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
  • 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
  • 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
  • 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 a method of processing an exposed photographic silver halide material coated from hydrophilic layers comprising thin tabular emulsion crystals rich in chloride.
• silver deposit can be attributed to the presence in conventional developers of silver halide complexing agents like, e.g., sulphite and thiocyanate ions, which make silver ions still more soluble.
• silver halide complexing agents like, e.g., sulphite and thiocyanate ions, which make silver ions still more soluble.
• the complex ions formed are effectively reduced to metallic silver nuclei. Growth of said nearly invisible fine nuclei leads to the formation of said silver deposit.
• the silver halide emulsions utilized in high-contrast room-light-handleable elements are slow speed emulsions.
• the desired slow speed is achieved by the use of small grain sizes and by the doping of the silver halide grains with appropriate doping agents that control photographic speed.
• sparingly soluble and non-reducible silver salts as, e.g., 5,5'-bis-1,2,4-triazolin-3-thiones or derivatives of 1,3,4-thiadiazole-2-thiols as described, e.g. in BE-P 606,550 and GB-P 1,120,963, 2-mercapto-1,3,4-thiadiazoles described in US-P 3,212,892.
• emulsion layer may contain auxiliary coating agents such as saponin, sodium lauryl sulphate, dodecylphenol polyethylene oxide ether and hexadecyltrimethyl ammonium bromide.
• EP-Specification 0 223 883 a method has been described which comprises the treating of a silver halide photographic material with an aqueous alkaline liquid in the presence of (i) a developing agent, (ii) a heterocyclic mercapto compound including an aliphatic group of at least 3 carbon atoms and (iii) a surface active agent, characterised in that said surface active agent is an anionic alkylphenoxy polyalkyleneoxy phosphate ester surfactant.
• EP-A 0 620 484 reduction of the so-called "pi-line" defect, especially for processed materials for non-destructive testing purposes, has been described.
• Such materials should comprise at least one vinyl sulphone compound as a hardening agent and at least one polyoxyalkylene compound as a surfactant in at least one of its hydrophilic layers.
• a processing method comprising a developing step wherein the developer comprises as a surfactant at least one anionic alkylphenoxy and/or alkoxy polyalkyleneoxy phosphate ester, sulphate ester, alkyl carboxylic, sulphonic or phosphonic acid and/or a salt thereof a remarkable improvement has been obtained.
• a similar result has been obtained as disclosed in EP-A's 0 621 506 and 0 620 483.
• silver chloride is the more soluble silver halide salt, and therefor especially suitable in rapid processing applications, the problem of sludge formation by processing light-sensitive silver halide materials comprising such grains is more pronounced.
• the said thin tabular grains with their large surfaces are desired, e.g., as they allow the adsorption of high amounts of spectral sensitiser(s), leading to strong absorption of incident radiation. As a result a high sensitivity can be expected. Furthermore, as scattering of incident radiation throughout parallel twin planes is reduced, sharpness of the processed material is expected to be better. And last but not least the covering power of thin tabular grains comprised in coated layers of forehardened materials is not reduced in the processing of the said materials.
• an exposed silver halide photographic material comprising at least one coated hydrophilic silver halide emulsion layer comprising tabular grains rich in chlqride, bounded by [100] or [111] major faces, characterised by the steps of developing, followed by fixing, rinsing and drying the said material, wherein developing proceeds in a developer, comprising hydroquinone in an amount from 0 to 30 g per litre, an auxiliary developer, as silver halide complexing agents alkali metal sulphite salts in an amount from 1 to 50 g per litre, at least 1 g of a compound corresponding to the formula (I), a precursor thereof, a derivative thereof and/or a metal salt thereof wherein
• the said heterocyclic aromatic ring is a pyridine, a pyrimidine, an imidazol, a benzimidazol, a thiazol, a benzothiazol or a derivative thereof.
• at least R or one of the ring substituents represents at least 3 oxyethylene units.
