EP0269740B1 - Verfahren zur behandlung eines schnellentwickelnden silberhalid-farbphotographischen materials - Google Patents

Verfahren zur behandlung eines schnellentwickelnden silberhalid-farbphotographischen materials Download PDF

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Publication number
EP0269740B1
EP0269740B1 EP19870902147 EP87902147A EP0269740B1 EP 0269740 B1 EP0269740 B1 EP 0269740B1 EP 19870902147 EP19870902147 EP 19870902147 EP 87902147 A EP87902147 A EP 87902147A EP 0269740 B1 EP0269740 B1 EP 0269740B1
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silver halide
colour
silver
processing
forth
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French (fr)
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EP0269740A1 (de
EP0269740A4 (de
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Kazuhiro Kobayashi
Shigeharu Koboshi
Masao Ishikawa
Masayuki Kurematsu
Yoko Matsushima
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Konica Minolta Inc
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Konica Minolta Inc
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    • 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
    • G03C7/00—Multicolour photographic processes or agents therefor; Regeneration of such processing agents; Photosensitive materials for multicolour processes
    • G03C7/30—Colour processes using colour-coupling substances; Materials therefor; Preparing or processing such materials
    • G03C7/407—Development processes or agents therefor
    • G03C7/413—Developers

Definitions

  • This invention relates to a method of processing a silver halide colour photographic light-sensitive material and, more particularly, to a method of processing a silver halide colour photographic light-sensitive material, in which a color developer can be excellent in the storage of long standing and a maximum colour density can satisfactorily be obtained and, further, a rapid development can be made.
  • silver halide colour photographic light-sensitive materials have been subjected to running treatments with an automatic processing apparatus installed at each photo-finishing laboratory.
  • an automatic processing apparatus installed at each photo-finishing laboratory.
  • it has been requested, as one of service improvements to users, to process users' photographic products and return the finished ones to them, within not only the same day when the photo-finishing orders were received and, but also several hours after receiving orders, recently, so that a rapid processing technolgy has been urgently demanded.
  • This invention relates to the above-mentioned technologies [1] and [3] out of those [1], [2] and [3].
  • the so-called light-sensitive materials for colour paper use generally contain silver chlorobromide as the silver halide composition thereof.
  • the silver bromide content mentioned in the above technology (1) of [1] is reduced, that is, the silver chloride content is increased, a development may be accelerated by themselves and the bromide ion concentration of a developer may also be reduced when a running treatment is kept on successively, so that the light-sensitive materials may have the characteristics that a development acceleration may readily be made and a low quantity replenishment of developer may also be possible.
  • DE-A-3412712 describes colour developers containing hydroxylamine or N-alkyl hydroxylamine as preservatives. These can be used with silver halide emulsions of various compositions.
  • the Examples of DE-A-3412712 describe the development of a material having silver chloro-bromide emulsion layers with silver bromide contents of, respectively, 80 mol % (blue-sensitive), 70 mol % (green-sensitive) and 50 mol % (red-sensitive).
  • the present inventors have studied on the methods of processing silver halide colour photographic light-sensitive materials having the above-mentioned silver halide content reduced suitably for paper use, and resultingly found that, while these light-sensitive materials may be processed more rapidly than the conventional type silver halide colour photographic light-sensitive materials using silver chlorobromide having a high silver bromide content (such as a 90 mol% silver bromide content), there is a problem that a maximum colour density, that is one of the most essential characteristics of light-sensitive materials, is lowered.
  • colour developers each contain an aromatic primary amine type colour developing agent such as paraphenylenediamine and so forth, hydroxylamine and sulfites used as a preservative for preventing the air-oxidation and so forth of the colour developing agent, benzyl alcohol for accelerating colour developments, other additives, and so forth.
  • aromatic primary amine type colour developing agent such as paraphenylenediamine and so forth
  • hydroxylamine and sulfites used as a preservative for preventing the air-oxidation and so forth of the colour developing agent
  • benzyl alcohol for accelerating colour developments, other additives, and so forth.
  • the inventors have also studied on the system using only a sulfite not any hydroxylamine as the preservative. Resultingly, the standing stability of the colour developer tested was maintained to some extent, however, an dye image was fogged seriously when processed with a long-stored colour developer.
  • a fog production may colosely relate to the deterioration of a colour developer used.
  • Fogs are particularly liable to be produced when raising a pH of a colour developer, a temperature for colour development process and a concentration of the colour developing agent contained in a colour developer. or when prolonging a storage of long standing of a colour developer. Therefore, the main cause of fog production is supposed to be the decomposed or oxidized products produced by partly decomposing or oxidizing the colour developing agent of the colour developer.
  • the above-mentioned decomposed or oxidized products of color developing agents include, for example, a semiquinone or quinoneimine that is an oxidized product of a colour developing agent, a paraaminophenol produced by receiving a deamination reaction or a quinonemonoimine that is the oxidized product thereof, the sulfurous acid addition products of quinonediimine or the quinonmonoimine or the oxidized products thereof, and so forth.
  • Some of these products make a coupling reaction with couplers upon oxidizing silver halide present in the unexposed areas of a light-sensitive material or make a coupling reaction directly with couplers so as to form a dye in the regions of the unexposed areas of a colour photographic light-sensitive material, where any dye ought not to be formed, and fogs are produced in white regions.
