US3794489A - Method of developing silver halide photosensitive material - Google Patents

Method of developing silver halide photosensitive material Download PDF

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Publication number
US3794489A
US3794489A US00206820A US3794489DA US3794489A US 3794489 A US3794489 A US 3794489A US 00206820 A US00206820 A US 00206820A US 3794489D A US3794489D A US 3794489DA US 3794489 A US3794489 A US 3794489A
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US
United States
Prior art keywords
developing
hydroquinone
photographic
silver halide
solution
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired - Lifetime
Application number
US00206820A
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English (en)
Inventor
A Arai
T Tajima
Y Tsuchiva
M Tanaka
K Ohkubo
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Fujifilm Holdings Corp
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Fuji Photo Film Co Ltd
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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
    • G03C1/00—Photosensitive materials
    • G03C1/005—Silver halide emulsions; Preparation thereof; Physical treatment thereof; Incorporation of additives therein
    • G03C1/06—Silver halide emulsions; Preparation thereof; Physical treatment thereof; Incorporation of additives therein with non-macromolecular additives
    • G03C1/42—Developers or their precursors
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03C—PHOTOSENSITIVE MATERIALS FOR PHOTOGRAPHIC PURPOSES; PHOTOGRAPHIC PROCESSES, e.g. CINE, X-RAY, COLOUR, STEREO-PHOTOGRAPHIC PROCESSES; AUXILIARY PROCESSES IN PHOTOGRAPHY
    • G03C5/00—Photographic processes or agents therefor; Regeneration of such processing agents
    • G03C5/26—Processes using silver-salt-containing photosensitive materials or agents therefor
    • G03C5/29—Development processes or agents therefor
    • G03C5/30—Developers
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03C—PHOTOSENSITIVE MATERIALS FOR PHOTOGRAPHIC PURPOSES; PHOTOGRAPHIC PROCESSES, e.g. CINE, X-RAY, COLOUR, STEREO-PHOTOGRAPHIC PROCESSES; AUXILIARY PROCESSES IN PHOTOGRAPHY
    • G03C5/00—Photographic processes or agents therefor; Regeneration of such processing agents
    • G03C5/26—Processes using silver-salt-containing photosensitive materials or agents therefor
    • G03C5/29—Development processes or agents therefor
    • G03C5/30—Developers
    • G03C5/3021—Developers with oxydisable hydroxyl or amine groups linked to an aromatic ring

Definitions

  • a photographic developing process which comprises developing an exposed light-sensitive silver halide emulsion layer of a photographic material with an alkaline solution in the presence of hydroquinone and a derivative of p-amino-phenol having the general formula:
  • the present invention relates to a method of developing a silver halide photosensitive material. More particularly, it has as an object additionally improving the developing activity of hydroquinone by the use of a developing agent comprising hydroquinone in combination with a specific type compound as hereinafter described.
  • Prior art Photosensitive material has heretofore been prepared by coating a photosensitive silver halide emulsion on a substrate such as glass plate, paper, plastic film, etc., followed by drying the coated product. After the thus prepared photosensitive material has been exposed to light, it is developed in a developer liquid which is an alkaline aqueous solution containing a developing agent as its essential ingredient, thereafter the developed material is subjected to stopping, fixation and water-rinsing treatments in sequence.
  • a developer liquid which is an alkaline aqueous solution containing a developing agent as its essential ingredient
  • one improved method includes high temperature processing, single-bath development and fixation, double bath stabilization treatment processes, etc.
  • One of the currently employed methods for shortening the time of development comprises adding a developing agent into a silver halide emulsion layer and then treating the layer in a highly alkaline aqueous solution containing an alkali agent and other photographic additives such as antioxidants and retarders and the like.
  • the characteristic feature of that method resides in enabling quick developing with a shortened developing reaction time which is due to the use of the highly increased pH of the processing liquid that can be only attained by the absence of a developing agent in the processing liquid without degrading its storability.
  • the silver halide photosensitive material to be employed in that method includes silver chloride emulsions and silver chlorobromide emulsions having a low silver bromide content which has a high rate of developing reaction.
  • R is, for example, an alkyl group having 1 to 6 carbon atoms
  • R for example, methyl or ethyl group
  • X is a, for example, methyl, ethyl and alkoxyl group having 1 to 6 carbon atoms.
  • each of X and X. is, for example, a hydrogen atom, a halogen atom, an alkyl group, an alkoxyl group, an alkyl-amino group, etc.
  • the emulsion incorporated with these compounds is likely to generate fogging which leads to another disadvantage in that the developing speed appreciably decreases when trying to prevent the fogging by adding a known fog inhibitor.