• anions are required to neutralise the total electrical charge of these N-heterocyclic aromatic onium compounds.
• Preferred anions are sulphonate anions, like methylsulphonate and the like, toluyl sulphonate, carbamate, benzoate, glutamate, perchlorate, sulphate etc.
• the said anions are p-toluyl sulphonate.
• This formula corresponds with (iso)ascorbic acid, which is, together with 1-ascorbic acid, a preferred form of formula (I).
• the compound(s) according to formula (I) preferably is(are) present in the developer solution in an amount comprised between 1 g and 50 g per litre.
• reducing precursor compounds have, e.g., been described in WO's 94/3834 and 94/16362, which are both incorporated herein by reference.
• ascorbic acid is not merely used in the developer as an antioxidant as, e.g., described in WO 93/12463, in JP-A's 4428673 and 55149936, in GB 1,266,533 and in US-P's 3,865,591; 4,756,997 and 4,839,259 and in the literature as, e.g., J. Am. Chem. Soc., 60 (1938), p. 99 and p. 2084; 61 (1939), p. 442; 64 (1942), p. 1561, 65 (1943), p. 1489; 66 (1944), p. 700 and 104 (1982), p. 6273.
• the developer liquid may contain any combination of hydroquinone as a developing agent and auxiliary developer known for use in the development of exposed photographic silver halide, but the absence of hydroquinone is not excluded.
• auxiliary developing compounds may be utilized p-methylaminophenol, a 1-phenyl-3-pyrazolidine-1-one, p-phenylenediamine derivatives and the like. Amounts of hydroquinone are lower than 30 g per litre and more preferably lower than 20 g per litre.
• auxiliary developer Preferred amounts of auxiliary developer are present in a concentration range of up to 10 mmoles per litre of developer, said auxiliary developer being preferably a 1-phenyl-3-pyrazolidine-1-one compound, well-known as a "phenidone" compound.
• the developer further comprises silver complexing compound(s) such as alkali metal sulphites, bisulphites, metasulphites or metabisulphites, but preferably it contains an alkali metal sulphite salt, and more preferably sodium sulphite, in an amount of less than 50, and more preferably in an amount of less than 40 g per litre of developer.
• the developer solution can be alkalised with alkaline metal hydroxides, phosphates, borates, carbonates and the like.
• the developer liquid or activator liquid may contain still other ingredients, e.g., metal complexing agents, an anti-fogging agent, e.g., alkali metal bromide, in amounts ranging from 0.01 to 0.4 moles per litre, a benzotriazole, a benzothiazole, a tetrazole, e.g., up to 0.06 g per liter of 1-phenyl-5-mercapto-tetrazole, solvents improving the dissolution of the developing agents, e.g., alcohols, polyethylene glycols and esters thereof and alkanolamines, surface active agents, development retarding or activating compounds, e.g., quaternary ammonium salts, and gelatin hardening agents, e.g., dialdehyde compounds such as glutardialdehyde.
• polyethylene glycols having a low molecular weight in the range from 200 to 400 is preferred.
• values of the pH of the developer solution are preferably in the range from 9.0 to 12.5, more preferably in the range of 9.5 to 12.0 and still more preferably from 9.5 to 11.0. Even at those relatively "lower” pH values, if compared with more frequently used alkaline pH values of 12.0 and more, the required sensitometry is still attained, which means that a developer having a composition according to this invention offers enough reactivity to get the required sensitivity for a material that is processed therein within a reasonable processing time.
• the present invention thus includes a method for developing, by means of the developer according to this invention, of any type of photographic silver halide emulsion layer material, e.g., a graphic art, micrographic and an X-ray recording material, after image-wise exposing the said material by means of suitable radiation sources, adapted to each application in particular, and immersing it into the developer the composition of which has been described hereinbefore, with the proviso that the said material comprises at least one coated hydrophilic silver halide emulsion layer containing tabular silver halide grains rich in chloride.
