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
  • G03C5/38—Fixing; Developing-fixing; Hardening-fixing
  • G03C5/383—Developing-fixing, i.e. mono-baths
• • 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
  • G03C8/00—Diffusion transfer processes or agents therefor; Photosensitive materials for such processes
  • G03C8/32—Development processes or agents therefor
  • G03C8/36—Developers
  • G03C8/365—Developers containing silver-halide solvents

Definitions

• the present invention relates to a developing solution and a method for developing an exposed photographic silver halide material.
• the formation of silver deposit can be attributed to the presence in conventional developers of silver halide complexing agents like, e.g., sulphite and thiocyanate ions, which are present for stability and speed.
• the complex ions formed are effectively reduced to metallic silver nuclei. Growth of said nearly invisible fine nuclei leads to the formation of said silver deposit.
• regularly cleaning of the automatic processing machines is required.
• a film is introduced into the processor as first film of a whole series of films, its first contact with the first stained roller releases the deposit from the said roller or disturbs the deposited layer.
• the unevenly distributed dirt or stain comes into contact again with the transported film surface so that it may be deposited onto said surface.
• This phenomenon is recurrently repeated, not only at the first roller, but also at the further rollers that are mounted onto the racks and is well-known as "pi-line” defect.
• the crystalline silver deposit may further cause damaging of the surface of the coated hydrophilic layers on the film and/or cause locally situated pressure phenomena, resulting in "artefacts", thereby seriously impeding the diagnostic value of the obtained image.
• the silver halide photographic material shows processed images with a diagnostic value, like, e.g., in medical imaging or in non-destructive testing, said diagnostic value may be impaired.
• sparingly soluble and non-reducible silver salts as, e.g., 5,5'-bis-1,2,4-triazoline-3-thiones or derivatives of 1,3,4-thiadiazole-2-thiols as described, e.g. in BE-P 606,550 and GB-P 1,120,963, 2-mercapto-1,3,4-thiadiazoles described in US-P 3,212,892.
• emulsion layer may contain auxiliary coating agents such as saponin, sodium lauryl sulphate, dodecylphenol polyethylene oxide ether and hexadecyltrimethyl ammonium bromide.
• EP-Specification 0 223 883 a method to reduce the appearance of silver deposit has been described which comprises the treating of a silver halide photographic material with an aqueous alkaline liquid in the presence of (i) a developing agent, (ii) a heterocyclic mercapto compound including an aliphatic group of at least 3 carbon atoms and (iii) a surface active agent, characterised in that said surface active agent is an anionic alkylphenoxy polyalkyleneoxy phosphate ester surfactant.
• EP-A 0 620 484 reduction of the so-called "pi-line" defect, already mentioned hereinbefore, especially for processed materials for non-destructive testing purposes, has been described.
• Such materials should comprise at least one vinyl sulphone compound as a hardening agent and at least one polyoxyalkylene compound as a surfactant in at least one of its hydrophilic layers.
• a processing method comprising a developing step wherein the developer comprises as a surfactant at least one anionic alkylphenoxy and/or alkoxy polyalkyleneoxy phosphate ester, sulphate ester, alkyl carboxylic, sulphonic or phosphonic acid and/or a salt thereof a remarkable improvement has been obtained.
• a similar result has been obtained as disclosed in EP-A's 0 621 506 and 0 620 483.
• a developer having a low pH value between 9.6 and 11.0, preferably between 9.6 and 10.3, and comprising hydroquinone in an amount from 0 to less than 30 g per litre, an auxiliary developing agent, and as silver halide complexing agents alkali metal sulphite salts, preferably sodium salts, in an amount from 0 to less than 50 g per litre, more preferably to less than 40 g per litre, and thiocyanate salts in amounts from 0.1 to 3 g, more preferably from 0.5 to 2.5 g per litre, and at least 1 g per litre of a compound corresponding to the formula (I), a precursor thereof, a derivative thereof and/or a metal salt thereof wherein
• This formula corresponds with (iso)ascorbic acid.
• iso-ascorbic acid and 1-ascorbic acid are both preferred.
• This formula corresponds with tetramethyl reductic acid.
