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
  • G03C5/305—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
  • G03C1/00—Photosensitive materials
  • G03C1/005—Silver halide emulsions; Preparation thereof; Physical treatment thereof; Incorporation of additives therein
  • G03C1/0051—Tabular grain emulsions
• • 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
  • G03C1/035—Silver halide emulsions; Preparation thereof; Physical treatment thereof; Incorporation of additives therein characterised by the crystal form or composition, e.g. mixed grain
  • G03C2001/03535—Core-shell grains
• • 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
  • G03C1/035—Silver halide emulsions; Preparation thereof; Physical treatment thereof; Incorporation of additives therein characterised by the crystal form or composition, e.g. mixed grain
  • G03C2001/03558—Iodide content
• • 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
  • G03C2005/3007—Ascorbic acid
• • 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
  • G03C2200/01—100 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
  • G03C2200/03—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
  • G03C2200/34—Hydroquinone
• • 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
  • G03C2200/40—Mercapto compound
• • 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
  • G03C5/16—X-ray, infrared, or ultraviolet ray processes
  • G03C5/17—X-ray, infrared, or ultraviolet ray processes using screens to intensify X-ray images
• • 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

Definitions

• the present invention relates to a processing method of exposed light-sensitive black-and-white silver halide materials having silver halide grains in their light-sensitive hydrophilic layers.
• the film materials are coated with relatively high amounts of silver, in order to provide a suitable sensitometry even if a low radiation dose is applied to the patient as is always desirable.
• ⁇ 111 ⁇ tabular silver halide grains permits coating of lower amounts of silver, if compared e.g. with grains having a more globular shape like cubic grains as applied before practical application of said tabular grains, there remains the need to provide an acceptable image tone after development of materials having light-sensitive silver halide layers containing said tabular grains, optionally containing cubic grains.
• radiographic film materials single-side as well as duplitized or double-side coated in its light-sensitive layer(s) with one or more spectrally sensitized silver halide emulsion(s) in order to get a diagnostic image having a desired cold blue-black image tone.
• an exposed black-and-white silver halide photographic film material comprising in one or more hydrophilic light-sensitive layer(s) thereof a binder and silver halide grains being ⁇ 111 ⁇ or ⁇ 100 ⁇ tabular silver bromo(chloro)iodide or silver chloro(bromo)iodide grains having an average aspect ratio of from 1.2 to 50 and having silver iodide in an amount of less than 5 mole %, and more preferably less than 3 mole % based on silver (with at least part of it at their grain surface), said method comprising the steps of developing in a developer, fixing in a fixer, rinsing and drying, characterized in that in said developing step the developer comprises an alkali soluble agent or compound having preventing silver dissolution properties, wherein said alkali soluble compound, as presented in the description hereinafter and in the claims, is a mercapto-azole compound having alkali soluble groups.
• said silver halide grains are ⁇ 111 ⁇ or ⁇ 100 ⁇ tabular silver bromo (chloro)iodide or silver chloro (bromo)iodide grains having an average aspect ratio of from 1.2 to 50. It is understood that the halide, first mentioned in the composition as described, is present therein in the highest amount, expressed in molar amounts, based on silver.
• all of said silver halide grains have a silver iodide content of from 0.1 up to 1 mole % based on silver.
• silver iodide content of from 0.1 up to 1 mole % based on silver.
• the method of processing of a light-sensitive black-and-white silver halide photographic material thus comprises the steps of developing, fixing, rinsing and drying, wherein during said processing said developer comprises, besides one or more developing agent(s), one or more agent(s) preventing oxidation thereof and agent(s) providing pH buffering in running equilibrium conditions during said processing, at least one alkali-soluble agent having preventing silver dissolution properties as set forth hereinbefore, wherein said agent or compound is present in the developer solution in an amount of from 5 x 10 -5 up to 1 x 10 -3 mole per liter of said developer, more preferably from 5 x 10 -5 up to 1 x 10 -3 mole per liter.
• a compound according to the general formula (I) having a molecular weight of e.g. 160 this corresponds with an amount in mg of from 8 up to 160 mg/l of developer solution.
