EP0851282B1 - Verfahren zur Verarbeitung eines photographischen lichtempfindlichen Silberhalogenidmaterials - Google Patents

Verfahren zur Verarbeitung eines photographischen lichtempfindlichen Silberhalogenidmaterials Download PDF

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Publication number
EP0851282B1
EP0851282B1 EP97203819A EP97203819A EP0851282B1 EP 0851282 B1 EP0851282 B1 EP 0851282B1 EP 97203819 A EP97203819 A EP 97203819A EP 97203819 A EP97203819 A EP 97203819A EP 0851282 B1 EP0851282 B1 EP 0851282B1
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EP
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Prior art keywords
developer
silver
silver halide
processing
group
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EP97203819A
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English (en)
French (fr)
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EP0851282A1 (de
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Ann Verbeeck
Peter Verrept
Freddy Henderickx
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Agfa Gevaert NV
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Agfa Gevaert NV
Agfa Gevaert AG
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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
    • G03C1/0051—Tabular grain emulsions
    • G03C1/0053—Tabular grain emulsions with high content of silver chloride
    • 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
    • G03C5/305—Additives other than 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
    • G03C2200/00—Details
    • G03C2200/03—111 crystal face
    • 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
    • G03C2200/00—Details
    • G03C2200/52—Rapid processing
    • 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
    • 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
    • G03C5/31—Regeneration; Replenishers

Definitions

  • This invention is related to a method for processing of a light-sensitive black-and-white silver halide photographic material comprising tabular silver halide emulsions rich in silver chloride.
  • Tabular silver halide grains are well-known for practical use since the early eighties: if present in one or more light-sensitive hydrophilic layers of a silver halide photographic material a high covering power can be expected, even for forehardened silver halide photographic materials as e.g. disclosed in US-A 3,414,304.
  • tabular grains rich in silver chloride are more preferred than tabular grains rich in silver bromide.
  • tabular grains rich in silver chloride can provide a high sensitivity in silver halide photographic materials coated from such emulsions. Even in a total processing time of up to 50 seconds with low regeneration amounts of hardener-free processing solutions suitable images are obtained without leaving dye stain, generated from huge amounts of spectral sensitizer. Moreover a suitable black image tone is attained.
  • a method has been found of processing an image-wise exposed black-and-white light-sensitive silver halide photographic material comprising a support coated on one or both sides thereof with hydrophilic layers, wherein at least one of said layers comprises one or more emulsions having tabular silver halide crystals rich in silver chloride, said method comprising the steps of developing, fixing, rinsing and drying, further characterised in that said developing step proceeds in a black-and-white developer comprising one or more organic compounds inhibiting development, more preferably one or more benzotriazole compounds in an amount of from 0.1 mmole up to 1 mmole per liter of developer ready-for-use, and in that said black-and-white developer is substantially free from bromide ions.
  • developer compositions in general organic compounds as benzotriazoles, nitroindazoles and mercaptotetrazoles are known for years to act as developing inhibiting agents having an anti-fogging influence on the image-forming process.
  • bromide ions present in the developer and in the developer replenisher are well-know as a developer restrainer.
  • Developer compositions combining benzotriazoles and bromide ions are well-known from the patent literature as e.g. from EP-A 0 428 455, wherein in the black-and-white developer benzotriazoles are present in an amount of from 0.1-0.3 g/l and wherein sodium bromide is present in an amount of from 1 to 4 g in order to develop the forehardened radiographic materials used therein.
  • Said compounds are also used in the development of e.g. black-and-white materials comprising cubic grains spectrally sensitized in the red wavelength region as described in US-A 5,464,730, wherein the developer has a specified low bromide concentration of 0.01 mol/l or less and a pH of 9.8 or less, permitting stable processing of the silver halide material for a long period of time with only little variation of photographic properties of the processed material, although amounts of replenisher are reduced to less than 200 ml per m 2 .
  • the developer may contain substantially no bromide ions.
  • benzotriazole compounds are preferred organic compounds inhibiting development for use in the black-and-white developer composition of the present invention wherein no bromide ions are present.
  • Preferred benzotriazole compounds have a structure corresponding with the general formula (I), wherein R represents a hydrogen atom, a halogen, an alkyl group, an amino group, a hydroxy group, a carboxy group, a sulphonic acid group, an alkoxycarbonyl group, an acylamide group or a sulfonamide group.
  • More specifically preferred benzotriazole compounds present in the developer used in the method of the present invention are selected from the group consisting of benzotriazole (I.1), 5-methylbenzotriazole (I.2), 4-methylbenzotriazole (I.3), 6-aminobenzotriazole (I.4), 5-chlorobenzotriazole (I.5), 5-carboxy-benzotriazole (I.6) and 5-trifluoromethyl-benzotriazole (I.7), the formulae of which are given hereinafter.
  • Other useful benzotriazoles are 5-bromobenzotriazole and 5-butyl-benzotriazole. 5-methylbenzotriazole is particularly preferred.
  • a decrease of fog and an increase of speed occurs in the absence of bromide ions if the benzotriazole compound(s) is(are) added in amounts in the range of from 0.1 mmole up to 1 mmole per litre of developer ready-for use in order to get the highest covering power.
  • the black-and-white developer used in the method of the present invention moreover comprises thiocyanate ions in an amount of from 5 mmoles up to 25 mmoles per litre of developer ready-for-use, wherein the presence of other silver complexing ions or silver solvent(s) is not excluded.
  • said black-and-white developer comprises developing agents selected from the group consisting of hydroquinone, ascorbic acid, reductic acid or derivatives thereof.
  • ascorbic acids for the black-and-white developer used in the method of the present invention, an enediol type ascorbic acid, an enaminol type ascorbic acid, an endiamin type ascorbic acid, a thioenol type ascorbic acid, and an enamin-thiol type ascorbic acid may be used. These compounds are e.g. described in US-A 2,688,549 and in JP-A 62-237443, etc..
  • Ascorbic acids used in the present invention can be used as the form of the alkali metal salts such as lithium salts, sodium salts, potassium salts, etc..
  • Ascorbic acid is used for the developer in the amount of generally from 1 to 100 g, and preferably from 5 to 80 g per liter of the developer.
  • the ecologically questionable "hydroquinone" (iso)ascorbic acid, 1-ascorbic acid and tetramethyl reductic acid are preferred as main developing agent in the developer.
  • the developer for use in the present invention further doesn't contain a development inhibitor such as potassium bromide which is one of the essential characteristics of the black-and-white developer used in the method of this invention.
  • a development inhibitor such as potassium bromide which is one of the essential characteristics of the black-and-white developer used in the method of this invention.
  • Potassium iodide however may be used in minor amounts of from about 10 to 100 mg per litre of developer as in those amounts it merely acts as a developing activator.
  • the developer may contain a surface active agent, a hard-water softener etc.. So the developer commonly contains a chelating agent.