  • a light-sensitive material comprising three emulsion layers, i.e., blue-, green- and red-sensitive layers
  • the fog production on each unexposed layer will appear in a mixed colour, so that these fogs and the mixed colour will seriously deteriorate a photographic image quality.
  • the present inventors have studied on the methods of processing silver halide colour photographic light-sensitive materials capable of maintaining the preservability of a colour developer, inhibiting fogs and, particularly, preventing a maximum colour density from lowering and, further, suitable for a rapid processing. Resultingly, the inventors have found the fact that the above-mentioned problems can be solved by processing the silver halide colour photographic light-sensitive materials each having a specific silver halide composition, in the presence of a specific preservative, so that this invention has finally been achieved.
  • an object of this invention to provide a method of processing a silver halide colour photographic light-sensitive material, in which the photographic characteristics cannot be deteriorated by fog and so forth, a colour developer is excellent in long standing stability and, particularly, a maximum colour density of a dye image obtained is also excellent and, further, a rapid processing can be performed.
  • the above-mentioned object of the invention can be achieved in a method of processing a silver halide colour photographic light-sensitive material having a plurality of silver halide emulsion layers, comprising the steps of exposing imagewise to light and then processing in at least a colour developing step, wherein
  • the compounds represented by Formula [I] (hereinafter called the compounds of the invention) are used as the preservatives.
  • R1 and R2 each represent an alkyl or alkoxy group having 1 to 3 carbon atoms.
  • the alkyl groups each having 1 to 3 carbon atoms represented by R1 and R2 include those each having substituents including, for example, a hydroxyl group, an amino group, an alkoxy group, a sulfonic acid group, a carboxylic acid group, a halogen atom (such as a chlorine atom, a fluorine atom, a bromine atom and so forth), and an alkenyl group (such as an allyl group and so forth).
  • the typical examples of the alkyl groups each represented by R1 and R2 include a methyl group, an ethyl group, a hydroxyethyl group, an i-propyl group, a n-propyl group and so forth.
  • the alkoxy groups each represented by R1 and R2 include, for example, a methoxy group, an ethoxy group and so forth.
  • R1 and R2 are allowed to couple to each other to complete such a ring as the heterocyclic rings of piperidine or morpholine,
  • R1 and R2 each represent alkyl groups at least one of R1 and R2 has a substituent.
  • the above-exemplified compounds of the invention are usually used in the form of salts such as a chloride, a sulfate, a p-toluene sulfate, an oxalate, a phosphate, an acetate and so forth.
  • the concentration of the compounds of the invention used in a colour developer is of the same degree as that of hydroxylamine usually used as a preservative.
  • the concentration thereof is, preferably, from 0.5 g per liter to 50 g per liter and, more preferably, from 1 g per liter to 20 g per liter.
  • the colour developing agents used in the colour developers of the invention it is allowed to use any of the aromatic primary amine type colour developing agent which are usually used.
  • such colour developing agents are preferably a paraphenylenediamine type colour developing agent having at least one water-soluble group (i.e., a hydrophilic group) on the amino group or the benzene nucleus thereof.
  • the above-mentioned water-soluble groups substituted onto the amino group or the benzene nucleus include, preferably, the following groups: -(CH2) n -CH2OH, -(CH2) m -NHSO2-(CH2) n -CH3, -(CH2) m O-(CH2) n -CH3, -(CH2CH2O) n C m H 2m+1 (in which m and n each are an integer of not less than 0), and a -COOH group, a -SO3H group and so forth may be preferably given as the examples thereof.
  • the most preferable ones are (CH2) m NHSO2 (CH2) n CH3 (in which m and n each are an integer of from 0 to 5).
  • the above-mentioned colour developing agents are usually used within the range of, preferably, from 1 g to 100 g per liter of a colour developer used and, more preferably, from 3 g to 50 g.
  • ions of a bromide may be used in the form of potassium bromide or the like, as an antifogging agent.
  • concentration of the bromide ions is the lower, the better, because a developing time may also shortened.
  • a fog production is increased, because the antifogging effect is decreased.
  • a silver halide colour photographic light-sensitive material having at least one silver halide emulsion layer whose silver chloride content is increased, no fog is increased even if the bromide ion concentration is lowered, that is preferable.
  • the bromide ion concentration is preferably not more than 1.3x10 ⁇ 2 mol per liter, more preferably not more than 8.4x10 ⁇ 3 mol per liter and, especially not more than 3.0x10 ⁇ 3.
  • the colour developers used in the invention are allowed to contain arbitrarily various components usually added thereto, including, for example, alkalizing agents such as sodium hydroxide, sodium carbonate and so forth, an alkali-metal sulfite, an alkali-metal hydrogensulfite, an alkali-metal thiocyanate, an alkali-metal halide, a polystyrene sulfonic acid, a water softener, benzyl alcohol, ethylene glycol, diethylene glycol, triethanolamine, a thickening agent, a development accelerator, and so forth.