• said mercapto azole compound is a compound selected from the group consisting of tetrazoles, triazoles, benzotriazoles, imidazoles, benzimidazoles, oxazoles, benzoxazoles, thiazoles, benzthiazoles, selenazoles, benzselenazoles, diazoles, indazoles, iso-oxazoles, iso-thiazoles and oxadiazoles .
• said alkali soluble agent having preventing dissolution properties being a mercapto azole compound is represented by formula (II) or a salt thereof, wherein the alkali soluble group is a carboxylic acid group:
• said mercapto azole compound is present in the developer in an amount of from 20 up to 50 mg per 100 ml of developer ready-for-use.
• Other agents or compounds suitable for use in the developer solution in the processing method of the present invention are represented by the formulae (III) to (XXVI) hereinafter
• the developer solution may be any of the solutions which is used in order to develop a photographic material, i.a. a starting solution, a seasoned developer, a developing solution ready-for-use or the concentrated developer compositions thereof.
• the developer solution chemistry in the processor is the replenishment developer solution chemistry, whether or not with a supplementary additive mixed therewith, said supplementary additive being the developer starter solution.
• Said "fresh developer” is defined as the developer present in the developer unit of the processor before any film has passed, or in the alternative, the developer in which a very little amount of film was run, well before a steady state or equilibrium situation is reached (e.g. resulting in a "half-seasoned” developer).
• developer replenisher solution is defined as the unused developer present in the developer container which is, in the method of the present invention, mixed in the developer unit with developer starter solution in order to prepare the "fresh developer” solution defined hereinbefore. It is clear that said “developer replenishing solution” is added further to the developer unit as the film is being processed, acting as a commonly used “replenisher” too.
• the “seasoned developer” is defined as the developer present in the developer unit of the processor after processing enough film in order to reach a steady-state or an equilibrium situation, depending on the amounts of replenisher used. In order to reach said steady-state, the said developer is topped up with the "developer replenisher solution” defined hereinbefore. The said “seasoned developer” is the same as the developer in "running equilibrium conditions”.
• the said developer solution comprises a mixture of a developer starter solution and developer replenisher solution, wherein it is understood that both solutions have been mixed before addition to the developer unit or tank of the automatic processor.
• an additional step is the step of adding of a developer starter solution to the developer replenisher solution which is present in the said developer unit or tank.
• said developer starter solution is preferably added before starting processing, although it is not excluded to add the said developer starter solution during processing, i.e. after the processing has been started, before an equilibrium or seasoned state has been reached.
• the method of the present invention comprises the step of mixing of developer starter solution and fixer replenishing solution in a developer unit or tank of the said processor.
• said developer starter solution is mixed with the developer replenishing solution in the processor before starting processing.
• the developer starter solution is a buffering solution. Said buffering solution alters pH of the developer to the required value: so in a preferred embodiment said developer starter solution alters pH to a value in the range from - 0.3 up to + 0.3 units of the pH of the developer solution after seasoning.
• said developer starter solution is water or an alkaline solution.
• an amount of developer starter solution is proportional to tank volume of the developer solution in the processor.
• an amount of developer starter solution is less than 10 % of volume of replenisher solution with which it is mixed upon starting processing.
• Developer solutions may contain glutardialdehyde as hardening agent but in a preferred embodiment, favourable with respect to ecology, the developer is free thereof.
• the light-sensitive black-and-white silver halide photographic materials processed in the developing composition by the method according to the present invention should be hardened to such an extent that in a developing step free from hardening agents no problems occur as e.g. "sludge formation" in form of troubles due to lack of physical strength properties of the materials.
• 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 II. Vinyl sulfonyl hardeners are nowadays preferred as instant hardeners, which is e.g. not the case with formaldehyde.
• a main developing agent is present in the developer, wherein said agent is selected from the group consisting of hydroquinones and reductones or a combination thereof, wherein said reductones preferably are members selected from the group consisting of 1-ascorbic acid, iso-ascorbic acid, and reductic acid.