  • the particularly preferred chelating agent are diethylenetriaminepentaacetic acid, triethylenetetraaminehexaacetic acid, 1,3-diaminopropanol tetraacetic acid, glycol ether diamine-tetraacetic acid, hydroxyethylethylenediaminetriacetic acid, 2-phosphonobutane-1,2,4-tricarboxylic acid, 1,1-diphosphonoethane-2-carboxylic acid, nitritotrimethylenephosphoric acid, ethylenediaminetetraphosphonic acid, diethylenetriaminepentaphosphonic acid, 1-hydroxypropylidene-1,1-diphosphonic acid, 1-aminoethylidene-1,1-diphosphonic acid, 1-hydroxyethylidene-1,1-diphosphonic acid, and the salts of them, without however being
  • a 1-phenyl-3-pyrazolidone or, depending on the type of photographic material, a p-aminophenol together with ascorbic acid and/or hydroquinone derivatives there are 1-phenyl-3-pyrazolidone, 1-phenyl-4,4'-dimethyl-3-pyrazolidone, 1-phenyl-4-methyl-4-hydroxymethyl-3-pyrazolidone, l-phenyl-4,4'-dihydroxymethyl-3-pyrazolidone, 1-phenyl-5-methyl-3-pyrazolidone, 1-p-aminophenyl-4,4'-dimethyl-3-pyrazolidone, 1-p-tolyl-4,4-dimethyl-3-pyrazolidone, 1-p-tolyl-4-methyl-4-hydroxymethyl-3-pyrazolidone, etc..
  • the 3-pyrazolidone series developing agent is preferably used in an amount of from 0.001 mole/liter to 1.2 moles/liter.
  • the p-aminophenol series developing agent being used in the present invention, there are N-methyl-p-aminophenol, p-aminophenol, N-( ⁇ -hydroxyethyl)-p-aminophenol, N-(4-hydroxyphenyl-glycine, 2-methyl-p-aminophenol, p-benzylaminophenol, etc..
  • a developing agent as N-methyl-p-aminophenol is particularly preferred.
  • Preferred pH values of the developer used in the method of the present invention are from 8.5 up to 10.3.
  • Alkaline agents which can be used for adjusting pH of the black-and-white developer include a pH controlling agent such as sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, sodium tertiary phosphate, potassium tertiary phosphate, etc.
  • sulphite preservative for the black-and-white developer in the present invention there are sodium sulphite, potassium sulphite, lithium sulphite, ammonium sulphite, sodium bisulphite, potassium metabisulphite, etc..
  • the amount of the sulphite is generally at least 0.01 mole/liter, and preferably at last 0.02 mole/liter. Also, the upper limit of the amount of the sulphite is preferably 2.5 moles/liter.
  • a particularly suitable developer solution is the one comprising a reduced amount of sulphite, and in a preferred embodiment even no sulphite, and instead thereof ascorbic acid which acts as a main developer and anti-oxidant as well.
  • Such a composition is called a "low-sludge" developer.
  • the black-and-white developer is substantially free from hardening agents (free from the commonly used glutaric dialdehyde as dialdehyde hardener) and still more preferred is that the said fixing step further proceeds in a fixer which is substantially free from aluminum ions, in order to have a processing cycle wherein no hardener is present in the processing solutions.
  • a particularly suitable fixer solution comprises an amount of less than 25 g of potassium sulphite per liter without the presence of acetic acid wherein said fixer has a pH value of at least 4.5, in order to make the fixer solution quasi odourless.
  • the presence of a-ketocarboxylic acid compounds may be useful as described in EP-A's 0 620 483, 0 726 491 and in RD 16768, published March 1978.
  • replenishing of the processing solutions in the developing and/or fixing step proceeds with replenishing amounts of 200 ml or less per m 2 of processed silver halide photographic material and more preferably in amounts of from 50 up to 150 ml/m 2 .
  • Preferred minimum regeneration or replenishment amounts are from 20 to 100 ml/m 2 , more preferred from 25 to 75 ml/m 2 and still more preferred from 25 to 50 ml/m 2 of developed material.
  • the developer solution used in the method according to the present invention should be replenished not only for decrease of the liquid volume due to cross-over into the next processing solution but also for pH-changes due to oxidation of the developer molecules.
  • the processing proceeds within a total processing time of 90 seconds or less and more preferred in a time of from 30 to 60 seconds.
  • Hydrophilic colloid layers may comprise as hydrophilic colloids proteins such as gelatin derivatives, graft polymers of gelatin and other polymers, albumin, casein, etc.; cellulose derivatives such as hydroxyethyl cellulose, carboxymethyl cellulose, cellulose sulphuric acid esters, etc.; saccharose derivatives such as sodium alginate, dextran, starch derivatives, etc.; and various synthetic hydrophilic polymers such as polyvinyl alcohol, polyvinyl alcohol partial acetal, poly-N-vinylpyrrolidone, polyacrylic acid, polymethacrylic acid, polyacrylamide, polyvinyl imidazole, polyvinyl pyrazole, etc., can be used.
  • hydrophilic colloids proteins such as gelatin derivatives, graft polymers of gelatin and other polymers, albumin, casein, etc.
  • cellulose derivatives such as hydroxyethyl cellulose, carboxymethyl cellulose, cellulose sulphuric acid esters, etc
  • gelatin in addition to lime-processed gelatin, acid-processed gelatin or enzyme-processed gelatin may be used and also, the hydrolysed products or enzyme-decomposition products of gelatin can be used.
  • binders dextran having an average molecular weight of not more than 50,000 or polyacrylamide together with gelatin may be used.
  • the layer binder should of course dispose of an acceptably high number of functional groups, which by reaction with an appropriate hardening agent can provide a sufficiently resistant layer.
  • functional groups are especially the amino groups, but also carboxylic groups, hydroxy groups, and active methylene groups.
  • the silver halide photographic emulsions and light-insensitive hydrophilic colloid layers present in the materials processed according to the method of the present invention may contain an inorganic or organic hardening agent.
  • hardening agents chromium salts (e.g., chromium alum and chromium acetate), aldehydes (e.g., formaldehyde, glyoxal, and glutaraldehyde), N-methylol compounds (e.g., dimethylolurea and methylol dimethylhydrantoin), dioxane derivatives (e.g., 2,3-bihydroxydioxane), active vinyl compounds (e.g., 1,3,5-triacryloyl-hexahydro-s-triazine, bis(vinylsulfonyl)-methyl ether, and N,N'-methylenebis[ ⁇ -(vinylsulfonyl)propionamide), active halogen compounds (e
  • mucochloric acid and mucophenoxychloric acid can be used alone or as a combination of them.
  • Formaldehyde and phloroglucinol can e.g. be added respectively to the protective layer(s) and to the emulsion layer(s).
  • the active vinyl compounds described in JP-A's 53-41221, 53-57257, 59-162546 and 60-80846 and the active halogen compounds described in US-A 3,325,287 are preferred.
  • the light-sensitive black-and-white silver halide photographic material to be processed comprises a support coated on one or both sides thereof with hydrophilic layers, wherein at least one of said layers comprises one or more emulsions having tabular silver halide crystals rich in silver chloride.
  • Tabular grains having tabular crystals rich in chloride for use in one or more hydrophilic emulsion layer(s) of silver halide photographic materials can be bound by ⁇ 111 ⁇ or ⁇ 100 ⁇ major faces.
  • Tabular silver halide grains having a ⁇ 111 ⁇ crystal habit promoted since 1982 as applicable in photographic materials for practical use are defined as crystals possessing two parallel faces with a ratio between the diameter of a circle having the same area as these faces, and the thickness, being the distance between the two major faces, equal to at least 2.
  • Emulsions with crystals rich in chloride were commonly directed to applications in the field of less sensitive materials as e.g. graphic arts materials, duplicating materials, radiographic hard-copy materials, diffusion transfer reversal materials and black-and-white or colour print materials are well-known.