  • alkalizing agents such as sodium hydroxide, sodium carbonate and so forth
  • an alkali-metal sulfite such as sodium hydroxide, sodium carbonate and so forth
  • an alkali-metal sulfite such as sodium hydroxide, sodium carbonate and so forth
  • an alkali-metal sulfite such as sodium hydroxide, sodium carbonate and so forth
  • the other additives which may be added into the above-mentioned colour developers include, for example, firstly, the compounds for rapid processing liquids such as alkali iodides, nitrobenzoimidazole, mercaptobenzoimidazole, 5-methyl-benzotriazole, 1-phenyl-5-mercaptotetraazole and so forth and, secondly, antistaining agents, sludge preventing agents, interlayer effect accelerators, chelating agents and so forth.
  • the chelating agents mainly used in developers include, for example, an aminopolycarboxylate and an organic phosphonate.
  • the badly soluble organic solvents particularly represented by benzyl alcohol are liable to produce tar when a color developer is used for a long period of time and, especially, in a low replenishment type running process and such tar adheres to a light-sensitive paper being processed.
  • a fatal trouble may sometimes be caused to seriously damage the commercial value of the paper.
  • the badly soluble organic solvents have a poor solubility to water, therefore, there are not only the trouble of preparing a colour developer itself with a stirrer, but also a limitation to the development acceleration effect even if the stirrer is used due to the poor solubility of the solvent.
  • the processing method of the invention may also be applied to a system containing benzyl alcohol, however, from the viewpoint of a rapid processing, one of the preferable embodiments is a system not containing any benzyl alcohol.
  • the colour developers of the invention at a pH value of not lower than 9.90 and, usually, at a pH value of not higher than 13, because the upper limit of the pH values relates to the fog produced in a dye image. It is generally known that a rapid processing can be performed by making the pH value of a colour developer higher to some extent. However, when a processing is made with a long standing colour developer, a fog increase cannot be neglected. In the processing method of the invention, it wag found such an unexpected effect that, when the compounds of the invention were used as preservatives, there was none of the fog increase which has been liable to produce when making a pH value of a colour developer higher and has hereto fore been considered to cause the deterioration in the long standing stability of a colour developer. This fact indicates that a processing can be performed at a pH range more higher than the pH range heretofore in use and that the method of the invention is suitable for a rapid processing.
  • the processing temperature used therein is the higher, the more preferable, provided that it is within the range of from not lower than 30°C to not higher than 50°C, because a rapid processing can be made.
  • a processing should be made at a temperature of not too higher but from not lower than 33°C to not higher than 45°C.
  • any system can be applied thereto, provided that such system uses a colour developer containing the aforementioned compounds of the invention.
  • These systems include, for example, firstly. a monobath processing system and, secondly, various other systems such as a spray system of spraying a processing liquid, a web system of bringing a light-sensitive material into contact with a carrrying member impregnated with a processing liquid, or a developing system using a viscous processing liquid.
  • a series of the processing steps substantially comprises the three steps, i.e., a colour developing step, a bleach-fixing step and a washing or the alternative stabilizing step.
  • the bleach-fixing step may be separated into a bleaching step and a fixing step or may be carried out in a bleach-fixing bath in which both of the bleaching and fixing are carried out in a single bath.
  • Bleaching agents which may be used in the bleach-fixer used in the invention are the metal complex salts of organic acids.
  • Such complex salts include an aminopolycarboxylic acid, or those coordinated the metal ions of cobalt, copper or the like with such an organic acid as oxalic acid, citric acid or the like.
  • the most preferable example of the organic acids used to produce the metal complex salts of such an organic acid as mentioned above is a polycarboxylic acid.
  • These poly- carboxylic acids or aminopolycarboxylic acids are allowed to be the alkali-metal salts, ammonium salts or water-soluble amine salts thereof.
  • the typical examples thereof may be given as follows.
  • bleaching agents are used in an amount of from 5 to 450 g per liter and, more preferably, from 20 to 250 g per liter.
  • a bleach-fixer contains, besides such a bleaching agent as mentioned above, a silver halide fixing agent and, if required, a preservative that is a liquid containing a sulfite.
  • a bleach-fixer comprising an iron (III) ethylenediaminetetraacetate bleaching agent and a small amount of such a halide as ammonium bromide that is other than the above-mentioned silver halide fixing agent; a bleach-fixer comprising, on the contrary to the above, a large amount of such a halide as ammonium bromide; and a peculiar bleach-fixer comprising the combination of an iron (III) ethylenediaminetetraacetate bleaching agent and a large amount of such a halide as ammonium bromide.
  • ammonium bromide the above-mentioned halides used for this purpose inclide, hydrochloric acid, hydrobromic acid, lithium bromide, sodium bromide, potassium bromide, sodium iodide, potassium iodide, ammonium iodide and so forth.
  • the above-mentioned silver halide fixing agents contained in the bleach-fixers include the compounds capable of producing a water-soluble complex salt upon reaction with silver halide such as those used in an ordinary fixing treatment.
  • Such compounds are typically represented by thiosulfates such as potassium thiosulfate, sodium thiosulfate and ammonium thiosulfate; thiocyanates such as potassium thiocyanate, sodium thiocyanate and ammonium thiocyanate; thiourea; thioether; and so forth.
  • These fixing agents are used in an amount within the range where they may be dissolved, that is, not less than 5 g per liter and generally from 70 g to 250 g per liter.
