EP0189604A1 - Procédé pour la production d'une image argentique comprenant un traitement de stabilisation-fixage - Google Patents
Procédé pour la production d'une image argentique comprenant un traitement de stabilisation-fixage Download PDFInfo
- Publication number
- EP0189604A1 EP0189604A1 EP85200096A EP85200096A EP0189604A1 EP 0189604 A1 EP0189604 A1 EP 0189604A1 EP 85200096 A EP85200096 A EP 85200096A EP 85200096 A EP85200096 A EP 85200096A EP 0189604 A1 EP0189604 A1 EP 0189604A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- process according
- silver halide
- halide emulsion
- silver
- mole
- 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.)
- Granted
Links
- 229910052709 silver Inorganic materials 0.000 title claims abstract description 43
- 239000004332 silver Substances 0.000 title claims abstract description 43
- 238000000034 method Methods 0.000 title claims abstract description 17
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 title claims abstract description 11
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 5
- -1 silver halide Chemical class 0.000 claims abstract description 51
- 239000000463 material Substances 0.000 claims abstract description 26
- 239000000839 emulsion Substances 0.000 claims abstract description 20
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Natural products NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims abstract description 11
- UMGDCJDMYOKAJW-UHFFFAOYSA-N aminothiocarboxamide Natural products NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 claims abstract description 11
- 229910052783 alkali metal Inorganic materials 0.000 claims abstract description 9
- 125000001183 hydrocarbyl group Chemical group 0.000 claims abstract description 6
- 125000002373 5 membered heterocyclic group Chemical group 0.000 claims abstract description 4
- 125000004070 6 membered heterocyclic group Chemical group 0.000 claims abstract description 4
- 239000007864 aqueous solution Substances 0.000 claims abstract description 4
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 4
- 239000001257 hydrogen Substances 0.000 claims abstract description 4
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims abstract description 4
- 229930195734 saturated hydrocarbon Natural products 0.000 claims abstract description 3
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 claims description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 5
- 239000000243 solution Substances 0.000 claims description 4
- 239000004133 Sodium thiosulphate Substances 0.000 claims description 3
- 230000003064 anti-oxidating effect Effects 0.000 claims description 3
- 239000007800 oxidant agent Substances 0.000 claims description 3
- AKHNMLFCWUSKQB-UHFFFAOYSA-L sodium thiosulfate Chemical group [Na+].[Na+].[O-]S([O-])(=O)=S AKHNMLFCWUSKQB-UHFFFAOYSA-L 0.000 claims description 3
- 235000019345 sodium thiosulphate Nutrition 0.000 claims description 3
- 229910021607 Silver chloride Inorganic materials 0.000 claims description 2
- HKZLPVFGJNLROG-UHFFFAOYSA-M silver monochloride Chemical compound [Cl-].[Ag+] HKZLPVFGJNLROG-UHFFFAOYSA-M 0.000 claims description 2
- 229910001961 silver nitrate Inorganic materials 0.000 claims description 2
- AFBBKYQYNPNMAT-UHFFFAOYSA-N 1h-1,2,4-triazol-1-ium-3-thiolate Chemical compound SC=1N=CNN=1 AFBBKYQYNPNMAT-UHFFFAOYSA-N 0.000 claims 1
- 239000007788 liquid Substances 0.000 description 19
- 150000001875 compounds Chemical class 0.000 description 11
- 239000003795 chemical substances by application Substances 0.000 description 7
- 230000006641 stabilisation Effects 0.000 description 6
- 230000003019 stabilising effect Effects 0.000 description 5
- 239000003381 stabilizer Substances 0.000 description 5
- 108010010803 Gelatin Proteins 0.000 description 4
- 229920000159 gelatin Polymers 0.000 description 4
- 239000008273 gelatin Substances 0.000 description 4
- 235000019322 gelatine Nutrition 0.000 description 4
- 235000011852 gelatine desserts Nutrition 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- 150000001340 alkali metals Chemical class 0.000 description 3
- 238000005406 washing Methods 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 2
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 description 2
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 description 2
- 230000002378 acidificating effect Effects 0.000 description 2
- 239000012190 activator Substances 0.000 description 2