• Said 1-ascorbic acid, iso-ascorbic acid and reductic acid are the more preferred forms from the ascorbic acid type developers according to the formula (XXVII) wherein in the formula (XXXIV) each of A, B and D independently represents an oxygen atom or NR' 1 ;
• iso-ascorbic acid and l-ascorbic acid are both preferred.
• the compound(s) according to the formula (XLI) preferably is(are) present in the developer solution in an amount comprised between 1 g and 100 g per litre, although a preferred amount of from 20 up to 50 g per litre is sufficient in many cases.
• Examples of reducing precursor compounds suitable for use in the developer of the present invention have, e.g., been described in WO's 94/3834 and 94/16362.
• 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-A'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.
• said antioxidant or agent preventing oxidation is selected from the group consisting of a sulfite salt, 1-ascorbic acid, iso-ascorbic acid, reductic acid, salts and derivatives and combinations thereof.
• a combination of high amounts of ascorbic acid type compounds and low amounts of sulfite is therefore highly preferred as the presence of sulfite normally leads to undesirable odours in the processing.
• Low amounts of sulfite as e.g. disclosed in EP-A 0 738 400 are therefore preferred: amounts of less than 0.4 mole per liter of developer are satisfactory in order to prevent oxidation by air oxygen.
• a preferred phenidone compound used in the method of the present invention is 4,4'-hydroxymethyl-methyl-1-phenyl-3-pyrazolidine-1-one, which is present in amounts of from 0.5 g up to 5 g/litre of developer. Especially if iodide ions are present in the developing solution, said preferred phenidone compound is present in lower amounts as has been disclosed in US-A 5,296,342.
• a pH buffering agent is present, wherein said buffering agent is selected from the group consisting of carbonates, phosphates and borates and combinations thereof. More particularly carbonate buffers applied may be those described in EP-A's 0 565 459 and 0 736 802 (together with borate) and in US-A's 5,648,205 and 5,738,979; whereas borate buffers may be those as described in GB-A 2,292,813 and in US-A's 5,702,875; 5,756,271 and 5,853,964 and phosphate buffers as in US-A's 5,585,610; 5,744,279; 5,858,612 and 5,876,907.
• the said processing further comprises the step of replenishing the developer composition in an amount of less than 200 ml/m2 and, moreover, the said replenishing proceeds with a replenisher having the same composition as the developer composition.
• EP-A 0 874 276 it is recommended, as further described in EP-A 0 962 820, in particular for photographic materials having silver halide, coated in an amount, expressed as an equivalent amount of silver nitrate of less than 6 g/m 2 that the said material has a buffering capacity of less than 6 mmole/m 2 , preferably of less than 4 mmole/m 2 and even more preferably less than 2.5 mmole/m 2 , wherein said buffering capacity is defined as the amount of alkali, expressed in mmole/square meter required to bridge across pH differences between the material and the developer.
• said processing proceeds in a total dry-to-dry processing time of less than 100 seconds.
• the method of the present invention is not restricted to the processing of materials coated with such low amounts of silver halide and that also silver halide materials more rich in coated amounts of silver, as e.g. double-side coated materials for non-destructive testing purposes having an amount of silver up to 20 g per sq.m. and per side of the support, said amount of silver being expressed as an equivalent amount of silver nitrate, as disclosed e.g. in EP-A 0 698 817.
• the developer solution is buffered between a value of from 9.0 up to 11.0 by buffering compounds having a concentration of from 0.3 up to 1.0 mole/litre and more preferably from 0.3 up to 0.7 mole/litre.
• Particularly suitable buffering compounds in the developing solution are carbonates as has also been shown in EP-A 0 565 459 wherein the use of ascorbic acid developers with high concentrations of carbonate buffering is illustrated.
• the high carbonate level provides a high degree of pH buffering and also provides aeration protection via reduced oxygen solubility in the developing solution.
• Use of highly buffered ascorbic acid developers has been disclosed e.g. in US-A 5,503,965, wherein the instability of ascorbic acid developers has been tackled not only by the use of highly buffering solutions but in addition by the use of replenisher solutions having a higher pH.