• the compound(s) according to the formula (I) preferably is(are) present in the developer solution in an amount comprised between 1 g and 50 g per litre.
• reducing precursor compounds have, e.g., been described in WO's 94/3834 and 94/16362, which are both incorporated herein by reference.
• ascorbic acid is not merely used in the developer as an antioxidant as, e.g., described in WO 93/12463, in JP-A's 4428673 and 55149936, in GB 1,266,533 and in US-P's 3,865,591; 4,756,997 and 4,839,259 and in the literature as, e.g., J. Am. Chem. Soc., 60 (1938), p. 99 and p. 2084; 61 (1939), p. 442; 64 (1942), p. 1561, 65 (1943), p. 1489; 66 (1944), p. 700 and 104 (1982), p. 6273.
• An essential feature in accordance with this invention is the presence in the developer of an additional amount of at least 0.1 g to 3 g per litre of potassium thiocyanate as a silver complexing -agent.
• An equivalent amount of a thiocyanate salt, having a cation different from potassium may be added.
• the developer liquid may contain any combination of hydroquinone as a developing agent and auxiliary developing agent known for use in the development of exposed photographic silver halide. If hydroquinone is absent the said auxiliary developing agent may still be present.
• auxiliary developing compounds may be utilized p-methylaminophenol, a 1-phenyl-3-pyrazolidine-1-one, p-phenylenediamine derivatives and the like. Amounts of hydroquinone from 0 to less than 30 g per litre can be present and more preferred lower than 20 g per litre.
• Preferred amounts of auxiliary developer are present in a concentration range of 0 up to 10 mmoles per litre of developer, said auxiliary developer being preferably a 1-phenyl-3-pyrazolidine-1-one compound.
• the developer further comprises silver complexing compound(s) such as alkali metal sulphites, bisulphites, metasulphites or metabisulphites.
• it contains an alkali metal sulphite salt, and more preferably sodium sulphite, in an amount from 0 to 50, and more preferably in an amount from 0 to 40 g per litre of developer, which is substantially lower than amounts set forth, e.g., in EP 0 538 947, wherein developer compositions have been described for use in the processing of non-destructive testing materials.
• the developer solution can be alkalised with alkaline metal hydroxides, phosphates, borates, carbonates and the like.
• the developer liquid or activator liquid may contain still other ingredients, e.g.
• metal complexing agents an anti-fogging agent, e.g. alkali metal bromide, in amounts ranging from 0.01 to 0.4 moles per litre, a benzotriazole, a benzothiazole, a tetrazole, e.g., up to 0.06 g per liter of 1-phenyl-5-mercapto-tetrazole, solvents improving the dissolution of the developing agents, e.g., alcohols, polyethylene glycols and esters thereof and alkanolamines, surface active agents, development retarding or activating compounds, e.g., quaternary ammonium salts, and gelatin hardening agents, e.g., dialdehyde compounds such as glutardialdehyde.
• an anti-fogging agent e.g. alkali metal bromide
• solvents improving the dissolution of the developing agents e.g., alcohols, polyethylene glycols and esters thereof and alkanolamines
• developer according to this invention does not contain thiosulphate ions as is the case, e.g., for monobath compositions having a combined developing and fixation action as is demonstrated, e.g., in US-P 3,867,151.
• the pH of the developer solution according to this-invention which is in the range of 9.6 to 11.0, and more preferably in the range of 9.6 to 10.3.
• the present invention thus includes a method for developing, by means of the developer according to this invention, any type of photographic silver halide emulsion layer material, e.g., a graphic art, a micrographic or an X-ray recording material, after image-wise exposing the said material by means of suitable radiation sources, adapted to each application in particular, and immersing it into the said developer.
• any type of photographic silver halide emulsion layer material e.g., a graphic art, a micrographic or an X-ray recording material
• the development process according to the present invention is advantageously applied in automatic processing equipment, preferably one containing conveyer rollers as described, e.g., in US-P 3,025,779 and 3,545,971, in a time between 5 and 45 seconds at a temperature between 25 and 40°C.
• the concentration of the compounds corresponding to the formula (I) and the pH is maintained at a constant value by replenishment with unoxidised developing agent, thereby adding a concentrated alkali hydroxide solution under controlled constant redox potential as has been illustrated in EP-A 0 552 511, which is incorporated herein by reference.