- 238000004090 dissolution Methods 0.000 description 2
- XMBWDFGMSWQBCA-UHFFFAOYSA-N hydrogen iodide Chemical compound I XMBWDFGMSWQBCA-UHFFFAOYSA-N 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 230000003287 optical effect Effects 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
- 239000004297 potassium metabisulphite Substances 0.000 description 2
- 235000010263 potassium metabisulphite Nutrition 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- GEHJYWRUCIMESM-UHFFFAOYSA-L sodium sulfite Chemical compound [Na+].[Na+].[O-]S([O-])=O GEHJYWRUCIMESM-UHFFFAOYSA-L 0.000 description 2
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000003213 activating effect Effects 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 125000003342 alkenyl group Chemical group 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 125000003710 aryl alkyl group Chemical group 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 235000010323 ascorbic acid Nutrition 0.000 description 1
- 229960005070 ascorbic acid Drugs 0.000 description 1
- 239000011668 ascorbic acid Substances 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 150000002391 heterocyclic compounds Chemical class 0.000 description 1
- 238000005286 illumination Methods 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 230000005499 meniscus Effects 0.000 description 1
- 230000009972 noncorrosive effect Effects 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- CMCWWLVWPDLCRM-UHFFFAOYSA-N phenidone Chemical compound N1C(=O)CCN1C1=CC=CC=C1 CMCWWLVWPDLCRM-UHFFFAOYSA-N 0.000 description 1
- 229940100890 silver compound Drugs 0.000 description 1
- 150000003379 silver compounds Chemical class 0.000 description 1
- 235000010265 sodium sulphite Nutrition 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 150000003567 thiocyanates Chemical class 0.000 description 1
- DHCDFWKWKRSZHF-UHFFFAOYSA-L thiosulfate(2-) Chemical compound [O-]S([S-])(=O)=O DHCDFWKWKRSZHF-UHFFFAOYSA-L 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 239000003021 water soluble solvent Substances 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
- the present invention relates to a process for the production of a silver image including a stabilisation-fixing treatment of an image-wise exposed and developed photographic silver halide emulsion material to obtain an image having improved heat and/or light stability.
- Stabilising baths for exposed and developed photographic silver halide emulsion layers which contain a large variety of organic mercapto compounds are state of the art and particulars concerning such baths are described, e.g. in the book "Modern Photographic Processing” Vol. 2 of Grant Haist - A Wiley Interscience Publication - (1979) New York - p. 210-227.
- the stabilising agent forms an insoluble non-lightsensitive silver compound while the fixing agent forms a soluble silver complex.
- solubility of said compounds in a given medium varies inter alia with the pH-value of the medium.
- one compound may be effective as stabilising agent as well as a fixing agent depending on the pH-value of the processing bath.
- a solution is used containing at least one compound (A) and (B).
- Compound (A) is an iodide of alkali metals and ammonium.
- Compound (B) corresponds to the following general formula : wherein :
- a process for the production of a silver image including a stabilising-fixing treatment of said image formed by development of an imagewise exposed photographic silver halide emulsion material is provided wherein the imagewise exposed and developed silver halide emulsion material is treated with an aqueous solution containing an alkali metal thiosulphate and a cyclic thiourea compound corresponding to the following general formula (X) or a corresponding tautomeric structure thereof : wherein :
- Table 1 contains a list of specific compounds within the scope of the above general formula (X) with a literature reference for their preparation.
- the specified heterocyclic compounds are simply dissolved in water together with the other ingredients.
- the pH of the treating liquid is in the acidic range, e.g. in the range of 6 to 4.
- Small amounts of water-soluble solvents, e.g. acetic acid and water-miscible alcohols may be added to improve the dissolution of the cyclic thiourea compound.
- the treating liquids used according to the present invention contain an anti-oxidizing agent to shield the cyclic thiourea compound from aerial oxidation.