• pH of the developer replenisher In order to compensate during processing for a decrease of pH due to the oxidation of ascorbic acid type developing agents, if present, to oxalic acid it is recommended to provide pH of the developer replenisher to be higher as e.g. in EP-A 0 573 700 and in US-A 5,869,218 and more particularly about 0.5 higher than the developer itself as in US-A 5,503,965; although depending on the composition of the developer pH differences of 0.1 to 0.3 pH units may be sufficient as disclosed in US-A 5,738,979. In the alternative mixtures of two pyrazolidones may compensate for pH drop as has been suggested in EP-A 0 588 408.
• Ascorbic-acid type developers used in the method of the present invention preferably have a pH in the range from 9-11, but lower values as e.g. in US-A's 5,702,875; 5,756,271; 5,853,964 and 5,858,610 are not excluded.
• Alkalizing agents providing the desired pH are e.g. those described in US-A 5,821,041.
• the developing solution has a regeneration rate less than 150 ml/m2 and pH of the developing solution in running equilibrium conditions is between 9.5 and 9.9, with a pH difference between the seasoned developer and the developer replenisher between 0.3 and 0.6.
• the method according to the present invention it is further preferred that, in order to provide constant sensitometric and physical properties of silver halide photographic materials after rapid processing in solutions, replenished with minimum amounts of said solutions and in order to specifically minimize the differences between the freshly prepared fixer solution and the fixer solution after seasoning that upon starting of the processing the said fixer solution comprises a mixture of a fixer starter solution and a fixer replenisher solution and in that said fixer solution is replenished with the said fixer replenishing solution as disclosed in EP-A 0 851 286.
• said method comprises the step of mixing a fixer starter solution and a fixer replenisher solution in a fixer unit or tank of the said processor.
• the film material to be processed is a light-sensitive black-and-white silver halide photographic material which is a single-side or double-side coated material, coated on a subbed support with one or more light-sensitive silver halide emulsion layers.
• said material is a radiographic material as for such material having diagnostic value it is of utmost importance to provide an image having an optimized image quality for the medicamentn, also with respect to more perceptible characteristics as image tone in order to make said medicinaln able to formulate unambiguous conclusions after having viewed said image.
• cubic silver bromo (chloro)-iodide grains having an average crystal diameter of 0.1 up to 1 ⁇ m may be present.
• the said light-sensitive silver halide emulsions present individually or as a mixture of different emulsions are present in one or more adjacent layers at one side or at both sides of the support material and grains or crystals present therein may be cubic grains (whether or not with rounded corners as a consequence e.g. of use of grain growth modifiers, such as e.g.
• Emulsions comprising crystals having a habit selected from the group consisting of a ⁇ 100 ⁇ tabular, a ⁇ 111 ⁇ tabular and a cubic habit and mixtures thereof, suitable for use in the method of the present invention have e.g. been described in BE 93001438, in EP-A's 0 288 949, 0 528 480, 0 555 897, 0 573 373, 0 574 331, 0 592 616, 0 614 111, 0 622 668, 0 581 065, 0 678 772, 0 704 750, 0 709 730, 0 724 193, 0 731 382, 0 736 797, 0 786 694, 0 770 909, 0 809 135, 0 809 139, 0 843 207, 0 851 282, 0 862 083, 0 862 088, 0 866 362, 0 890 873, 0 908 764, 0 911 6
• Emulsions comprising crystals having a habit selected from the group consisting of a ⁇ 100 ⁇ tabular grains rich in silver chloride, suitable for use in the method of the present invention have e.g. been described in EP-A's 0 534 395, 0 653 669, 0 584 815, 0 584 644, 0 617 317, 0 617 321, 0 645 670, 0 672 940, 0 670 515, 0 670 514, 0 767 400, 0 768 567, 0 843 207, 0 911 688, 0 949 536; in US-A's 5,292,632; 5,320,938; 5,356,764; 5,558,982; 5,565,315; 5,641,620; 5,663,041 and in Research Disclosure No.394 (1997), p.83-89.
