAMPLE 3 A photosensitive paper of silver chloride was treated with a stabilizing solution having the following composition in the same way as in Example 1.
- EXAMPLE 5 A photosensitive paper of silver chloride was treated with a solution having the following composition in the same way as in Example 1.
- EXAMPLE 6 A film coated with the emulsion of silver chloride bromide (silver bromide 10%) which contains gelatine and hydroquinone, was exposed, developed and then treated with a stabilizing solution having the following composition in the same way as in Example 1.
- silver chloride bromide silver bromide 10%
- EXAMPLE 7 A photosenstive paper of silver chloride was. treated with a stabilizing solution having the following composition in the same way as in Example 1.
- EXAMPLE 8 A photosensitive paper of silver chloride was treated with a solution having the following composition in the same way as in Example 1.
- EXAMPLE 10 A photosensitive paper prepared by coating the emulsion of silver chlorobromide (silver bromide 10%) containing gelatine and hydroquinone, was exposed, developed and then treated with stabilizing solution having the following composition in the same way as in Example 1.
- EXAMPLE 11 A photosenstive paper of silver chloride was treated with the following solution in the same way as in Example 1.
- ammonium thiocyanateg borax2 g.
- the treated paper was then immersed in a 0.1% aqueous solution of potassium salt of 2-mercapto-4-phenyl- 1,3,4-thiadiazoline-5-thione for 2 seconds.
- EXAMPLE 12 A photosensitive paper of silver chloride was treated with a stabilizing solution having the following composition in the same way as in Example 1.
- ammonium thiocyanate250 g ammonium thiocyanate250 g.
- EXAMPLE 17 A photosensitive paper of silver chloride was treated with a solution of the following composition in the same way as in Example 1.
- the photosensitive material thus treated in which the unexposed silver chloride was converted to the stabilized silver complex salt was then dipped for about 2 seconds in a solution having the following composition and dried.
- EXAMPLE 18 The efiect of our invention is further illustrated by 10 the following comparison of the following three stabilizing solutions: (1) a stabilizing solution containing ammoniurn thiocyanate alone (Recipe 3), (2) a stabilizing solution containing ammonium thiocyanate and a thiol compound (Recipes 1 and 2) and (3) a stabilizing solution containing a thiol compound alone (Recipes 4 and 5).
- a photographic silver chloride emulsion layer containing hydroquinone was exposed, developed in an activator solution containing 5% NaOH and 0.01% KBr, and then subjected to the stabilizing treatment with the following stabilizing solutions:
- the photosensitive paper thus treated was placed under the following conditions:
- the resulting color of the image is shown in the following table.
- a process for the production of photographic stable visible images in a silver halide photographic emulsion layer containing latent images which comprises developing said latent images in an alkaline solution and stabilizing said layer by applying an aqueous solution containing a silver complex-forming agent and between 0.01% and 0.8%, based on the weight of said silver complex forming agent, of a thiol compound, said silver complex-forming agent being a member selected from the group consisting of an alkali metal thiocyanate and ammonium thiocyanate and said thiol compound being a member selected from the group consisting of Z-mercaptoimidazole, Z-rnercaptobenzimidazole, S-ethoxycarbonyl-mercapto-4-methyl thiazole, Z-mercaptobenzothiazole,
- a stabilizing solution containing a silver complexforming agent and between 0.01% and 0.8%, based on the weight of said silver complex-forming agent, of a thiol compound said silver complex-forming agent being a member selected from the group consisting of an alkali metal thiocyanate and ammonium thiocyanate and said thiol compound being a member selected from the group consisting of Z-mercaptoimidazole, Z-mercaptobenzimidazole, S-ethoxycarbonyl-mercapto-4-methyl-thiazole, 2-mercapt0benzothiazole,
Landscapes
- Physics & Mathematics (AREA)
- General Physics & Mathematics (AREA)
- Silver Salt Photography Or Processing Solution Therefor (AREA)
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP4711961 | 1961-12-25 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| US3627531A true US3627531A (en) | 1971-12-14 |
Family
ID=12766261
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| US753699A Expired - Lifetime US3627531A (en) | 1961-12-25 | 1968-08-19 | Stabilizing developed silver halide emulsions with heterocyclic thiol compounds |
Country Status (3)
| Country | Link |
|---|---|
| US (1) | US3627531A (enrdf_load_stackoverflow) |
| DE (1) | DE1422872B2 (enrdf_load_stackoverflow) |
| FR (1) | FR1335294A (enrdf_load_stackoverflow) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4500632A (en) * | 1981-09-09 | 1985-02-19 | Fuji Photo Film Co., Ltd. | Process for stabilizing silver images |
| US4672043A (en) * | 1985-02-19 | 1987-06-09 | Eastman Kodak Company | Stabilization of developed electrophoregrams |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE3436862A1 (de) * | 1984-10-08 | 1986-04-10 | Tetenal Photowerk GmbH & Co, 2000 Norderstedt | Verfahren zur stabilisierung eines farbfotografischen materials sowie ein stabilisierungsbad zur verwendung in diesem verfahren |
-
1962
- 1962-09-17 FR FR909620A patent/FR1335294A/fr not_active Expired
- 1962-10-13 DE DE19621422872 patent/DE1422872B2/de active Granted
-
1968
- 1968-08-19 US US753699A patent/US3627531A/en not_active Expired - Lifetime
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4500632A (en) * | 1981-09-09 | 1985-02-19 | Fuji Photo Film Co., Ltd. | Process for stabilizing silver images |
| US4672043A (en) * | 1985-02-19 | 1987-06-09 | Eastman Kodak Company | Stabilization of developed electrophoregrams |
Also Published As
| Publication number | Publication date |
|---|---|
| DE1422872B2 (de) | 1976-01-29 |
| FR1335294A (fr) | 1963-08-16 |
| DE1422872A1 (de) | 1971-12-16 |
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