  • the advantages of said emulsions with crystals rich in chloride regarding higher development and fixing rates, are however highly appreciated. As nowadays the tendency is present to get materials processed in shorter processing times, it is highly appreciated to combine said advantages with a high sensitivity for application in high-sensitive materials, an object which can be realized as has e.g. been described in EP-A 0 678 772.
  • Tabular silver halide grains rich in chloride, bounded by ⁇ 111 ⁇ major faces and/or the preparation method thereof and/or materials in which said grains are incorporated have also been described in e.g. US-A's 4,399,215; 4,400,463; 4,804,621; 5,061,617; 5,275,930; 5,286,621; 5,292,632; 5,310,644; 5,320,938; 5,356,764; in the published EP-A's 0 503 700, 0 533 189, 0 647 877 and 0 678 772.
  • Compounds that are useful as crystal habit modifier of crystals rich in silver chloride besides the most frequently used adenine include substances disclosed in EP-A's 0 481 133 and 0 532 801 and in US-A's 5,176,991; 5,176,992; 5,178,997; 5,178,998; 5,183,732; 5,185,239; 5,217,858; 5,221,602; 5,252,452; 5,264,337; 5,272,052; 5,298,385; 5,298,387; 5,298,388; 5,399,478; 5,405,738; 5,411,852 and 5,418,125.
  • the halide distribution in the tabular grains can be homogenous over the whole crystal volume.
  • phases differing in silver halide composition are present over the crystal volume said crystal is said to have a core-shell structure. More than one shell can be present and between different phases it may be recommended to have a phase enriched in silver iodide by applying the so-called conversion technique during preparation.
  • Iodide ions can be provided by using aqueous solutions of inorganic salts thereof as e.g.
  • Iodide ions can also be provided by organic compounds releasing iodide ions as has e.g. been described in EP-A's 0 561 415, 0 563 701, 0 563 708, 0 649 052 and 0 651 284 and in WO 96/13759.
  • iodide ions provided by organic agents releasing iodide ions are preferred such as mono iodide acetic acid, mono iodide propionic acid, mono iodide ethanol and even hydrogels containing iodide ions, capable to generate iodide ions.
  • the black-and-white silver halide photographic material to be processed according to the method of the present invention comprises tabular silver halide grains rich in chloride which are ⁇ 111 ⁇ tabular grains accounting for at least 50 % of the total projected area of all grains, having an average aspect ratio of more than 2 and an average grain thickness of from 0.05 up to 0.30 ⁇ m. More preferably said silver halide grains rich in chloride are selected from the group consisting of chloride, chloroiodide, chlorobromide or chlorobromoiodide.
  • Bromide ion concentrations of up to 25 mole % based on the total silver amounts are contemplated, but in order to avoid a strong inhibition of the processing, the tabular silver chlorobromoiodide emulsion crystals used according to the present invention preferably have an amount of silver bromide of at most 10 mole %. In order to reduce the amount of replenisher in the processing, it is even more preferable to reduce the amount of bromide ions to less then 5 mole %.
  • Bromide ions can be provided from at least one inorganic and/or organic agent providing bromide ions.
  • Emulsions comprising silver chlorobromoiodide or chloroiodide tabular crystals may be built up so that an amount of 20 to 100 mole %, and even an amount of 50 to 100 mole % of the total amount of iodide ions is located at the surface of the said emulsion crystals as e.g. in EP-A 0 678 772 cited hereinbefore.
  • Iodide ions can be present in one or more shell regions, in form of zones wherein iodide ions are concentrated locally.
  • Distributions of silver halide crystals rich in chloride over the whole population of a silver halide emulsion may be homogenous or heterogenous, depending on the precipitation methods used.
  • Tabular silver halide grains rich in chloride, bounded by ⁇ 100 ⁇ major faces are however not excluded and may be present in one or more hydrophilic light-sensitive silver halide layers of black-and-white photographic materials which are processed according to the method of the present invention.
  • the preparation method of such tabular grains rich in chloride bounded by ⁇ 100 ⁇ major faces and/or materials in which said grains can be incorporated have been described in e.g.
  • ⁇ 100 ⁇ tabular grains rich in silver chloride although been developed later than corresponding ⁇ 111 ⁇ tabular grains are the subject of intensive studies as no crystal habit modifier is required in their preparation: ⁇ 100 ⁇ tabular grains have a more stable crystal habit than ⁇ 111 ⁇ tabular grains rich in chloride.
  • thin tabular grains accounting for at least 50 % of the total projective surface area of all grains, more preferred for at least 70 % and still more preferred for at least 90 %, may be present, said grains having an average crystal diameter of from 0.3 to 3.0 ⁇ m, more preferred from 0.5 to 2.5 ⁇ m and still more preferred from 0.5 to 1.5 ⁇ m, for an average thickness of the tabular grain from 0.05 up to 0.30 ⁇ m, more preferred from 0.05 to 0.25 ⁇ m and still more preferred from 0.06 to 0.20 ⁇ m.
  • Average aspect ratios of the tabular grains obtained after calculation from the ratio of diameter to thickness measured for each grain can be in the range 2:1 to 100:1, more preferred from 5:1 to 50:1 and still more preferred from 5:1 to 20:1 or even from 8:1 to 20:1.
  • Preferred boundary values of grain thickness mentioned hereinbefore are related with the fact that particularly the requirement of high sensitivity and the particular advantages of spectrally sensitized tabular grains should be combined.
  • tabular grains compared to normal globular grains are a high covering power at high forehardening levels , a high developability and higher sharpness thanks to a reduced degree of cross-over, especially in double side coated spectrally sensitised materials.
  • preferred tabularities (ratio of aspect ratio and grain thickness expressed in mm) of at least 40 are highly appreciated as such high values are decisive for the high spectral sensitivity of the emulsion grains which strongly depends on its specific surface area.
  • Said tabular grains rich in chloride may further be doped with whatever a dope as e.g. with group VIII metal ions like Rh 3+ , Ir 4+ , Ru 2+ and Co 2+ or with Cd 2+ , Zn 2+ or Pb 2+ or even with a mixture thereof.
  • group VIII metal ions like Rh 3+ , Ir 4+ , Ru 2+ and Co 2+ or with Cd 2+ , Zn 2+ or Pb 2+ or even with a mixture thereof.
  • Other suitable dopants used during precipitation or chemical ripening of the silver chloride or silver chlorobromide emulsion crystals may be e.g. Fe, Ni, Ru, Rh, Pd, Os, Pt, Hg, Tl and Au.
  • ruthenium, rhodium and iridium are preferred.
  • Combinations of one or more dopant(s) may be added, in the same or different preparation steps of silver halide crystals rich in silver chloride having a tabular crystal habit.
  • the said dopants can be divided homogeneously or heterogeneously over the total crystal volume. So in the core or in the shell or even at the crystal surface, as is e.g. the case when conversion techniques are applied, the said halide ions and/or the said dopants may be concentrated.
  • An important factor influencing growth of silver nuclei in the preparation of silver halide grains rich in chloride is the choice of and the amount of protective colloid present in the reaction vessel or added simultaneously with one of the solutions added thereto during nucleation and further, eventually, after nucleation, during physical ripening before and/or during growth of the nuclei formed.
  • gelatin The most well-known and practically used hydrophilic colloidal binder during precipitation of silver halide crystals rich in silver chloride is gelatin.
  • Gelatin may, however, be replaced in part or integrally by synthetic, semi-synthetic, or natural polymers.