• This invention allows the use of low regeneration amounts of the developer, having a composition as described hereinbefore: low regeneration amounts of developing solution from 50 to 250 ml/m 2 of photographic material are possible and even more preferred from 50 to 150 ml/m 2 .
• Silver halide emulsions incorporated in at least one photosensitive layer in a suitable layer arrangement of the said materials which can be processed in a developer according to this invention are composed of silver bromide, silver bromoiodide, silver chloride, silver chlorobromide, silver chloroiodide and silver chlorobromoiodide.
• Photosensitive silver halide emulsion layer(s) present in silver halide photographic materials used in the method according to this invention may be of any type or composition used in silver halide photography and may be present in whatever a layer arrangement used in the art of photography.
• the present invention is illustrated by the following example without, however, limiting it thereto.
• Method A makes use of the GEVASET 437N automatic processor, trademarked product from Agfa-Gevaert, which has a tank volume of only 1 litre per tank.
• the temperature and the processing velocity are made variable. As there is only one roller before entering and after leaving every bath, there is no danger to disturb the outlook of the film surface. Moreover the agitation of the developer is reduced to a negligable extent and the developer tank is followed by two fixation tanks and one rinsing tank, both having a content of 1 litre. At a velocity of 25 cm/min, the film is immersed into the developer tank for 46 seconds at a temperature of 30°C. The developer is not regenerated.
• the silver deposit has the occasion to grow by agglomeration.
• the filtration was carried out under vacuum suction with a Büchner filter apparatus with a filtration paper Rotband Nr 589-5, the weight of which was determined before the operation started. After filtration the filter was rinsed with about 1 l of demineralised water, in order to remove the soluble salts of the developer. The filter paper was dried in an oven for 1 hour at 80°C, whereafter it was cooled for 90 minutes and weighed again. The difference in weight obtained gives an idea about the amount of silver deposit. After 4 weeks the procedure was repeated in order to detect the velocity of sedimentation. From the resulting filtrate a sample was taken to determine the amount of silver therein by means of A.A.S..
• STRUCTURIX D4 trademarked product from Agfa-Gevaert for industrial radiography (non-destructive testing)
• This material is double-side coated and contains an amount of ca. 21 g of silver, expressed as the equivalent amount of silver nitrate per square metre.
• the said material has been chosen in some experiments in order to reduce the amount of film to a minimum.
• the following silver halide-materials A and B were prepared in order to be coated identically to the STRUCTURIX D4 material as the normally present cubic crystals having 99 mole % of silver bromide and 1 mole % of iodide ions used therein.
• Material A contains a cubic silver chlorobromoiodide emulsion having 97.6 mole % of silver chloride, 2 mole % of silver bromide and 0.4 mole % of silver iodide.
• This emulsion was prepared at a pH value of 5.0 and a constant pAg value of 7.35. Its grain size was 0.30 ⁇ m and its gesi (ratio of the amount, in grams, of gelatin to silver expressed as the equivalent amount of silver nitrate) was 0.5.
• the said emulsion was optimally sulphur and gold sensitised.
• Material B contains a cubic silver bromide emulsion having 100 mole % of silver bromide. This emulsion was prepared at a constant pAg value of 8.2. Its grain size was 0.33 ⁇ m and its gesi was 0.4. The said emulsion was optimally sulphur and gold sensitised.
• the graphic material SPR712p (trademarked product from Agfa-Gevaert, having an emulsion rich in chloride: 83.6 mole % of chloride, 16 mole % of bromide and 0.4 mole % of iodide) was chosen.
• This material, called material C is single-side coated and contains an amount of ca. 7.5 g of silver, expressed as the equivalent amount of silver nitrate per square metre.
• This material has AgBr(I) tabular crystals containing 1 mole % of iodide in its emulsion layers. It was prepared as described in EP-A 0 577 886 and was coated as follows: The emulsion was stabilised with 4-hydroxy-6-methyl-1,3,3a,7-tetra-azaindene and after addition of the normal coating additives the solutions were coated simultaneously together with a protective layer containing 1.1 g gelatine per m 2 and per side on both sides of a polyethylene terephthalate film support having a thickness of 175 ⁇ m. The resulting photographic material contained per side an amount of silver halide corresponding to 3.5 grams of AgNO 3 per m 2 .