• Said ⁇ 100 ⁇ tabular grains are preferably accounting for at least 30% and more preferably at least 50% of the total projective area of all grains, having at least 90 mole% of silver chloride, not more than 1 mole% of silver iodide and more preferably 0.1 up to 0.4 mole % at the grain surfaces.
• the said light-sensitive silver halide emulsions present individually or as a mixture of different emulsions are present in one or more adjacent layers at one side or at both sides of the support material and grains or crystals present therein are ⁇ 111 ⁇ or ⁇ 100 ⁇ tabular grains rich in silver bromide (more than 50 mole % of bromide) or rich in silver chloride (more than 50 mole % of chloride).
• Said tabular grains preferably account 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 %, further have an average crystal diameter (equivalent circular diameter leading to an equal total flat surface as the preferred hexagonal ⁇ 111 ⁇ or rectangular ⁇ 100 ⁇ grain) of from 0.3 to 3.0 ⁇ m, more preferably from 0.5 to 2.5 ⁇ m and still more preferably from 0.5 to 1.5 ⁇ m, for an average thickness of the tabular grain from 0.05 up to 0.30 ⁇ m, more preferably from 0.05 to 0.25 ⁇ m.
• an average crystal diameter equivalent circular diameter leading to an equal total flat surface as the preferred hexagonal ⁇ 111 ⁇ or rectangular ⁇ 100 ⁇ grain
• Average aspect ratios of the ⁇ 111 ⁇ or ⁇ 100 ⁇ tabular grains obtained after calculation from the ratio of diameter to thickness measured for each grain are in the range 2:1 to 100:1, more preferably from 5:1 to 50:1 and still more preferably from 5:1 to 20:1 or even from 8:1 to 20:1.
• Variation coefficients calculated over grain diameters or thicknesses are preferably less than 0.40, more preferably less than 0.30 and even more preferably in the range from 0.10-0.20, thereby being indicative for the degree of homogeneity of the grain distribution in an emulsion.
• a crystal habit modifier being a habit stabilizer
• Preferred crystal habit modifiers which are useful in the preparation of ⁇ 111 ⁇ tabular grains for use in the method of the present invention have e.g.
• Iodide ions can be provided by using aqueous solutions of inorganic salts thereof as e.g. potassium iodide, sodium iodide or ammonium iodide and can be added apart (as solution providing conversion) or in a double-jet step together with a silver salt solution as e.g. silver nitrate. Iodide ions can also be provided by organic compounds releasing iodide ions as has e.g.
• 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 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.
• recommended amounts present in the material used in the method of the present invention preferably have a calcium content of less than 10 mg/sq.m. as in US-A 5,723,267, more preferably of less than 5 mg/sq.m. and still more preferably of less than 3 mg/sq.m..
• Dyes absorbing in the blue wavelength region of the visible spectrum for use as spectral sensitizers for cubic and/or tabular silver halide grains can be used as those described in JP-A 01-196031 and in US-A's 4,494,212; 4,952,491 and 5,376,523.
• spectral sensitization as described in EP-A 0 890 873 can advantageously be applied. The same applies to the other regions of the visible spectrum as the green wavelength region (see e.g.
• spectral sensitizers described in EP-A 0 757 286.
• combinations of differing 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.
• 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.
• 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.
• Said protective antistress layer may comprise e.g. one or more organic compounds inhibiting development, like e.g. organic compound(s) inhibiting development is(are) preferably (a) benzotriazole compound(s) as disclosed in EP-A 0 866 362.
• Protective antistress layers present in the materials used in the method of the present invention 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 in 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 as can be applied 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. 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 prepared in silica may offer an alternative as has been disclosed e.g. in EP-A's 0 528 476, 0 649 051 and 0 682 287 .
• one or more subbing layers e.g. filter layers, antistatic agent(s), filter dyes for safety-light purposes etc. may be present.
• intermediate layers eventually containing filter or antihalation dyes that absorb scattering light and thus promote the image sharpness have been described in e.g.
• Backing layers applied to a material having at least one emulsion layer at one side of a light-sensitive silver halide material used in the method of the present invention 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, used in the method of the present invention, more particularly 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.