  • Synthetic substitutes for gelatin are e.g. polyvinyl alcohol, poly-N-vinyl pyrrolidone, polyvinyl imidazole, polyvinyl pyrazole, polyacrylamide, polyacrylic acid, and derivatives thereof, in particular copolymers thereof.
  • Natural substitutes for gelatin are e.g. other proteins such as zein, albumin and casein, cellulose, saccharides, starch, and alginates.
  • the semi-synthetic substitutes for gelatin are modified natural products e.g. gelatin derivatives obtained by conversion of gelatin with alkylating or acylating agents, by grafting of polymerizable monomers on gelatin or prehardened gelatins with blocked functional groups as a consequence of this prehardening treatment, cellulose derivatives such as hydroxyalkyl cellulose, carboxymethyl cellulose, phthaloyl cellulose, and cellulose sulphates and even potato starch.
  • modified natural products e.g. gelatin derivatives obtained by conversion of gelatin with alkylating or acylating agents, by grafting of polymerizable monomers on gelatin or prehardened gelatins with blocked functional groups as a consequence of this prehardening treatment, cellulose derivatives such as hydroxyalkyl cellulose, carboxymethyl cellulose, phthaloyl cellulose, and cellulose sulphates and even potato starch.
  • Part of gelatin may further be replaced with a synthetic or natural high-molecular material.
  • gelatin having a lower methionine content is often used in the preparation of tabular ⁇ 111 ⁇ silver halide crystals rich in chloride.
  • the most preferred gelatin used has a methionine content of from 1 to 60 ⁇ mole/g depending on each specific case. More preferably gelatin having a methionine content of from 1 to 50 ⁇ mole/g, and still more preferably amounts from 1 to 30 ⁇ mole/g (4400 p.p.m.) may be preferably used: according to US-A 4,713,323, oxidized gelatin is defined as a gelatin having a methionine content of less than 30 ⁇ mole/g.
  • Another factor which may be important in the nucleation and/or grain growth mechanism of ⁇ 111 ⁇ tabular grains rich in chloride is the calcium content of gelatin used as a colloidal binder.
  • the calcium content is about 0.4 %, which corresponds with about 100 mmole/kg, measured at the end of the preparation process of inert gelatin.
  • Complex-bound calcium ions strongly decrease the electric potential carried by gelatin.
  • Substantially "calcium free gelatin" is thus defined as gelatin with a calcium content at a level below 40 ppm which corresponds with the analytical detection limit.
  • the precipitation reaction of the tabular silver chloride, silver chlorobromoiodide and/or silver chloroiodide emulsion crystals proceeds in a dispersing medium wherein the ratio by weight of gelatin to an equivalent amount of silver nitrate is up to 0.35, unless e.g. colloidal silica is used in order to replace gelatin partially or totally. It is clear that this condition will be not fullfilled either when use is made in the reaction vessel, in part or integrally of a non-aqueous medium, of a non-aqeous solvent instead of water, as has been disclosed e.g. in US-A's 5,478,718 and 5,541,051.
  • the emulsion mixture is normally cooled to about 40°C, before or after adding a flocculate being a polymeric compound as e.g. polystyrene sulphonic acid, providing as a anionic polymer a behaviour depending on pH.
  • a flocculate being a polymeric compound as e.g. polystyrene sulphonic acid, providing as a anionic polymer a behaviour depending on pH.
  • a flocculate being a polymeric compound as e.g. polystyrene sulphonic acid, providing as a anionic polymer a behaviour depending on pH.
  • a flocculate being a polymeric compound as e.g. polystyrene sulphonic acid, providing as a anionic polymer a behaviour depending on pH.
  • the pH of the said dispersing medium is adjusted with an acid to a value in order to get a qualitatively good flocculate.
  • Said flocculate may become decanted and
  • adenine to an allowable residual amount (preferably at most 0.3 mg/g of gelatin) or applying an ultrafiltration washing procedure as disclosed e.g. in Research Disclosure, Vol. 102, Oct. 1972, Item 10208, Research Disclosure Vol. 131, March, Item 13122 and Mignot US-A 4,334,012.
  • Said ultrafiltration technique may be applied on-line during the whole precipitation, in order to reduce the increasing amount of water, thus avoiding dilution of the reaction vessel and increasing amounts of soluble salts like the mainly occurring potassium nitrate. Examples thereof have been described e.g. in EP-A 0 577 886.
  • a technique also called ultrafiltration it is not necessary to use polymeric flocculating agents that may disturb the coating composition stability before, during or after the coating procedure. Such procedures are disclosed e.g. in Research Disclosure Vol. 102, Oct. 1972, Item 10208, Research Disclosure Vol. 131, March, Item 13122 and US-A 4,334,012.
  • ultrafiltration may be proceeded in order to get the desired pH and pAg values, required when performing further treatment steps as e.g. addition to coating solutions.
  • Any washing step may further be performed by means of halide containing water, preferably water containing chloride ions.
  • Redispersion may further be performed by addition of extra hydrophilic colloid.
  • values of gesi and/or sisi defined as ratio by weight of silica (if present) to silver, said silver being expressed as equivalent amount of silver nitrate
  • any useful protective colloid cited hereinbefore as an alternative of gelatin or gelatin in modified form may be used.
  • iodide ions at the surface of silver chloroiodide or silver chlorobromoiodide tabular crystals already set forth hereinbefore is not only preferred from the viewpoint of crystal habit stability but particularly preferred as upon spectral sensitization an improved adsorption of the spectral sensitizer and an improved light absorption is obtained and as the quantum efficiency detected in the photochemical processes is increased.
  • Useful methine dyes such as those described by F.M. Hamer in "The Cyanine Dyes and Related Compounds", 1964, John Wiley & Sons include cyanine dyes, merocyanine dyes, complex cyanine dyes, complex merocyanine dyes, holopolar cyanine dyes, hemicyanine dyes, styryl dyes and hemioxonol dyes.
  • Particularly valuable dyes are those belonging to the cyanine dyes, merocyanine dyes, complex merocyanine dyes.
  • selected useful green light absorbing spectral sensitisers are e.g. anhydro-5,5'-dichloro-3,3'-bis(n-sulphobutyl)-9-ethyloxacarbocyanine hydroxide or anhydro-5,5'-dichloro-3,3'-bis(n-sulphopropyl)-9-ethyl-oxacarbocyanine hydroxide.
  • a suitable mixture of spectral sensitizers that is applied is anhydro-5,5'-dichloro-3,3'-bis(n-sulphobutyl)-9-ethyl oxacarbocyanine hydroxide or anhydro-5,5'-dichloro-3,3'-bis(n-sulphopropyl)-9-ethyloxacarbocyanine hydroxide together with anhydro-5,5'-dicyano-1,1'-diethyl-3,3'-di(2-acetoxy-ethyl)ethyl-imidacarbocyanine bromide.
  • Dyes absorbing in the blue wavelength region of the visible spectrum for use as spectral sensitizers for cubic and/or tabular silver halide grains rich in chloride have been described in JP-A 01-196031 and in US-A's 4,494,212; 4,952,491 and 5,376,523.
  • spectral sensitizers may be used as well as mixtures of emulsions being the same or different, wherein each part may be spectrally sensitized with another spectral sensitizer or with another combination of spectral sensitizers.
  • Spectral sensitizers having asymmetrical heterocycles may be useful with respect to improvements in residual colouration after processing.
  • spectral sensitization can occur simultaneously with or even precede completely the chemical sensitization step.