  • the bleach-fixers are also allowed to contain various types of pH buffers independently or in combination, such as boric acid, borax, sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, sodium bicarbonate, potassium bicarbonate, acetic acid, sodium acetate, ammonium hydroxide and so forth. Further, they may also contain various types of optical brightening agents, defoaming agents or surface active agents.
  • suitable preservatives such as the bisulfurous acid addition products of hydroxylamine, hydrazine or aldehyde compounds, and so forth; organic chelating agents such as aminopolycarboxylic acid, and so forth; stabilizers such as nitro alcohol, nitrates, and so forth; organic solvents such as methanol, dimethylsulfoxide, dimethylsulfoxide, and so forth; and the like.
  • the bleach-fixers used in the invention are allowed to contain various bleach accelerators such as those described in Japanese Patent O.P.I. Publication No. 280-1971; Japanese Patent Examined Publication Nos. 8506-1970 and 556-1971; Belgian Patent No. 770,910; Japanese Patent Examined Publication Nos. 8836-1970 and 9854-1978; Japanese Patent O.P.I. Publication Nos. 71634-1979 and 42349-1974; and so forth.
  • the bleach-fixers are used at a pH value of not lower than 4.0 and, generally, within the range of from not lower than pH 5.0 to not higher than pH 9.5.
  • the processing temperature is not higher than 80°C that is 3°C or more lower than the temperature of a processing liquid used in a colour developing tank and preferably 5°C or more lower than and, further desirably not higher than 55°C so as to inhibit evaporation or the like.
  • the above-mentioned colour developing step carried out with a colour developer containing the compounds of the invention and the above-mentioned bleach-fixing step are followed by a washing or a stabilizing step substituting for the washing step.
  • the stabilizing step applicable to the invention which substitutes for the washing step, will be described below.
  • the pH value thereof is within the range of, preferably, from 5.5 to 10.0 and, more preferably, from pH 6.3 to 9.5 and, particularly, from pH 7.0 to 9.0.
  • any generally known alkalizers or acidifyers may be used.
  • the processing temperature in the stabilizing step is within the range of from 15°C to 60°c and preferably from 20°C to 45°C. From the viewpoint of rapid processing, the processing time is the shorter, the better. However, it is usually from 20 seconds to 10 minutes and most preferably from 1 minute to 3 minutes. In the case of a multi-tank stabilizing step, it is preferred that the processing time may be more shorter in a preceding tank, while it may be more longer in a successive tank. It is particularly desirable that the processing time in each tank should be 20% to 50% longer than in the preceding tank, respectively.
  • none of any washing step is needed at all. It is, however, allowed to carry out a rinse, a surface cleaning and so on with a small amount of water for a very short time, if required.
  • a preferable method of supplying a stabilizer substituting for washing water to a stabilizing step applicable to the invention is to supply it to a successive bath and then to overflow from a preceding bath. It is the matter of course that a processing may also be made in a single tank.
  • the methods of adding the aforementioned compounds there are various methods including, for example, a method in which a concentrated liquid is added into a stabilizing tank, another method in which the aforementioned compounds and other additives are added into the stabilizer substituting for washing water to be supplied to a stabilizing tank so as to make a supply liquid to the replenisher for the stabilizer substituting for washing water. The addition thereof may be made in any methods.
  • a 'processing made with a stabilizer' means a stabilizing processing in which, after processing with a bleach-fixer, a stabilizing process is immediately carried out without any washing process substantially.
  • the processing liquid used in the above-mentioned stabilizing process is called a 'stabilizer substituting for washing water'.
  • the processing tank is called a 'stabilizing bath' or a 'stabilizing tank'.
  • the advantages of the invention may effectively be displayed when the stabilizing tank system is composed of one to five tanks and, at the very most, not more than nine tanks.
  • the compounds of the invention represented by the foregoing Formula [I] are used as a preservative to be contained in the aforementioned colour developers and the silver halides of at least one silver halide emulsion layer of the silver halide colour photographic light-sensitive material are substantially composed of silver chlorobromide grains each having a silver chloride content of not less than 20 mol%.
  • '--- be substantially composed of silver chloride' mentioned herein means that '--- be allowed to contain a small amount of silver iodide grains, besides the silver chlorobromide grains'.
  • silver chlorobromide grains not containing any silver iodide grain are most preferable.
  • At least one silver halide emulsion layer may be satisfactorily be used, provided that the silver chloride content thereof is not less than 20 mol%, preferably not less than 30 mol%, more preferably not less than 60 mol% and preferably in particular not less than 80 mol%.
  • the above-mentioned requirement may be satisfied either by everyone of a blue-sensitive layer, a green-sensitive layer and a red-sensitive layer or by only one layer.
  • the requirement is satisfied by at least one of the green-sensitive layer and the red-sensitive layer and it is more preferable that the above-mentioned requirement is staisfied by the blue-, green- and red-sensitive layers for the viewpoint of the rapid processing.
  • the crystals of silver halide grains which are substantially silver chlorobromide may be of the normal, twinned or the others.
  • the ratios of [100] plane to [111] plane may freely be selected.
  • the crystal structures of the silver halide grains may be uniform from the inside through the outside of each grain or may be layer-like from the inside through the outside both heterogeneous from each other, (that is called a core/shell type).