• 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 can be applied and 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 supports suitable for use herein can be found in RD's Nos.
• materials having subbed supports are preferably providing permanent antistatic character thanks to electronic conductivity of polyethylene dioxythiophene (PEDT) as those described in EP-A 0 602 713 and in EP-A 1 031 875.
• PEDT polyethylene dioxythiophene
• black-and-white photographic materials can be used 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.
• said black-and-white silver halide photographic materials 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).
• 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.
• a preferred laser imager we refer to the laser imager MATRIX LR 3300, trade name product marketed by Agfa-Gevaert.
• Suitable single-side coated materials for use in the processing of the present invention have e.g.
• 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.
• Useful multilayer assemblies have e.g. been described in EP-A 0 770 909.
• 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.
• An improved set of blue-light-emitting screens has e.g. been described in US-A 5,381,015.
• 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.
• 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.
• the term "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 minimize 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.
• invention is characterized by means for connecting each cell to adjacent cells in the stack in a closed manner and according to a second aspect, the invention is characterised in that the roller is a drive roller.
• the roller is a drive roller.
• 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, characterized in that the developing cell is a closed cell and the developing liquid contains an ascorbic acid developing agent.
• 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, characterized in that the developing cell is a closed cell and the developing liquid contains an ascorbic acid developing agent.
• Material No.1 MAMMORAY MR6 Film (trademarked product from Agfa-Gevaert N.V.) No. 37450058 (having in the light-sensitive emulsion layer a silver bromoiodide emulsion having monodisperse cubic crystals with an average grain diameter of 0.7 ⁇ m and a variation coefficient thereupon of about 0.15).
• Material No.2 CURIX ORTHO Film (trademarked product from Agfa-Gevaert N.V.) No. 39445055 having in the light-sensitive layers at both sides of the film support a silver bromoiodide emulsion (99 mole % of AgBr, 1 mole % of AgI, based on silver) having ⁇ 111 ⁇ tabular crystals with an average volume equivalent diameter of 0.70 ⁇ m and an average grain thickness of 0.23 ⁇ m.
• a silver bromoiodide emulsion 99 mole % of AgBr, 1 mole % of AgI, based on silver
• Material No.3 CURIX ORTHO Film (trademarked product from Agfa-Gevaert N.V.) 39475106 having in the light-sensitive layers at both sides of the film support a silver bromoiodide emulsion (99.9 mole % of AgBr, 0.1 mole % of AgI, based on silver) having ⁇ 111 ⁇ tabular crystals with an average volume equivalent diameter of 0.55 ⁇ m and an average grain thickness of 0.13 ⁇ m.
• a silver bromoiodide emulsion 99.9 mole % of AgBr, 0.1 mole % of AgI, based on silver
• Material No.4 FUJI HRE30 Film (trademarked product from Fuji Photo Film, Japan) 3068601 having in the light-sensitive layers at both sides of the film support having in the light-sensitive layers at both sides of the film support a silver bromoiodide emulsion (99.9 mole % of AgBr, 0.1 mole % of AgI, based on silver) having ⁇ 111 ⁇ tabular crystals with an average volume equivalent diameter of 0.55 ⁇ m and an average grain thickness of 0.15 ⁇ m.
• FUJI HRE30 Film trademarked product from Fuji Photo Film, Japan
• the “inventive processing” (inv.) was run in a processing cycle according to the processing method of the present invention, wherein the "inventive developer” G138i ( ID ) was used, differing from the “comparative” in that compound (II) was added in an amount of 10 ( ID1 ), 25 ( ID2 ) and 50 mg ( ID3 ) per 100 ml of developer.
• the same fixer G334 was used.
• an increased amount of compound (II) added to the developer composition in the processing provides an improved image tone for the correspondingly processed material, if compared with a material coated with a comparative developer having no such additive in its composition. Only if present in the highest amounts as applied in the present example said compound (II) may have an influence on fog (suppressing fog, speed and gradation which become slightly increased for fog and decreased for both speed and gradation respectively, at lower levels of said compound).