  • Suitable supersensitizers are e.g. heterocyclic mercapto compounds containing at least one electronegative substituent as described e.g. in US-A 3,457,078, nitrogen-containing heterocyclic ring-substituted aminostilbene compounds as described e.g. in US-A 2,933,390 and US-A 3,635,721, aromatic organic acid/formaldehyde condensation products as described e.g. in US-A 3,743,510, cadmium salts, and azaindene compounds.
  • heterocyclic mercapto compounds containing at least one electronegative substituent as described e.g. in US-A 3,457,078, nitrogen-containing heterocyclic ring-substituted aminostilbene compounds as described e.g. in US-A 2,933,390 and US-A 3,635,721, aromatic organic acid/formaldehyde condensation products as described e.g. in US-A 3,743,510, cadmium salts, and azainden
  • the surface of the silver halide grains rich in chloride may be treated with slightly oxidizing compounds as e.g. toluene thiosulphonic acid and/or corresponding salts thereof in order to reduce small silver specks to grow to fog centers in an uncontrolled manner.
  • slightly oxidizing compounds as e.g. toluene thiosulphonic acid and/or corresponding salts thereof in order to reduce small silver specks to grow to fog centers in an uncontrolled manner.
  • thiosulphate, thiocyanate, thioureas selenium e.g. selenosulphate, selenocyanate, selenoureas; tellurium e.g. tellurosulphate, tellurocyanate, telluroureas; sulphites, mercapto compounds, rhodamines etc..
  • the emulsions can be sensitized also by means of gold-sulphur ripeners, gold-selenium ripeners, gold-sulphur-selenium ripeners, or by means of reductors e.g.
  • tin compounds as described in GB 789,823, amines, hydrazine derivatives, formamidine-sulphinic acids, and silane compounds although care should be taken in order to prevent the emulsion from fog formation in an uncontrollable way.
  • Normal amounts of gold compounds are in the range from 1 x 10 -5 to 2.5 x 10 -5 moles per mole of silver halide.
  • the silver halide photographic emulsions being used in the processing method of the present invention can further contain various kinds of compounds in addition to the silver halide adsorptive materials in the chemical sensitization step in the present invention for preventing the occurrence of fog in the production steps, the storage and photographic processing of the photographic materials or stabilizing the photographic performance of the photographic materials.
  • the silver halide photographic emulsions can contain any of the compounds known as antifoggants or stabilizers such as azoles (e.g., benzothiazolium salts, nitroimidazoles, nitrobenzimidazoles, chlorobenzimidazoles, bromobenzimidazoles, nitroindazoles, benzotriazoles, and aminotriazoles); mercapto compounds (e.g., mercaptothiazoles, mercaptobenzothiazoles, mercaptobenzimidazoles, mercaptothiazoles, mercaptotetrazoles, mercaptopyrimidines, and mercaptotrizines); thioketo compounds (e.g., oxadolinethione); azaindenes (e.g., triazaindenes, tetraazaindenes,in particular, 4-hydroxy-substituted (1,3,3,a,7)tetraazaindenes
  • the mercapto compounds described in JP-A 60-80839, the heterocyclic compounds described in JP-A-57-164735, and the complex salts of heterocyclic compounds and silver can preferably be used.
  • a sensitizing dye is used as silver halide adsorptive material in the chemical sensitization step, if necessary, a spectral sensitizing dye for other wavelength region may be added to the emulsion.
  • the photographic element may further comprise various kinds of coating physical property modifying addenda as described in RD's Nos. 36544 (1994) and 38957 (1996), Chapter IX, wherein coating aids, plasticizers and lubricants, antistats and matting agents have been described.
  • Development acceleration can be accomplished for materials which are processed according to the method of the present invention by incorporating in emulsion layer(s) or adjacent layers various compounds, preferably polyalkylene derivatives having a molecular weight of at least 400 such as those described in e.g. US-A's 3,038,805; 4,038,075 and 4,292,400 as well as in EP-A's 0 634 688 and 0 674 215.
  • the photographic element may further comprise various other additives such as e.g. compounds improving the dimensional stability of the photographic element, ultraviolet absorbers and spacing agents.
  • Suitable ultraviolet absorbers have e.g. been described in RD's Nos 36544 (1994) and 38957 (1996), Chapter VI, wherein also suitable optical brighteners are mentioned.
  • Spacing agents may be present of which, in general, the average particle size is comprised between 0.2 and 10 ⁇ m. Spacing agents can be soluble or insoluble in alkali. Alkali-insoluble spacing agents usually remain permanently in the photographic element, whereas alkali-soluble spacing agents usually are removed therefrom in an alkaline processing bath.
  • Suitable spacing agents can be made e.g. of polymethyl methacrylate, of copolymers of acrylic acid and methyl methacrylate, and of hydroxypropylmethyl cellulose hexahydrophthalate. Other suitable spacing agents have been described in US-A 4,614,708.
  • suitable as a binder material can be added at a later stage of the emulsion preparation e.g. after washing, in order to establish optimal coating conditions and/or in order to establish the required thickness of the coated emulsion layer.
  • a gelatin to silver halide ratio silver halide being expressed as the equivalent amount of silver nitrate, ranging from 0.3 to 1.0 is then obtained.
  • Another binder may also be added instead of or in addition to gelatin.
  • Useful vehicles, vehicle extenders, vehicle-like addenda and vehicle related addenda have been described e.g. in Research Disclosures Nos 36544 (1994) and 38957 (1996), Chapter II.
  • any thickening agent Prior to coating any thickening agent may be used in order to regulate the viscosity of the coating solution, provided that they do not particularly affect the photographic characteristics of the silver halide light-sensitive photographic material.
  • Preferred thickening agents include aqueous polymers such as polystyrene sulphonic acid, dextran, sulphuric acid esters, polysaccharides, polymers having a sulphonic acid group, a carboxylic acid group or a phosphoric acid group as well as colloidal silica.
  • Polymeric thickeners well-known from the literature resulting in thickening of the coating solution may even be used in combination with colloidal silica.
  • Patents concerning thickening agents are e.g. US-A 3,167,410; Belgian Patent No. 558.143 and JP-A's 53-18687 and 58-36768. Negative effects on physical stability possibly resulting from the addition of polymeric compounds can be avoided by exclusion of those compounds and by restricting extra additions of colloidal silica.
  • hydrophilic colloidal layer compositions on a support by slide-hopper or curtain-coating techniques, wherein said compositions have gelatin in low amounts in order to provide a ratio by weight of gelatin to silver halide expressed as an equivalent amount of silver nitrate in the range from 0.05 to 0.4
  • thickening agents composed of synthetic clay and anionic macromolecular polyelectrolytes wherein said synthetic clay is present in an amount of at least 85 % by weight versus the total amount of thickening agents are recommended as has been disclosed in EP-Application No. 96201653, filed June 13, 1996.
  • a light-sensitive silver halide photographic material is disclosed in EP-Application No. 96202601, filed September 18, 1996, wherein said material comprises a support and one or more hydrophilic colloidal silver halide emulsion layers having silver halide crystals with colloidal silica as a protective colloid the said layer(s) having a gesi, defined as ratio by weight of gelatin to silver, in the range from 0 to less than 0.05 and a sisi, defined as ratio by weight of silica to silver, in the range from 0.01 to less than 0.10, wherein said weight of silver in the calculation of gesi and sisi is expressed as an equivalent amount of silver nitrate.
  • Photographic material having thin emulsion layers e.g. layers with a layer thickness of less than 5 ⁇ m, containing less than 5 g of gelatin, preferably about 3 g/m 2 and more preferably about 2 g/m 2 offer the advantage that besides rapid processing applicability and the rapid drying of the wet processed material an improvement in sharpness is observed.