  • these silver halide grains may be of such a type that a latent image may be formed mainly on the surface of the grains or may be of such a type that a latent image may be formed inside the grains.
  • tabular silver halide grains may also be used. (See Japanese Patent O.P.I. Publication No. 113934-1983 and Japanese Patent Application No. 170070-1984)
  • the particularly preferable silver halide grains used in the invention include those of the substantially mono-disperse type and, further, the core/shell type grains.
  • Monodisper silver halide grains preferably used in the invention are those in which, when observing the emulsion thereof with an electron micrograph, each of the silver halide grains seems to be uniform in both shape and size and each of the grains has the ratio S/ r of the standard deviation S of the grain size distribution to the average grain size r of. preferably, not more than 0.22 and, more preferably, not more than 0.15.
  • Standard deviation S of a grain size distribution may be obtained by the following equation:
  • an average grain size r mentioned herein is an average diameter of the grains.
  • the silver halide grains used in the silver halide emulsions of the invention may be prepared in any one of an acid process, a neutral process and an ammonia process.
  • the silver halide grains relating to the invention are preferably prepared in such a manner as described above.
  • the composition containing the above-mentioned silver halide grains is called a silver halide emulsion in this specification.
  • the above-mentioned silver halide emulsions may be chemically sensitized with various sensitizers, for example, an active gelatin; sulfur sensitizers including allylthiocarbamide, thiourea, cystine and so forth; selenium sensitizers; reduction sensitizers including a stannous salt, thiourea dioxide, a polyamine and so forth; noble-metal sensitizers including gold sensitizers such as, typically, potassium aurithiocyanate, potassium chloroaurate, 2-aurothio-3-methylbenzothiazolium chloride and so forth, or sensitizers of the water-soluble salts of ruthenium, palladium, platinum, rhodium, iridium and so forth such as, typically, ammonium chloropalladate, potassium chloroplatinate, sodium chloropalladate (some kinds of which work as the sensitizers, anti-fogging agents or the like according to the amounts added).
  • sensitizers may be used independently or in suitable combination.
  • a combination use of a gold sensitizer and a sufur sensitizer, a gold sensitizer and a selenium sensitizer, or other combinations may be chemically sensitized after adding a sulfur-containing compound and are also allowed to contain at least one kind of nitrogen-containing heterocyclic compounds each having at least one kind of hydroxyzaindenes and mercapto groups, upon, before, during or after applying the chemical ripening.
  • the silver halides used in the invention may be optically sensitized by adding a suitable spectral sensitizing dye in an amount of from 5x10 ⁇ 8 to 3x10 ⁇ 3 mol to mol of the silver halides.
  • a suitable spectral sensitizing dye in an amount of from 5x10 ⁇ 8 to 3x10 ⁇ 3 mol to mol of the silver halides.
  • Various types of the spectral sensitizing dyes may be used independently or in combination. Those advantageously used in the invention include, for example, the following dyes.
  • the spectral sensitizing dyes used in blue-sensitive silver halide emulsions include those described in, for example, West German patent Nos. 929,080; U.S. Patent Nos. 2,231,658, 2,493,748, 2,503,776, 2,519,001, 2,912,329, 3,656,959, 3,672,897, 3,694,217, 4,025,349 and 4,046,572; British Patent No. 1,242,588; Japanese Patent Examined Publication Nos. 14030-1969 and 24844-1977; and the like.
  • the spectral sensitizing dyes used in green-sensitive silver halide emulsions typically include a cyanine dye, a merocyanine dye or a compositer cyanine dye such as those described in, for example, U.S. Patent Nos. 1,939,201, 2072,908, 2,739,149 and 2,945,763; British Patent No. 505,979; and the like.
  • the spectral sensitizing dyes used in red-sensitive silver halide emulsions typically include a cyanine dye, a merocyanine dye or a composite cyanine dye such as those described in, for example. U.S. Patent Nos.
  • the cyanine dyes, merocyanine dyes or the composite cyanine dyes such as those described in U.S. Patent Nos. 2,213,995, 2,493,748 and 2,519,001; West German Patent No. 929,080; and the like, may also be used advantageously in green- or red-sensitive silver halide emulsions.
  • spectral sensitizing dyes may be used independently or in combination.
  • the photographic light-sensitive materials of the invention may be optically sensitized to desired wavelength regions in a spectral sensitizing process using cyanine dyes or merocyanine dyes independently or in combination.
  • the particularly preferable spectral sensitizing processes include, for example, those described in Japanese Patent Examined Publication Nos. 4936-1968, 22884-1968, 18433-1970, 37443-1972, 28293-1973, 6209-1974 and 12375-1978; Japanese Patent O.P.I. Publication Nos. 23931-1977, 51932-1977, 80118-1979, 153926-1983, 116646-1984 and 116647-1984; and so forth, which are concerning the combination of benzimidazolocarbocyanine and benzooxazolocarbocyanine.
  • spectral sensitizing dyes are added into a silver halide emulsion relating to the invention, they are dissolved in advance in a hydrophilic organic solvents such as methyl alcohol, ethyl alcohol, acetone, dimethyl formamide, fluoroalcohol such as those described in Japanese Patent Examined Publication No. 40659-1975 and so forth, so as to be a dye solution and then used.