- Suitable anti-oxidizing agents are ascorbic acid and compounds yielding sulphite ions such as sodium sulphite and potassium metabisulphite.
- the present image-stabilising process makes it possible to eliminate the customary washing procedure and yet to obtain a satisfactory stable print.
- the treatment of the developed silver image with the above aqueous solution containing alkali metal thiosulphate ions and the cyclic thiourea compound corresponding to the general formula (X) may be preceded by a rinsing treatment but such is not strictly necessary.
- the image-stabilising liquids used according to the present invention do not alter the binding properties of gelatin, so that no sticky gelatin silver halide emulsion layers are obtained as is the case when using stabilising liquids based on thiocyanates. Further no particular odour is produced and toxicity and corrosivity are very low.
- the stabilising-fixing treatment according to the present invention is particularly effective for the stabilisation of silver images obtained by means of silver halide emulsion layers wherein the silver halide is for at least 50 mole % silver chloride.
- the present stabilising-fixing treatment is very effective when used in conjunction with silver halide emulsion layers having a silver halide coverage, the silver halide being expressed in an equivalent amount of silver nitrate, not higher than 4 g per sq.m.
- the treatment according to the present invention provides image stabilisation in a short time.
- Stabilising treatment according to the present invention may be terminated in 30 s at room temperature (20°C) and may be terminated in 15 s at 35 °C.
- the stabilising-fixing treatment can be used for photographic black-and-white papers and films, e.g. graphic art film materials, but is likewise applicable for the image stabilisation of photographic colour materials wherein residual silver halide may not remain.
- the photographic materials may contain already before the exposure some or all of the developing agent(s) used in the development step.
- the developing agents When the developing agents are present already in the photographic material during the exposure the development may be carried out with a so-called activator bath which is an alkaline aqueous liquid being free from developing agents and activates these agents already present in the photographic material.
- the silver images stabilised according to the present invention show a very low darkening in the non-image area under circumstances of heat, humidity and/or light-exposure.
- the washing liquid likewise incorporates a said cyclic thiourea compound, e.g. in an amount up to 1x10 mole per liter.
- the application of the treating liquids used in the processing of photographic silver halide emulsion materials may proceed by immersion but more advantageously proceeds by meniscus coating using a lick-roller, sponge or resilient roller to limit the volume of applied liquid .
- an image-wise exposed silver halide emulsion material according to the present invention it is in favour of effective stabilisation to keep the pH of the liquid(s) containing said cyclic thiourea compound in the acidic range and therefore to eliminate as much as possible of the alkaline developing or development activating liquid from the material before applying the stabilising liquid.
- Such may proceed by squeegee, e.g. with rollers or by applying an intermediate rinsing step.
- Said photographic material was treated in unexposed state for 10 s at 20°C with an alkaline aqueous activator liquid having the following composition :
- the developed material was led between squeegee rollers to remove the major part of adhering alkaline liquid and was then dipped for 5 s at 20 °C into a fixing or stabilising-fixing liquid as defined in the following Table 2.
- Liquid no. 1 contained per liter 198.5 g (0.80 mole) of sodium thiosulphate.5 water and 25 g of potassium metabisulphite.
- Liquid no. 2 had the same composition as liquid no. 1 but included in addition thereto per liter 10 g of 2-thio-hexahydropyrimidone-2.
- the fixing-stabilisation was followed by rinsing.
- the rinsing was effected by conveying the material for 10 s at 20 °C through a tray containing plain water.
- the efficiency of the stabilisation was determined by measuring the change in optical density ( ⁇ D) obtained after keeping one strip (i) of the processed material for 3 days in the dark at 35 °C at 80 % relative humidity and another strip (ii) for 4 h in a XENOTEST (trade name) exposure apparatus wherein the strip was subjected to a white light illumination of 180,000 lux.