  • the black-and-white photographic material may contain several light-insensitive layers at the side of the support carrying said light-sensitive emulsion layer(s), e.g. a protective antistress layer which can be split up into two layers, one of them being an underlying interlayer or an outermost afterlayer coated or sprayed on top of the "basic" protective antistress layer.
  • a protective antistress layer which can be split up into two layers, one of them being an underlying interlayer or an outermost afterlayer coated or sprayed on top of the "basic" protective antistress layer.
  • said protective antistress layer comprises one or more organic compounds inhibiting development.
  • Said organic compound(s) inhibiting development is(are) preferably (a) benzotriazole compound(s).
  • said benzotriazole compound(s) preferably has(have) a structure corresponding to the general formula (I) already given hereinbefore. More preferably said compound(s) is(are) selected from the group consisting of benzotriazole, 5-methylbenzotriazole, 4-methylbenzotriazole, 6-aminobenzotriazole, 5-chlorobenzotriazole, 5-carboxy-benzotriazole and 5-trifluoromethyl-benzotriazole.
  • said organic compounds inhibiting development are present in the protective antistress layer in an amount of from 0.001 mmole up to 0.010 mmole per gram of silver, expressed as an equivalent amount of silver nitrate, coated per square meter of the said material.
  • said sulphite ions being replaced by anti-oxidants as e.g. 1-ascorbic acid, reductic acid, erythorbic acid, iso-ascorbic acid, derivatives thereof and/or salts thereof, then a low-sludge developer is provided.
  • Said anti-oxidants if moreover replacing common developing agents as e.g. hydroquinone lead to a particularly useful ecologically justified low-sludge developer.
  • the fixer solution is free from aluminum ions
  • the light-sensitive black-and-white silver halide photographic materials processed according to the method of the present invention should be hardened to such an extent that in a fixation step free from aluminum ions no problems as e.g. sludge formation or troubles with physical properties of the materials occur.
  • a survey of hardening agents available in order to foreharden coated hydrophilic gelatinous layers of the said photographic materials has been given e.g. in Research Disclosure 38957, Chapter IIb.
  • aluminum salt solutions as e.g.
  • aluminum sulphate may be spray-coated onto or coated in an afterlayer onto the protective antistress layer or another outermost layer of the photographic material, in favour of hardening of the surface layer and in favour of physical properties obtained for the processed material after fixation in a fixer free from hardening aluminum ions, especially with respect to surface glare, pressure sensitivity and unevenness in the processing.
  • one or more subbing layers e.g. filter layers, antistatic agent(s), filter dyes for safety-light purposes etc. may be present.
  • Protective antistress layers preferably contain coating aids and coating physical property modifying addenda mentioned in RD's Nos. 36544 and 38957, published September 1994 and 1996 respectively, Chapter IX. Antistatic properties are especially preferred in order to prevent blackening after processing in form of sparks etc. due to abrupt decharging of electrostatic charges during production and/or handling before exposure and/or processing. It is highly preferred to add antistatic agents to the protective antistress layer or to an afterlayer coated thereupon as has been described e.g. in EP-A's 0 534 006, 0 644 454 and 0 644 456 and US-A's 4,670,374 and 4,670,376.
  • Abrasion resistance of these outermost layers may be improved as described in US-A's 4,766,059 and 4,820,615.
  • Spraycoating of afterlayers has been disclosed e.g. in US-A 5,443,640.
  • Non-imagewise blackening may alternatively be due to pressure sensitivity of the silver halide grains rich in chloride. Measures in order to prevent pressure sensitivity may be coating of enhanced amounts of binder as e.g. gelatin. This however is disadvantageous with respect to rapid processing and therefore as an alternative silver halide crystals rich in chloride prepared in silica may offer an alternative as has been disclosed e.g. in EP-A 0 528 476.
  • Backing layers applied to a material having at least one emulsion layer at one side of a light-sensitive silver halide material having emulsion crystals rich in chloride used in the image-forming systems essentially contain as ingredients hydrophilic colloids, one or more antihalation dye(s), matting agent(s), surfactant(s), antistatic agent(s), lubricant(s) and hardening agent(s), said ingredients being same as discussed hereinbefore.
  • Amounts of hydrophilic colloids may be chosen in order to prevent curl of the single side emulsion coated material, such as in US-A 5,155,013.
  • non-swelling hydrophobic polymers can be used in the backing layer as has e.g. been described in US-A 5,326,686. Further measures to prevent curling have been disclosed e.g. in JP-A's 02-24645; 02-85847 and 02-87138.
  • the support of the black-and-white photographic materials comprising silver halide emulsion having crystals rich in chloride, used for X-ray imaging may be a transparent resin, preferably a blue coloured polyester support like polyethylene terephthalate.
  • the thickness of such organic resin film is preferably about 175 ⁇ m.
  • Other hydrophobic resin supports are well known to those skilled in the art and are made e.g. of polystyrene, polyvinyl chloride, polycarbonate and polyethylene naphthalate.
  • the support is further provided with a substrate layer at both sides to have good adhesion properties between the adjacent layers and said support: one or more subbing layers known to those skilled in the art for adhering thereto a hydrophilic colloid layer may be present.
  • Suitable subbing layers for polyethylene terephthalate supports are described e.g. in US-A's 3,397,988, 3,649,336, 4,123,278 and 4,478,907.
  • a preferred layer arrangement wherein a subbing layer composition comprising as a latex copolymer vinylidene chloride, methylacrylate and itaconic acid has been covered with hydrophilic layers being at least one gelatinous dye containing layer comprising one or more dyes, at least one silver halide emulsion layer, at least one protective antistress layer, and optionally an afterlayer has been described in EP-A 0 752 617.
  • said hydrophilic layers have a swelling ratio of not more than 200 % and in said hydrophilic layers are coated simultaneously by the slide-hopper coating or by the slide-hopper curtain coating technique. Further information on suitable supports can be found in RD's Nos. 36544 and 38957, Chapter XV, published September 1994 and September 1996 respectively.
  • the silver halide grains or the silver halide emulsions in the present invention can be used for conventionally known all black-and-white photographic materials such as, for example, X-ray photographic materials, photographic materials for printing, photographic papers, photographic negative films, microfilms, direct positive photographic materials, super fine grain light-sensitive materials (for a LSI photomask, for a shadow mask, for a liquid crystal mask, for diffusion transfer type materials, for heat-developable photographic materials, for high-density digital recording photographic materials, photographic materials for holography, etc.
  • X-ray photographic materials photographic materials for printing, photographic papers, photographic negative films, microfilms
  • direct positive photographic materials for a LSI photomask, for a shadow mask, for a liquid crystal mask, for diffusion transfer type materials, for heat-developable photographic materials, for high-density digital recording photographic materials, photographic materials for holography, etc.
  • black-and-white silver halide photographic materials comprising tabular grains rich in chloride to be processed according to the method of the present invention are (single-side or double-side coated) radiographic materials or (single-side coated) laser-imaging materials wherein a laser source directed by digital information is "written" on a hard-copy laser film.
  • Suitable lasers may be gas lasers or solid state lasers.
  • a suitable gas laser a helium/neon gas laser is well-known (absorption maximum 633 nm).
  • As a solid state laser an infrared laser diode having a more bathochrome absorption maximum at 820 nm may be used, but nowadays also green- and blue-light laser sources are available, as e.g. a YAG-laser.