  • a hydrophilic organic solvents such as methyl alcohol, ethyl alcohol, acetone, dimethyl formamide, fluoroalcohol such as those described in Japanese Patent Examined Publication No. 40659-1975 and so forth, so as to be a dye solution and then used.
  • the spectral sensitizing dye solution may be added at any point of time, for example, at the beginning of, during or after chemically ripening a silver halide emulsion.
  • the solution may also be added in the step immediately before an emulsion coating step, if occasion demands.
  • a dye which is soluble by water or decolourizable by a colour developer may be added in the photographic component layers of the silver halide colour photographic light-sensitive materials of the invention.
  • the AI dyes include, for example, an oxanol dyestuff, a hemioxanol dyestuff, a merocyanine dyestuf, and an azo dyestuff.
  • these dyestuffs the oxanol dyestuffs, hemioxanol dyestuffs, merocyanine dyestuffs and so forth are useful.
  • the examples of the usable AI dyestuffs include those described in British Patent Nos.
  • AI dyestuffs are generally used in an amount of, preferably, from 2x10 ⁇ 3 to 5x10 ⁇ 1 mol per mol of silver contained in an emulsion layer and, more preferably, from 1x10 ⁇ 2 to 1x10 ⁇ 1 mol.
  • the silver halide emulsion layers relating to the invention may be able to contain couplers, respectively. Namely, the compounds capable of producing a dye upon reaction with the oxidized products of a colour developing agent.
  • couplers which may be used in the invention, various types of yellow couplers, magenta couplers and cyan couplers may be used without any special limitation. These couplers may be either of the so-called two-equivalent type or four-equivalent type. It is also allowed to combine these couplers with a diffusive dye-releasing type couplers and so forth.
  • the effective yellow couplers among the above-mentioned yellow couplers include, for example, an open-chained ketomethylene compound and, further, the so-called two-equivalent type couplers such as an active site-0-aryl-substituted coupler, an active site-0-acyl-substituted coupler, an active site-hydantoine compound-substituted coupler, an active site-0-urazol compound-substituted coupler and an active site-succinimide compound-substituted coupler, an active-site-fluorine-substituted coupler, an active site- chlorine or bromine-substituted coupler, an active site-0-sulfonyl-substituted coupler and so forth.
  • two-equivalent type couplers such as an active site-0-aryl-substituted coupler, an active site-0-acyl-substituted coupler, an active site-hydantoine compound-substi
  • magenta couplers used in the invention include, for example, the compounds of a pyrazolone type, a pyrazolotriazole type, a pyrazolinobenzimidazole type and an indazolone type. These magenta couplers may be not only four-equivalent type couplers, but also two-equivalent type couplers, similar to the case of the yellow couplers.
  • the typical examples of the magenta couplers include those described in U.S. Patent Nos.
  • the useful cyan couplers used in the invention include, for example, those of the phenol type, the naphthol type and so forth. These cyan couplers may be not only four-equivalent type couplers, but also two-equivalent type couplers, similar to the case of the yellow couplers.
  • the typical examples of the cyan couplers include those described in U.S. Patent Nos. 2,369,929, 2,434,272, 2,474,293, 2,521,908, 2,895,826, 3,034,892, 3,311,476, 3,458,315, 3,476,563, 3,583,971, 3,591,388, 3,767,411, 3,772,002, 3,933,494 and 4,004,929; West German Patent OLS No.
  • the couplers in combination, such as a non-diffusive DIR compound, a coloured magenta- or cyan-coupler, a polymer coupler, a diffusive DIR compounds and so forth.
  • the non-diffusive DIR compounds and the coloured magenta- or cyan-couplers may be referred to the description of Japanese Patent Application No. 193611-1984 applied by the present patent applicant, and the polymer couplers may be referred to the description of Japanese Patent O.P.I. Publication No. 72235-1986 applied by the present patent applicant.
  • Couplers which can be used in the invention into the photographic component layers of the invention may be the same as in the conventional methods.
  • the amounts of the couplers to be added are not limitative, but are preferably 1x10 ⁇ 3 to 5 mol per mol of the silver used and more preferably from 1x10 ⁇ 2 to 5x10 ⁇ 1 mol.
  • the silver halide colour photographic light-sensitive materials of the invention are also allowed to contain a variety of photographic additives in addition the the above-mentioned couplers.
  • these additves include an antifogging agent, a stabilizer, a UV absorbing agent, an anti-colour staining agent, an optical brightening agent, a colour image antifading agent, an antistatic agent, a hardening agent, a surface active agent, a plasticizing agent, a wetting agent and so forth each described in Research Disclosure, No. 17643.
  • the hydrophilic colloids used to prepare emulsions include any colloids, for example, gelatins, graft polymers of gelatin and other macromolecules, proteins such as albumin, casein and so forth, cellulose derivatives such as a hydroxyethylcellulose derivative, a carboxymethylcellulose and so forth, starch derivatives, synthetic hydrophilic macromolecules of a monomer or copolymer, such as polyvinyl alcohol, polyvinyl imidazole, polyacryl amide and so forth.