• any type of photographic silver halide emulsion layer material e.g., a graphic art, micrographic and an X-ray recording material
• tabular silver halide grains rich in chloride, coated in hydrophilic layers of materials to be processed according to the method of this invention are bounded by [100] or [111] major faces.
• Tabular silver halide grains rich in chloride, bounded by [100] major faces and/or the preparation method thereof and/or materials in which said grains are incorporated have been described in, e.g., US-P's 5,264,337; 5,275,930; 5,292,632; 5,310,635; 5,314,798; 5,320,938; in the published EP-A's 0 534 395, 0 569 971, 0 584 815, 0 584 644, 0 617 325, 0 618 492 and 0 653 669, which is incorporated herein by reference.
• 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 been described in, e.g., US-P's 4,399,215; 4,400,463; 4,804,621; 5,061,617; 5,176,991; 5,176,992; 5,178,997; 5,178,998; 5,183,732; 5,185,239; 5,217,858; 5,221,602; 5,264,337; 5,272,052; 5,275,930; 5,286,621; 5,292,632; 5,298,385; 5,298,387; 5,298,388; 5,310,644; 5,320,938; 5,356,764; in the published EP-A's 0 481 133, 0 503 700, 0 532 801, 0 533 189, 0 647 877 and 0 678 772, which are incorporated herein by reference.
• the said tabular silver halide grains rich in chloride comprised in silver halide photographic materials to be processed according to the method of this invention preferably have an average thickness over the total crystal population of less than 0.5 ⁇ m, more preferably of less than 0.3 ⁇ m and still more preferably from 0.05 ⁇ m to 0.2 ⁇ m.
• an average aspect ratio defined as the ratio, calculated from the measurements of the equivalent diameter of a circle having the same surface area as the different individual grains, and its thickness, is preferably higher than 2:1; more preferably higher than 5:1 and still more preferably higher than 8:1, up to a ratio of about 100:1.
• Silver halide emulsions incorporated in at least one photosensitive layer in a suitable layer arrangement of the said materials processed by the method according to this invention are composed of preferred amounts of chloride, in mole %, of at least 50 %, more preferably at least 70 % and even more preferably at least 90 %, up to 100 %.
• Other halides present are bromide, in amounts from 0 up to 50 mole% and iodide in amounts from 0 up to 2 mole %.
• processing steps according to the present invention are advantageously applied in automatic processing equipment, preferably containing conveyer rollers as described, e.g., in US-P 3,025,779 and 3,545,971, in a time from 5 to 45 seconds at a temperature from 25 to 40°C.
• concentration of the derivatives corresponding to formula (I) and the pH are maintained at a constant value by replenishment with unoxidised developing agent, thereby adding a concentrated alkali hydroxide solution under controlled constant redox potential as has been illustrated in EP-A 0 552 511, which is incorporated herein by reference.
• This invention allows the use of low regeneration amounts for the developer used in the developing step according to the method of this invention, having a composition wherein minimum regeneration amounts of developing solution from 50 to 250 ml/m 2 of photographic material are possible and even more preferred from 50 to 150 ml/m 2 .
• Photosensitive silver halide emulsion layer(s) present in silver halide photographic materials processed by the method according to this invention may be of any type or composition used in silver halide photography, provided that at least one layer comprises at least one thin tabular silver halide emulsion rich in chloride bounded by [100] or [111] major faces and may be present in whatever a layer arrangement used in the art of photography.
• So black-and-white silver halide films intended to be used for contact exposures form an important class of photographic films. These so-called contact films are used for proper reproduction on one hand and for dry dot-etching on the other hand. In modern pre-press graphic arts these contact materials are designed to be usable for several minutes under roomlight conditions, meaning light containing substantially no UV-light.
• the method for determining the silver deposit makes use of the GEVASET 437N automatic processor, trademarked product from Agfa-Gevaert, which has a tank volume of only 1 litre per tank.