  • As a preferred laser imager we refer to the laser imager MATRIX LR 3300, trade name product marketed by Agfa-Gevaert.
  • Double-side coated materials have e.g. been described in US-A 5,449,599, in EP-A's 0 610 608, 0 712 036 and 0 794.456. Double-side coated materials have e.g. been described in US-A's 5,397,687 and 5,660,966 and in EP-A's 0 678 772 and 0 754 972.
  • penetrating radiation which is high energy radiation belonging to the class of X-rays, ⁇ -rays and high energy elementary particle radiation, e.g. ⁇ -rays, electron beam or neutron radiation.
  • penetrating radiation For the conversion of penetrating radiation into visible light and/or ultraviolet radiation luminescent substances are used called phosphors.
  • Light emitted imagewise by intensifying screens as in medical diagnosis irradiates a contacting photographic silver halide emulsion layer film which after exposure is developed to form therein a silver image in conformity with the X-ray image.
  • the X-ray film comprises a transparent film support double-side coated with a silver halide emulsion layer. During the X-ray irradiation said film is arranged in a cassette between two X-ray conversion screens each of them making contact with their corresponding silver halide emulsion layer.
  • Phosphors suitable for use in the conventional radiographic system must have a high prompt emission on X-ray irradiation and low after-glow in favour of image-sharpness.
  • Typical blue-UV emitting phosphors are tantalates and hafniates and fluorohalides of barium and strontium.
  • particles a niobium doped, monoclinic M, yttriumtantalate phosphor and particles of an europium doped bariumfluorohalide phosphor are composing the screen.
  • Screen/film combinations may be symmetric or asymmetric: this means that screens differing in speed and/or radiation emitted therefrom are differing and/or that there is a difference in speed and/or contrast and/or spectral sensitivity at both sides of the film support.
  • processing apparatus In a conventional processing apparatus the sheet material is transported along a generally horizontal feed path, the sheet material passing from one vessel to another usually via a circuitous feed path passing under the surface of each treatment liquid and over dividing walls between the vessels.
  • processing machines having a substantially vertical orientation have also been proposed, in which a plurality of vessels are mounted one above the other, each vessel having an opening at the top acting as a sheet material inlet and an opening at the bottom acting as a sheet material outlet or vice versa.
  • substantially vertical is intended to mean that the sheet material moves along a path from the inlet to the outlet which is either exactly vertical, or which has a vertical component greater than any horizontal component.
  • the apparatus occupies only a fraction of the floor space which is occupied by a conventional horizontal arrangement.
  • the sheet transport path in a vertically oriented apparatus may be substantially straight, in contrast to the circuitous feed path which is usual in a horizontally oriented apparatus.
  • the straight path is independent of the stiffness of the sheet material and reduces the risk of scratching compared with a horizontally oriented apparatus.
  • it is important to avoid, or at least minimise leakage of treatment liquid from one vessel to another and carry-over as the sheet material passes through the apparatus.
  • the treatment liquid in one vessel is not contaminated by contents of the adjacent vessels, that is neither by the treatment liquid of the next higher vessel nor by vapours escaping from the next lower vessel.
  • the developing cell of the apparatus is a closed cell and the developing liquid contains an ascorbic acid developing agent as has been described in EP-Application No. 96201753, filed June 24, 1996.
  • a method of processing photographic sheet material by use of an apparatus comprising a plurality of processing cells so arranged to define a sheet material path through the apparatus, at least one of the cells constituting a developing cell containing a developing liquid, characterised in that the developing cell is a closed cell and the developing liquid contains an ascorbic acid developing agent.
  • any combination of a laser/film or screen(s)/film may be used, wherein said film may comprise ⁇ 111 ⁇ and/or ⁇ 100 ⁇ tabular silver halide crystals rich in silver chloride in combination with a processing unit as disclosed in that reference, the proviso that with minimum amounts of silver coated a sufficiently high covering power is attained in the film in rapid ecological processing (with e.g.
  • the thus obtained silver chloride tabular emulsion showed the following grain characteristics:
  • the mV-value of the emulsion was adjusted at +120 mV with sodium chloride and the pH-value at 5.5 with sodium hydroxide. Chemical ripening agents were adapted to the crystal size of the emulsions.
  • Chemical ripening agents were gold thiocyanate, sodium thiosulphate as a source of sulphur and toluene thiosulphonic acid was used as predigestion agent.
  • the amounts of each chemical ripening agent were optimized in order to obtain an optimal fog-sensitivity relationship after 2 hours at 57°C.
  • the resulting black-and-white photographic material contained per side an amount of silver halide corresponding to 3.5 grams of AgNO 3 per m 2 and an amount of gelatin corresponding to 2.8 g/m 2 .
  • an emulsion having cubic silver chloroiodide crystals was prepared having 99.8 mole % of silver chloride and 0.2 mole % of iodide and an average grain size of 0.57 ⁇ m.
  • the said cubic crystals were prepared in the following way: an amount of 880 ml of demineralized water was used as starting volume in the vessel, containing further 46 g of inert gelatin at 60°C. 2 ml of a solution of silver nitrate 0.3 molar was added. Two minutes later a sodium chloride 4N was added dropwise in order to adjust UAg to a potential difference vs. a S.C.E. reference electrode of + 138 ⁇ 2 mV.
  • the flocculation procedure could begin: pH was adjusted at a value of 3.3 with sulphuric acid, 3 M, and 4.5 g of polystyrene sulphonic acid was added slowly in 2 minutes. The washing procedure was performed in a discontinous way, adding 3 l of demineralized water, containing up to 8 mmole of sodium chloride per liter. After addition of inert gelatin to a ratio of gelatin to silver nitrate in the emulsion of about 0.5, the emulsion was peptized and was chemically ripened to an optimal fog-sensitivity relationship at 52°C, UAg having a value of about 160 mV.
  • 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 mmoles and 6 mmoles respectively.
  • Spectral sensitization was performed in the same way as for the tabular grains.
  • the emulsion having cubic crystals was coated in the same way and with the same coating amount of silver as for the tabular grains.
  • the concentrated black-and-white developer free from hardening agents should be diluted with the same amount of demineralized water (pH of developer ready-for-use: 10.46).
  • Composition of the fixer ammonium thiosulphate (60%) 710 ml boric acid 20.8 g sodium sulphite 45 g sodium acetate.3 aq. 58 g acetic acid 48.5 ml sulphuric acid 20 ml demineralised water to make 1 liter.
  • the fixer is used without further dilution.
  • A,B,C,... to J 10 differing black-and-white developer solutions were prepared, called A,B,C,... to J, wherein as is clear from the figures in Table 1 A', B', D' and G' have the same composition as A, B, D and G respectively and are differing in that the black-and-white material processed therein is coated from the comparative cubic silver chloroiodide grains where an accent is added to the characters, whereas the characters are left unchanged if the material processed in the corresponding chemistry is coated from tabular silver chloroiodide grains used in the method of the present invention.
  • the density as a function of the light dose was measured and therefrom were determined the following parameters:
  • developer F corresponding with a preferred embodiment of the method of this invention, the most suitable relationship is thus attained between fog-speed-contrast and covering power.
  • Example 2 The same emulsion having tabular grains rich in silver chloride as described in Example 1 was coated in the materials prepared in Example 2, except for the presence in the coating B of an amount of 3 mg per m 2 of 5-methyl-benztriazole in the protective layer, said protective layer further containing 1.3 g gelatine per m 2 per side on both sides of a polyethylene terephthalate film support having a thickness of 175 ⁇ m. Coating A was free from 5-methyl-benztriazole in the protective antistress layer.