• Emulsions A1 and A2 tabular silver chloroiodide emulsions
• Emulsion A1 In order to prepare Emulsion A1 the following solutions were prepared :
• a nucleation step was performed by introducing solution A and solution B1 simultaneously in dispersion medium C, both at a flow rate of 70 ml/min, during 30 seconds at a stirring rate of 500 r.p.m.. After a physical ripening time of 20 min during which the temperature was raised to 70°C, a first growth step was performed.
• Emulsion A1 thus obtained was consisting of an amount by number of more than 90 % of tabular grains having 2 parallel ⁇ 111 ⁇ -faces.
• the crystals were characterized by an average circular diameter of 0.85 ⁇ m and an average volume equivalent diameter dM of 0.64 ⁇ m and an average thickness of 0.14 ⁇ m.
• the silver halide composition was represented as AgCl(99%)I(1%).
• Emulsion A2 was prepared, analoguous as Emulsion A1, except for a few aspects.
• a nucleation step was performed by introducing solution A and solution B1 simultaneously in dispersion medium C, both at a flow rate of 70 ml/min, during 30 seconds at a stirring rate of 500 r.p.m.. After a physical ripening time of 20 min during which the temperature was raised to 70°C, a first growth step was performed.
• solution A maintaining first during 4 min a flow rate of 10.0 ml/min, then increasing the flow rate linearly to an end value of 19.80 ml/min
• an amount of a Lippmann emulsion 100 mole % of AgI, having very fine grains with a diameter of less than 0.050 ⁇ m was added to this dispersion medium in an amount in order to get a total amount of iodide of
• Emulsion A2 thus obtained was consisting of more than 90 % of tabular grains, by number, having 2 parallel ⁇ 111 ⁇ -faces.
• the crystals were characterized by an average aspect ratio of 6.2, an average circular diameter of 0.85 ⁇ m and an average volume equivalent diameter dM of 0.64 ⁇ m.
• the silver halide composition was represented as AgCl(99.3%)I(0.7%).
• the mV-value of the redispersed emulsions A and B were adjusted at +120 mV with sodium chloride and the pH-value at 5.5 with sodium hydroxide.
• anhydro-5,5'-dichloro-3,3'-bis-(n-sulphobutyl)-9-ethyl-oxacarbo-cyanine was added in an amount of 1.25 mmole per mole of silver.
• chemical ripening agents added after the spectral sensitizer, gold thiocyanate and sodium thiosulphate as a source of sulphur were added, whereas toluene thiosulphonic acid was used as predigestion agent.
• the amounts of each chemical ripening were optimized in order to obtain an optimal fog-sensitivity relationship after 2 hours at 57°C.
• each emulsion was stabilized with 1-p-carboxyphenyl-5-mercaptotetrazole and after addition of the normal coating additives the solutions were coated simultaneously together with a protective layer 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.
• the resulting photographic materials A1 and A2 were containing per side an amount of silver halide corresponding to 3.5 grams of silver per m 2 and an amount of gelatin corresponding to 2.80 g/m 2 .
• the processing was run in the developer A the composition of which is given hereinafter (the "comparative processing” (comp.) was run in the “comparative developer A” ( CDA ), followed by fixing in fixer A'(see composition given hereinafter) and rinsing at the indicated temperature of 35°C for a total processing time of 45 seconds.
• the “inventive processing” (inv.) was run in a processing cycle according to the processing method of the present invention, wherein the "inventive developer” ( IDA ) was used, differing from the “comparative” in that compound (II) was added in an amount of 50 mg ( IDA ) per 100 ml of developer. The same fixer A' was used.
• the density as a function of the light dose was measured and therefrom were determined the following parameters:
• Said compound (II) also has an influence on fog (suppressing fog and speed when added in the said amount of 50 mg/l as hereinbefore). Improved image tone seems to be more pronounced if silver iodide has been added at the grain surface of the silver chloroiodide grains in form of very fine Lippmann emulsion grains (smaller than 50 nm) having silver iodide in an amount of 100 mole % based on silver.

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