• the temperature and the processing velocity are made variable. As there is only one roller before entering and after leaving every bath, there is no danger to disturb the outlook of the film surface.
• the agitation of the developer is reduced to a negligable extent and the developer tank is followed by two fixation tanks and one rinsing tank, both having a content of 1 litre.
• the film is immersed into the developer tank for 46 seconds at a temperature of 30°C. The developer is not regenerated.
• the washing procedure was performed in a discontinous way, adding 3 1 of demineralised water, containing up to 8 mmole of sodium chloride pro liter, until pAg was reaching a value of about 7.3.
• the emulsion was peptised and was chemically ripened to an optimal fog-sensitivity relationship at 52°C, pAg having a value of about 6.95.
• Chemical ripening agents besides gold (in an amount of 0.019 mmole) and sulphur (tetramethyl thiodithiocarboxylic acid diamide in an amount of 0.061 mmole), were toluene thiosulphonic acid and iodide ions, both being predigestion agents in amounts of 0.02 and 8.6 mmoles respectively.
• a photographic material was prepared having on a subbed polyester base a gelatinous silver halide emulsion of which the silver halide consists for 99.7 % of silver chloride having an average grain size of 0.55 ⁇ m the preparation of which has been described above.
• said emulsion was spectrally sensitised with two spectral sensitisers, corresponding to the following formulae (see compound III and compound IV):
• spectral sensitisers were added consecutively in an amount of 0.1 mmole and 0.3 mmole per mole of silver nitrate respectively.
• the emulsion was further stabilised with 0.22 mmole of compound (V) and 0.68 mmole of compound (VI) per mole of silver nitrate.
• a coated amount of silver expressed as the equivalent amount of silver nitrate of 3.8 g per square meter and a gelatin to silver chloride (expressed in equivalent amount of silver nitrate) ratio of 0.35 was provided with a gelatin covering layer (anti-stress layer) of 1.30 g of gelatin per m2 on both sides of a polyethylene terephtalate film support having a thickness of 175 ⁇ m.
• a nucleation step was performed by introducing solution A and solution B1 simultaneously in dispersion medium C both at a flow rate of 30 ml/min during 30 seconds. After a physical ripening time of 15 min during which the temperature was raised to 70 °C and 97.5 g of gelatin and 1500 ml of water were added and the mixture was stirred for an additional 5 minutes.
• a growth step was performed by introducing by a double jet during 66 minutes solution A starting at a flow rate of 7.5 ml/min and linearly increasing the flow rate to an end value of 37.5 ml/min, and solution B1 at an increasing flow rate as to maintain a constant mV-value, measured by a silver electrode versus a saturated calomel electrode (S.C.E.), of +92 mV.
• the pH value of the said dispersing medium was adjusted to a value of 3.0 with sulphuric acid, and after the addition of 55.5 ml of polystyrene sulphonic acid the obtained flocculate was decanted and washed three times with an amount of 6 1 of demineralised water in order to remove the soluble salts present.
• Tabular silver chloride crystals having [111] major phase and a sphere equivalent average diameter of 1.20 ⁇ m were obtained, with an average thickness of 0.37 ⁇ m and thus an average aspect ratio of 3.3.
• a photographic material was further prepared having on a subbed polyester base a gelatinous silver halide emulsion of which the silver halide consists for 100 % of tabular silver chloride, the preparation and emulsion crystal characteristics have been given hereinbefore.
• a coated amount of silver expressed as the equivalent amount of silver nitrate of 3.8 g per square meter and a gelatin to silver chloride (expressed in equivalent amount of silver nitrate) ratio of 0.35 was provided with a gelatin covering layer (anti-stress layer) of 1.30 g of gelatin per m2 on both sides of a polyethylene terephtalate film support having a thickness of 175 ⁇ m.
• the temperature of A and B1 was established at 40°C.