  • the resulting black-and-white photographic materials A and B contained per side an amount of silver halide corresponding to 3.59 and 3.64 grams of AgNO 3 per m 2 respectively and an amount of gelatin corresponding to 2.8 g/m 2 .
  • the processing composition for the black-and-white development of the silver halide materials A and B is given hereinafter: demineralized water 700 ml sodium erythorbate 1aq. 61.5 g 4,4'-hydroxymethyl-methyl-phenidone 2 g potassium bromide 0 g potassium thiocyanate 1 g 5-chloro-benzotriazole 0.14 g aqueous potassium sulphite (655 g/l) 0 ml aqueous potassium carbonate (765 g/l) 125 ml aqueous potassium hydroxyde (755 g/l) 10 ml 1-hydroxy ethyl diphosphonic acid di-Na salt 1 g Polyethylene glycol (M.W.: 400) 20 ml pH (adjusted with acetic acid) 9.65 Water to make 1 l.
  • the concentrated low-sludge "ecological" black-and-white developer free from hardening agents, free from hydroquinone, free from bromide ions and free from sulphite should be diluted with the same amount of demineralized water (pH of developer ready-for-use: 10.46).
  • an organic compound inhibiting development as 5-methyl-benztriazole in minor amounts of about 20-25 ⁇ mole/m 2 in material B, is present in the protective antistress layer, covering power is enhanced, without further remarkably influencing the fog-speed relationship.

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Claims (13)

  1. Verfahren zur Verarbeitung eines bildmäßig belichteten, lichtempfindlichen, schwarzweißfotografischen Silberhalogenidmaterials mit einem Träger, der einseitig oder beidseitig mit hydrophilen Schichten beschichtet wurde, von denen mindestens eine Schicht eine oder mehrere Emulsionen mit silberchloridreichen Silberhalogenid-Tafelkörnern enthält, wobei das Verfahren die Schritte Entwickeln, Fixieren, Spülen und Trocknen umfaßt, dadurch gekennzeichnet, dass der Entwicklungsschritt in einem Schwarzweißentwickler erfolgt, der eine oder mehrere die Entwicklung hemmende organische Verbindungen in einer Menge von 0,1 mmol bis 1 mmol pro Liter gebrauchsfertigen Entwickler enthält, und dadurch, dass der Entwickler im wesentlichen frei von Bromid-Ionen ist.
  2. Verfahren nach Anspruch 1, dadurch gekennzeichnet, dass die die Entwicklung hemmende organische Verbindung eine Benztriazolverbindung ist bzw. die die Entwicklung hemmenden organischen Verbindungen Benztriazolverbindungen sind.
  3. Verfahren nach Anspruch 2, dadurch gekennzeichnet, dass die Benztriazolverbindung bzw. -verbindungen einen der allgemeinen Formel (I) entsprechenden Aufbau aufweist bzw. aufweisen,
    Figure 00460001
    in der R ein Wasserstoffatom, ein Halogenatom, eine Alkylgruppe, eine Aminogruppe, eine Eydroxylgruppe, eine Carboxylgruppe, eine Sulfonsäuregruppe, eine Alkoxycarbonylgruppe, eine Acylamidgruppe oder eine Sulfonamidgruppe bedeutet.
  4. Verfahren nach Anspruch 2, dadurch gekennzeichnet, dass die Benztriazolverbindung bzw. -verbindungen aus der Reihe Benzotriazol, 5-Methylbenzotriazol, 4-Methylbenzotriazol, 6-Aminobenzotriazol, 5-Chlorbenzotriazol, 5-Carboxybenzotriazol und 5-Trifluormethylbenzotriazol ausgewählt wird bzw. werden.
  5. Verfahren nach einem der Ansprüche 1 bis 4, dadurch gekennzeichnet, dass der Entwickler Entwicklersubstanzen aus der Reihe Hydrochinon, Ascorbinsäure, Reduktinsäure oder deren Abkömmlingen enthält.
  6. Verfahren nach einem der Ansprüche 1 bis 5, dadurch gekennzeichnet, dass der Entwickler weiterhin Thiocyanat-Ionen in einer Menge von 5 mmol bis 25 mmol pro Liter gebrauchsfertigen Entwickler enthält.
  7. Verfahren nach einem der Ansprüche 1 bis 6, dadurch gekennzeichnet, dass der Entwickler einen pH-Wert von 8,5 bis 10,3 aufweist.
  8. Verfahren nach einem der Ansprüche 1 bis 7, dadurch gekennzeichnet, dass der Entwickler frei von Härtemitteln ist.
  9. Verfahren nach einem der Ansprüche 1 bis 8, dadurch gekennzeichnet, dass der Fixierschritt in einem Fixiermittel, das im wesentlichen frei von Aluminium-Ionen ist, erfolgt.
  10. Verfahren nach einem der Ansprüche 1 bis 9, dadurch gekennzeichnet, dass die Verarbeitung in einer Gesamtverarbeitungszeit von 90 Sekunden oder weniger erfolgt.
  11. Verfahren nach einem der Ansprüche 1 bis 10, dadurch gekennzeichnet, dass es sich bei den silberchloridreichen Silberhalogenid-Tafelkörnern um {111}-Tafelkörner, die mindestens 50% der gesamten projizierten Oberfläche aller Körner ausmachen, ein durchschnittliches Aspektverhältnis größer als 2 und eine durchschnittliche Korndicke von 0,05 bis 0,30 µm aufweisen, handelt.
  12. Verfahren nach einem der Ansprüche 1 bis 11, dadurch gekennzeichnet, dass es sich bei den silberchloridreichen Silberhalogenid-Tafelkörnern um Körner aus der Reihe Silberchlorid, Silberchloridiodid, Silberchloridbromid und Silberchloridbromidiodid handelt.
  13. Verfahren nach einem der Ansprüche 1 bis 12, dadurch gekennzeichnet, dass weiterhin die Nachfüllung beim Entwicklungsschritt und/oder beim Fixierschritt mit Entwicklerund/oder Fixierbadnachfülllösungen in Mengen von 200 ml oder weniger pro m2 verarbeitetes Material erfolgt.
EP97203819A 1996-12-30 1997-12-05 Verfahren zur Verarbeitung eines photographischen lichtempfindlichen Silberhalogenidmaterials Expired - Lifetime EP0851282B1 (de)

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JPH0738073B2 (ja) * 1987-04-14 1995-04-26 富士写真フイルム株式会社 ハロゲン化銀写真感光材料の現像方法
JPH0619067A (ja) * 1992-07-01 1994-01-28 Fuji Photo Film Co Ltd 黒白ハロゲン化銀写真感光材料の現像方法
US5298372A (en) * 1992-07-03 1994-03-29 Fuji Photo Film Co., Ltd. Method for processing black-and-white silver halide photographic material
JPH0651452A (ja) * 1992-07-29 1994-02-25 Fuji Photo Film Co Ltd 黒白ハロゲン化銀写真感光材料の処理方法
JPH06138591A (ja) * 1992-10-23 1994-05-20 Konica Corp ハロゲン化銀写真感光材料の現像処理方法
JPH0990573A (ja) * 1995-09-28 1997-04-04 Konica Corp ハロゲン化銀写真感光材料の処理用固体現像補充剤及び現像処理方法

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