• This material has pure cubic AgCl crystals in its emulsion layers. It was prepared in the following way. A silver chloride emulsion having cubic silver chloride crystals was prepared by the double jet technique. The silver halide composition was 100 mole % of chloride and the average grain size was 0.55 ⁇ m. Therefor an amount of 615 ml of demineralised water was used as starting volume in the vessel, containing further 46 g of inert gelatin and 10.3 mmoles of sodium chloride at 60°C.
• the washing procedure was performed in a discontinous way, adding 3 1 of demineralised water, containing up to 8 mmole of sodium chloride pro liter, until pAg was reaching a value of about 7.3.
• the emulsion was peptised and was further chemically ripened to an optimal fog-sensitivity relationship at 52°C, pAg having a value of about 6.95.
• Chemical ripening agents besides gold (in an amount of 0.019 mmole) and sulphur (tetramethyl thiodithiocarboxylic acid diamide in an amount of 0.061 mmole), were toluene thiosulphonic acid and iodide ions, both being predigestion agents in amounts of 0.02 and 8.6 mmoles respectively.
• a photographic material was prepared having on a subbed polyester base a gelatinous silver halide emulsion of which the silver halide consists for 99.7 % of silver chloride having an average grain size of 0.55 ⁇ m the preparation of which has been described above.
• spectral sensitisers were added consecutively in an amount of 0.1 mmole and 0.3 mmole per mole of silver nitrate respectively.
• the emulsion was further stabilised with 0.22 mmole of compound (IV) and 0.68 mmole of compound (V) per mole of silver nitrate.
• a coated amount of silver expressed as the equivalent amount of silver nitrate of 3.8 g per m 2 and a gelatin to silver chloride (expressed in equivalent amount of silver nitrate) ratio of 0.35 was provided with a gelatin covering layer (anti-stress layer) of 1.30 g of gelatin per m 2 .
• compositions of the developers are given hereinafter.
• Amounts of compounds making part of the said developers are given in mmoles/litre, unless indicated in another way in the Table.
• Table 1 amounts, in mg/l, of deposited silver determined by means of method A described hereinbefore in Exhausted Developer (ED), after 24 hours (in mg/l)(ED24), after 4 weeks present in the filtrate (mg/l)(ED4W) as well as the Total Deposit (mg/l) (TD) and the rest amount of Deposited Silver in the Filtrate (DSF) are given for material A (rich in AgCl: 97.6 mole %) and for material B (rich in AgBr: 100 mole % ), the description of which has been given hereinbefore, in different developers DEV1, DEV2, DEV3 and DEV4 set forth hereinafter.
• the developers DEV3 and DEV4, according to this invention provide less silver deposit, for AgCl- as well as for AgBr-emulsions: -60 % and -27 % resp. for AgBr (vs. DEV1); -84 % and -78 % resp. for AgCl (vs. DEV2).
• the sensitometric properties are matching very well with those required in DEV1.
• DT development time
• the covering power defined as the ratio of the maximum density and the amount in grams of developed silver, is maintained in DEV3 versus in the normal developers (DEV1, respectively DEV2), with a trend to give an enhanced value for the cubic AgCl emulsion. This trend is fully in accordance with the invention disclosed in EP-A 0 678 772.
• SPR712P also a trademarked product from Agfa-Gevaert, having an emulsion rich in chloride: 83.6 mole % of chloride, 16 mole % of bromide and 0.4 mole % of iodide
• Table 6 A sensitometric evaluation of SPR712P (also a trademarked product from Agfa-Gevaert, having an emulsion rich in chloride: 83.6 mole % of chloride, 16 mole % of bromide and 0.4 mole % of iodide) is given in Table 6 wherein the effect of DEV6 and DEV7 is shown.

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• General Physics & Mathematics (AREA)
• Silver Salt Photography Or Processing Solution Therefor (AREA)

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Citations (11)

• 1996
  • 1996-01-19 EP EP96200136A patent/EP0732619A1/de not_active Withdrawn

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