• a nucleation step was performed by introducing solution A and solution B1 simultaneously in dispersion medium C both at a flow rate of 60 ml/min during 30 seconds. After a physical ripening time of 20 min during which the temperature was raised to 70 °C. Then a growth step was performed by introducing by a double jet during 64 minutes and 40 seconds solution A starting at a flow rate of 5 ml/min and linearly increasing the flow rate to an end value of 25 ml/min, and solution B1 at an increasing flow rate as to maintain a constant mV-value, measured by a silver electrode versus a saturated calomel electrode (S.C.E.), of +135 mV.
• S.C.E. saturated calomel electrode
• the pH value of the said dispersing medium was adjusted to a value of 3.0 with sulphuric acid, and after the addition of 37 ml of polystyrene sulphonic acid the obtained flocculate was decanted and washed three times with an amount of 6 l of demineralised water in order to remove the soluble salts present.
• the thus obtained silver chloride tabular emulsion showed a [100]-major faces.
• the average circle equivalent diameter d EM , average thickness d, average aspect ratio AR were obtained from electron microscopic photographs. Respective values of 1.58 ⁇ m; 0.42 ⁇ m and 3.8:1 were measured.
• a coated amount of silver expressed as the equivalent amount of silver nitrate of 3.8 g per square meter and a gelatin to silver chloride (expressed in equivalent amount of silver nitrate) ratio of 0.35 was provided with a gelatin covering layer (anti-stress layer) of 1.30 g of gelatin per m2 on both sides of a polyethylene terephtalate film support having a thickness of 175 ⁇ m.
• compositions of the developers Type of dev. DEV1 DEV2 DEV3 DEV4 DEV5 pH ready-for-use 10.5 10.0 10.0 10.0 10.0 Hydroquinone (mole/l) 0.27 0.18 0.18 0.18 - 1-phenyl-4-methyl-3-pyrazolidine-1-one (mmole/l) 4.6 4.6 4.6 4.6 4.6 Br - (mmole/l) 33.6 21 21 21 21 SO 3 -- (mole/l) 0.57 0.19 0.19 0.19 0.19 0.19 CO 3-- (mole/l) 0.22 0.44 0.44 0.44 0.44 0.44 0.44 0.44 0.44 0.44 0.44 Polyglycol (ml/l) (M.W. ca.
• Table 1 amounts, in mg/l, of deposited silver determined by means of the method described hereinbefore in Exhausted Developer (ED), after 24 hours (in mg/l)(ED24), after 4 weeks present in the filtrate (mg/l)(ED4W) as well as the Total Deposit (mg/l) (TD) and the rest amount of Deposited Silver in the Filtrate (DSF) are given for material A (regular cubic AgCl) and for materials B and C (tabular AgCl crystals with [111] and [100] major faces respectively), in the developers DEV1, DEV2 and DEV5.
• Samples of the coating materials A, B and C were exposed according to the ANSI procedure 1043. After processing in the developers mentioned in Table 2 for developing times of 11 seconds at 33°C, the sensitometric properties of each material was measured.
• sensitometric results are matching those obtained with DEV1 and material A (as described in EP-A No. 94203085, filed October 24, 1994) containing cubic AgCl emulsion crystals as has been illustrated in Table 2 for [111]-tabular AgCl crystals and for [100]-tabular AgCl crystals.
• the same sensitometric values can be obtained by using a developer with ascorbic acid instead of hydroquinone.
• high covering power obtained with cubic crystals rich in chloride, described in the non-published EP-A is confirmed.
• the covering power obtained for cubic crystals rich in chloride is always better than for [100] and [111] tabular grains rich in chloride, but the tendency is present that there is a relative increase in covering power, especially for the tabular [100] grains versus the cubic grains, if developing occurs in developers used in the method according to this invention.

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Citations (8)

• 1996
  • 1996-01-19 EP EP96200135A patent/EP0731382A1/fr not_active Withdrawn

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