  • each of R and R is an alkyl group having 1 to 4 carbon atoms and each of X, Y and Z is an alkyl group having 1 to 4 carbon atoms.
  • An object of this invention is to improve the photographic characteristics in a conventional rapid developing process using a photographic paper, by adding the abovementioned compound of the General Formula III into a silver halide emulsion layer and/or adjacent layer such as a protective layer of an undercoat layer containing a developing agent therein.
  • a further object of this invention is to employ a compound of the General Formula III as an essential developing agent having super additivity when combined with hydroquinone for developing monochromic and color photography.
  • a still further object of this invention is to accelerate the developing speed upon usual developing treatment by adding the compound of the General Formula III into either one of an emulsion layer, a protective layer or an undercoating layer of silver halide photosensitive material containing no developing agent added therein.
  • novel developing agent of the above General Formula III may be usually used in the form of stable salts such as hydrochloride or sulfate rather than in the form of free amine. More particularly the Compounds (III) identified hereinafter have proved to be very suitable for being applied in the process according to the present invention:
  • the compound represented by the General Formula HI is effective for the combination with either pure silver chloride, silver chlorobromide, pure silver bromide or silver iodobromide, but an outstanding effect is attained when it is combined with silver chlorobromide, pure silver bromide or with silver iodobromide emulsions each of which is known to have a slow developing activity.
  • the developing agent to be used in combination with the compound of the General Formula III in accordance with the present invention is not limited to any specific types, but it is possible to use any compounds which are conventionally used as photographic developing agents having reducing activity.
  • Examples of such developing agents include hydroquinone or its derivatives, catechol or its derivatives, ascorbic acid, etc.
  • the substrate to be used for supporting the silver halide photographic material may be any one of those materials so far as it can support a silver halide emulsion layer, and typically includes paper, plastic films, etc., which may be further provided with a baryta layer or an undercoating layer.
  • the silver halide emulsion to be used is intended to include silver halide photosensitive materials, and may contain gelatin or other synthetic resins such as poly (vinyl alcohol), poly (vinyl acetal), etc., as a binder.
  • a 500 ml. autoclave was charged with 19 g. of 4-amino- 2,3,6-trimethylphenol, prepared in a process as disclosed in British Pat. 1,126,219, 27 ml. of a 37% Formalin, 1.5 g. of a 10% Pd-C and 200 ml. of ethanol and, after gaseous hydrogen was introduced thereinto to a pressure of 54 atms., the charge was stirred at room temperature for about 24 hours.
  • the reaction mixture was filtered, the filtrate was distilled under reduced pressure to eliminate ethanol and the residue was distilled under a reduced pressure of 1 mm. Hg.
  • the distillate was collected with the raising of the temperature of the oil bath to 150 C. and was dissolved in 500 ml.
  • Example A In a similar manner as taught in Example A, there was obtained an end product in the form of white powdery crystals at a yield of 13.0 g. (42.5% of theoretical) from 19 g. of 4-amino-2,3,6-trimethylphenol, 15 ml. of an aqueous acetaldehyde, 1.5 g. of a 10% Pd-C and 200 ml. of ethanol.
  • EXAMPLE 1 To 400 cc. of a silver halide gelatin emulsion containing 50 g. of gelatin and 20 g. of a silver chlorobromide in which silver bromide amounted to 60 mol percent there were added, other than necessary film hardener and coating assistants, one or more developing agents as listed in the following Table 1 to form a coating liquid.
  • a photographic baryta paper of a weight of g./m. was coated with the coating liquid and then, before drying of the emulsion layer, after setting of the emulsion layer, with a solution consisting of 20* g. of gelatin, 6 cc.
  • EXAMPLE 2 To 400 cc. of a silver halide gelatin emulsion containing 50 g. of gelatin and 20 g. of silver iodobromide in which silver iodide amounted to 1.5 mol percent there were added necessary film hardeners and coating assistants to prepare a coating solution. A photographic baryta paper of a weight of 150 g./m. was coated with the coating solution and, while the emulsion layer was in a set but undried state, with a coating solution consisting of 30 g. of hydroquinone and 1.4 g. of 4-dimethylamino-2,3,6-
  • trimethylphenol hydrochloride as developing agents 2 g. I, of sodium benzenesulfinate as an antioxidant for develop- I EXAMPLE 3
  • a photographic baryta paper of a weight of 150 g./m. was coated with a coating solution consisting of 50 g. of gelatin, 35 g. of hydroquinone, 1.5 g. of 4-dimethylamino- 2,3,6-trimethylphenol hydrochloride, 2 g. of sodium benzenesulfinate as antioxidant for hydroquinone, 2 cc. of 30% formalin, 1.0 g. of a phosphorescent whitening agent, Blankophor -BUP supplied by Bayer A. G., and 1 liter of water.