  • colloids for example, gelatins, graft polymers of gelatin and other macromolecules, proteins such as albumin, casein and so forth, cellulose derivatives such as a hydroxyethylcellulose derivative, a carboxymethylcellulose and so forth, starch derivatives, synthetic hydrophilic macromolecules of a monomer or copolymer, such as polyvinyl alcohol, polyvinyl imidazole, polyacryl amide and so forth.
  • the supports of the silver halide colour photographic light-sensitive materials of the invention there may be given as the examples, a baryta paper, a polyethylene-coated paper, a synthetic polypropylene paper, a transparent support provided together with a reflection layer or using together with a reflector member including, for example, glass plates, polyester films such as those of cellulose acetate, cellulose nitrate or polyethyleneterephthalate, polyamide films, polycarbonate films, polystyrene films and so forth.
  • othe ordinary transparent supports may also be used. These supports are suitably selected to use according to the purposes of light-sensitive materials.
  • a variety of coating methods such as a dip-coating method, an air-doctor coating method, a curtain coating method, a hopper coating method and so forth may be applied. Itis also allowed to apply a simultaneous multilayer coating method for coating two or more layers at the same time, such as the methods described in U.S. Patent Nos. 2,761,791 and 2,941,898.
  • any positioning arrangement of each emulsion layer may be freely determined when coating the layers.
  • a blue-sensitive silver halide emulsion layer, a green-sensitive silver halide emulsion layer and a red-sensitive silver halide emulsion layer in order from a support side.
  • Each of these light-sensitive silver halide emulsion layers is allowed to comprise two or more element layers.
  • inter-layers having a suitable thickness to the light-sensitive materials.
  • a variety of layers such as a filter layer, a non-curling layer, a protective layer, an antihalation layer and so forth may suitably be used in combination so as to serve as the component layers.
  • These component layers are allowed to contain hydrophilic colloids as the binding agent, similar to the case of such an emulsion layer as mentioned before.
  • the component layers are also allowed to contain various photographic additives which may be added into such an emulsion layer as mentioned before.
  • the invention has been able to provide a method of processing a silver halide colour photographic light-sensitive material, in which a colour developer can be kept excellent in stability of long standing and, particularly, a satisfactory maximum colour density can be obtained without deteriorating photographic characteristics by fog and the like and, further, a rapid processing can be performed.
  • Sample A of the Invention A silver halide colour photographic light-sensitive material (hereinafter called Sample A of the Invention) was prepared by coating the following eight layers onto a polyethylene-laminated paper support. Every amount added stated herein indicates an amount added per square meter, unless otherwise specially stated.
  • the maximum colour reflection density of the yellow dye obtained when the colour development was made at 35°C and for 10 minutes was meadured by means of an optical densitometer Model PDA-65 (manufactured by Konishiroku Photo Ind. Co., Ltd.) and the obtained value was regarded as 100.
  • a processing time necessary for making the above-mentioned maximum colour reflection density of yellow dye be 80 was obtained and shown in Table 1.
  • This development convergence time is a time for developing a blue-sensitive emulsion layer having the most slowest rate of development, therefore, this time indicates the time for completing the development of a light-sensitive material.
  • Table 1 also shows the respective maximum colour reflection densities of yellow, magenta and cyan dyes obtained when processing a light-sensitive material for the above-mentioned development convergence time.
  • the samples were prepared in such a manner that, the silver bromide contents of the blue-, green- and red-sensitive silver chlorobromide emulsions of the silver halide colour photographic light-sensitive material (sample A) used in Example 1, such silver bromide contents thereof were changed, respectively, as shown in Table 3.
  • the resulted samples were processed in the same manner as in Example 1, except that the developer composition was changed to that shown below and the colour developments were made for 45 seconds, provided therein that the preservatives were changed as shown in Table 2.
  • Example 3 The same processing as in Example 1 was repeatedly applied to the samples prepared by changing the silver bromide contents to 45 mol% from those of the green- and red-sensitive silver chlorobromide emulsions of the light-sensitive materials used in Example 1, provided therein that the pH of the colour developer used was adjusted to 12 and the preservatives used were changed as shown in Table 3.
  • each development convergence time and the respective maximum colour reflection densities of the yellow, magenta and cyan dyes were measured and the results thereof are shown in Table 3 below.

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

Claims (4)

  1. Verfahren zur Verarbeitung eines lichtempfindlichen Halogensilber-Farbphotographiematerials mit mehreren Halogensilberemulsionsschichten, welches Verfahren die Schritte der bildweisen Belichtung und der nachfolgenden Verarbeitung jedenfalls in einem Farbentwicklungsschritt umfaßt, wobei
    (1) das in den genannten mehreren Halogensilberemulsionsschichten enthaltene Halogensilber im wesentlichen Chlorbromsilber ist, und
    (2) unter den genannten mehreren Halogensilberemulsionsschichten wenigstens eine Schicht Chlorbromsilber mit einem Chlorsilbergehalt nicht unter 20 Mol-% enthält,
    dadurch gekennzeichnet, daß
    (3) ein bei dem genannten Farbentwicklungsschritt verwendeter Farbentwickler wenigstens eine durch die Formel [1]
    Figure imgb0018
     dargestellte Verbindung enthält,
    worin R₁ und R₂ jeweils eine Alkylgruppe oder eine Alkoxygruppe mit 1 bis 3 Kohlenstoffatomen bedeuten, oder R₁ und R₂ unter Ringbildung miteinander gekoppelt sind, und in jenem Falle, wo R₁ und R₂ jeweils eine Alkylgruppe bedeuten, mindestens eine der Gruppen R₁ und R₂ einen Substituenten aufweist.