Landscapes
- Physics & Mathematics (AREA)
- General Physics & Mathematics (AREA)
- Silver Salt Photography Or Processing Solution Therefor (AREA)
- Nitrogen Condensed Heterocyclic Rings (AREA)
Priority Applications (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| EP85200096A EP0189604B1 (fr) | 1985-01-29 | 1985-01-29 | Procédé pour la production d'une image argentique comprenant un traitement de stabilisation-fixage |
| DE8585200096T DE3565014D1 (en) | 1985-01-29 | 1985-01-29 | Process for the production of a silver image including a stabilisation-fixing treatment |
| JP1462286A JPS61183645A (ja) | 1985-01-29 | 1986-01-24 | 安定化定着処理を含む銀像の製造方法 |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| EP85200096A EP0189604B1 (fr) | 1985-01-29 | 1985-01-29 | Procédé pour la production d'une image argentique comprenant un traitement de stabilisation-fixage |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| EP0189604A1 true EP0189604A1 (fr) | 1986-08-06 |
| EP0189604B1 EP0189604B1 (fr) | 1988-09-14 |
Family
ID=8193991
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| EP85200096A Expired EP0189604B1 (fr) | 1985-01-29 | 1985-01-29 | Procédé pour la production d'une image argentique comprenant un traitement de stabilisation-fixage |
Country Status (3)
| Country | Link |
|---|---|
| EP (1) | EP0189604B1 (fr) |
| JP (1) | JPS61183645A (fr) |
| DE (1) | DE3565014D1 (fr) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0356581A1 (fr) * | 1988-08-09 | 1990-03-07 | Agfa-Gevaert N.V. | Méthode de traitement d'un matériau photographique à émulsion d'halogénure d'argent |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH07119974B2 (ja) * | 1987-12-16 | 1995-12-20 | 富士写真フイルム株式会社 | ハロゲン化銀感光材料の現像処理方法 |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| FR2075615A5 (en) * | 1970-01-15 | 1971-10-08 | Agfa Gevaert Ag | N-and s-heterocyclic stabilizers for photo-g |
| GB1285696A (en) * | 1968-09-19 | 1972-08-16 | Kodak Ltd | Processing method for photodevelopable silver halide recording materials |
| US3854947A (en) * | 1973-05-16 | 1974-12-17 | E Ritchey | Process and solution for fixing an image on silver halide prints |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0189603A1 (fr) * | 1985-01-29 | 1986-08-06 | Agfa-Gevaert N.V. | Procédé pour la production d'une image argentique comprenant un traitement de stabilisation-fixage |
-
1985
- 1985-01-29 DE DE8585200096T patent/DE3565014D1/de not_active Expired
- 1985-01-29 EP EP85200096A patent/EP0189604B1/fr not_active Expired
-
1986
- 1986-01-24 JP JP1462286A patent/JPS61183645A/ja active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB1285696A (en) * | 1968-09-19 | 1972-08-16 | Kodak Ltd | Processing method for photodevelopable silver halide recording materials |
| FR2075615A5 (en) * | 1970-01-15 | 1971-10-08 | Agfa Gevaert Ag | N-and s-heterocyclic stabilizers for photo-g |
| US3854947A (en) * | 1973-05-16 | 1974-12-17 | E Ritchey | Process and solution for fixing an image on silver halide prints |
Non-Patent Citations (2)
| Title |
|---|
| PATENTS ABSTRACTS OF JAPAN, vol. 7, no. 234 (P-230)[1379], 18th October 1983; & JP - A - 58 122 536 (MITSUBISHI SEISHI K.K.) 21-07-1983 * |
| PATENTS ABSTRACTS OF JAPAN, vol. 9, no. 68 (P-344)[1791], 28 March 1985; & JP - A - 59 201 056 (KONISHIROKU SHASHIN KOGYO K.K.) 14-11-1984 * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0356581A1 (fr) * | 1988-08-09 | 1990-03-07 | Agfa-Gevaert N.V. | Méthode de traitement d'un matériau photographique à émulsion d'halogénure d'argent |
Also Published As
| Publication number | Publication date |
|---|---|
| EP0189604B1 (fr) | 1988-09-14 |
| DE3565014D1 (en) | 1988-10-20 |
| JPS61183645A (ja) | 1986-08-16 |
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