  2. Verfahren gemäß Anspruch 1, dadurch gekennzeichnet, daß der Chlorsilbergehalt nicht unter 30 Mol-% liegt.
  3. Verfahren gemäß Anspruch 1, dadurch gekennzeichnet, daß der Farbentwickler wenigstens eine Entwicklersubstanz des p-Phenylendiamintyps mit wenigstens einer an den Benzolring bzw. eine daran hängende Aminogruppe gebundene Alkylsulfonamidoalkylgruppe enthält.
  4. Verfahren gemäß einem der Ansprüche 1 bis 3, dadurch gekennzeichnet, daß der Farbentwickler bis zu 1,3 x 10⁻² Mol pro Liter Bromidionen als Antischleiermittel enthält.
EP19870902147 1986-03-26 1987-03-25 Verfahren zur behandlung eines schnellentwickelnden silberhalid-farbphotographischen materials Expired - Lifetime EP0269740B1 (de)

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AU592642B2 (en) * 1986-04-16 1990-01-18 Konishiroku Photo Industry Co., Ltd. Color developer for silver halide material
EP0243100B1 (de) * 1986-04-19 1991-09-25 Konica Corporation Verfahren zur Behandlung eines farbphotographischen lichtempfindlichen Silberhalogenidmaterials
DE3789792D1 (de) * 1986-07-26 1994-06-16 Konishiroku Photo Ind Behandlungslösung eines lichtempfindlichen farbphotographischen Silberhalogenidmaterials und Verfahren zu dessen Behandlung.
JPH0218556A (ja) * 1988-07-06 1990-01-22 Fuji Photo Film Co Ltd ハロゲン化銀カラー写真感光材料の処理方法
JPH087418B2 (ja) * 1988-10-03 1996-01-29 富士写真フイルム株式会社 ハロゲン化銀カラー写真感光材料の処理方法
JP2670887B2 (ja) * 1989-07-28 1997-10-29 富士写真フイルム株式会社 ハロゲン化銀カラー写真感光材料の処理方法
US5176987A (en) * 1989-07-28 1993-01-05 Fuji Photo Film Co., Ltd. Method for processing silver halide color photographic materials
DE69030847T2 (de) * 1989-07-31 1997-09-18 Fuji Photo Film Co Ltd Verfahren zur Verarbeitung von farbphotographischem Silberhalogenidmaterial
JPH0363646A (ja) * 1989-08-01 1991-03-19 Fuji Photo Film Co Ltd ハロゲン化銀カラー写真感光材料の処理方法
DE69027267T2 (de) * 1989-09-07 1996-10-17 Fuji Photo Film Co Ltd Verfahren zur Verarbeitung eines farbfotografischen Silberhalogenidmaterials

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JPS513219A (ja) * 1974-06-25 1976-01-12 Konishiroku Photo Ind Shashinkankozairyono seizohoho
JPS5195849A (ja) * 1975-02-10 1976-08-23 Karaashashinyogenzozai
JPS6015056B2 (ja) * 1976-06-15 1985-04-17 富士写真フイルム株式会社 カラ−写真処理方法
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JPS57185434A (en) * 1981-05-11 1982-11-15 Fuji Photo Film Co Ltd Processing method for color photography
JPS59160142A (ja) * 1983-03-02 1984-09-10 Fuji Photo Film Co Ltd ハロゲン化銀カラ−感光材料の処理方法
JPS59160141A (ja) * 1983-03-02 1984-09-10 Fuji Photo Film Co Ltd ハロゲン化銀カラ−感光材料の処理方法
JPH068956B2 (ja) * 1983-04-04 1994-02-02 富士写真フイルム株式会社 ハロゲン化銀カラ−感光材料の処理方法
DE3346621A1 (de) * 1983-12-23 1985-07-04 Agfa-Gevaert Ag, 5090 Leverkusen Farbfotografisches aufzeichnungsmaterial und entwicklungsverfahren
JPS62500793A (ja) * 1984-11-19 1987-04-02 ザ　ダウ　ケミカル　カンパニ− エポキシ樹脂の全ハロゲン化物含量低下方法
EP0243096B1 (de) * 1986-04-18 1994-02-09 Konica Corporation Verfahren zur Behandlung eines lichtempfindlichen farbphotographischen Silberhalogenidmaterials
DE3789792D1 (de) * 1986-07-26 1994-06-16 Konishiroku Photo Ind Behandlungslösung eines lichtempfindlichen farbphotographischen Silberhalogenidmaterials und Verfahren zu dessen Behandlung.

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DE3787952D1 (de) 1993-12-02
AU591274B2 (en) 1989-11-30
WO1987006026A1 (fr) 1987-10-08
EP0269740A4 (de) 1989-07-26
JPS6311938A (ja) 1988-01-19
AU7208387A (en) 1987-10-20
DE3787952T2 (de) 1994-04-07

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