  • a specimen of printing paper containing no 4-dimethylamino-2,3,6 trimethylphenol hydrochloride therein was prepared in the similar procedure.
  • the specimen containing the 4- dimethyl-amino-2,3,6 trimethylphenol hydrochloride in its subbing layer exhibited excellent sensitometric characteristics corresponding to higher sensitivity, maximum density and gamma than those of the comparative specimen.
  • EXAMPLE 4 A coating solution was prepared by adding necessary film hardeners and coating assistants to 400 cc. of a silver halide gelatin emulsion containing 50 g. of gelatin and 20 g. of a silver chlorobromide in which silver bromide amounted to 50 mol percent. The coating solution was applied to a photographic baryta paper of a weight of 150 g./m. to form a printing paper.
  • the printing paper thus obtained was exposed in a fixed quantity of exposure and developed with a developing solution of the following composition.
  • Changes in black ening density with developing time were plotted in the FIG. 1 in the accompanying drawing, in which the curves 1 to 5 corresponded to a sole or combined developing agent as indicated in the following table.
  • EXAMPLE 5 To a silver halide emulsion containing g. of gelatin and 40 g. of a silver chlorobromide (A'gBr 60 mol percent) per kg. there were added 30 g. of hydroquinone per kg. of emulsion and other necessary additives and the emulsion was applied to a photographic baryta paper of a weight of g./m. and dried.
  • a silver chlorobromide A'gBr 60 mol percent
  • the printing paper thus produced was exposed through an optical wedge and developed for 4 seconds in an activating solution as indieated in Example 1 or an activation solution obtained by adding to the activation solution of Example 1 0.9 g., per liter of the solution, of the compound of Example A and, after stabilization with a stabilizing solution contain- TABLE 2.ACTIVATING SOLUTION, RELATIVE SENSITIV- IIY, MAXIMUM DENSITY AND CONTRAST Containing the compound of example A 1 51 Not containing the compound of example A.
  • Example A remarkably accelerates development by hydroquinone.
  • EXAMPLE 6 The silver halide emulsion as employed in Example 5 was added with 1.8 g., per kg. of emulsion, of the compound obtained in Example A and other required additives, and applied to a photographic baryta paper of a weight of 150 g./m. and dried.
  • the printing paper thus obtained and a printing paper prepared by using the same emulsion except for not containing the compound of Example A were exposed through an optical wedge, developed for 4 seconds in an activating solution prepared by adding g. of hydroquinone to per 1 liter of the activating solution as employed in Example 1, stabilized with a stabilizing solution containing ammonium thiocyanate and subjected to a sensitometry for determination of relative sensitivity, maximum density and contrast.
  • the results were as summarized in the following Table 3.
  • the process of the present invention is applicable not only to silver halide photosensitive materials containing a developing agent in an emulsion layer but also to more conventional ones containing no developing agents in the emulsion layer, e.g., photographing or printing, was to obtain a good result.
  • a photographic developing process which comprises developing an exposed light-sensitive silver halide emulsion layer of a photographic material with an alkaline solution in the presence of hydroquinone and a derivative of p-amino-phenol having the general formula:
  • each of R R X, Y and Z is an alkyl group containing 1 to 4 carbon atoms, said hydroquinone and said derivative of p-amino-phenol being present in said emulsion layer, a layer adjacent to said emulsion layer or in said alkaline solution.
  • a photographic developing process wherein said hydroquinone is incorporated in said emulsion layer, and said derivative is incorporated in said alkalne solution.
  • a photographic developing process wherein said hydroquinone is incorporated in a layer adjacent to said emulsion layer and said derivative is incorporated in said alkaline solution.
  • a photographic developing process wherein said hydroquinone is incorporated in said alkaline solution, and said derivative is incorporated in a layer adjacent said emulsion layer.
  • a photographic developing process wherein said hydroquinone is incorporated in said emulsion layer in an amount of from 5 to 500 grams per mole of light-sensitive silver halide.
  • a photographic developing process wherein said hydroquinone is present in said alkaline solution in an amount of from 1 to 70 grams per liter of said alkaline solution.
  • a photographic developing process according to claim 1, wherein said derivative is selected from the group consisting of 4-dimethylamino-2,3,6-trimethyl phenol hydrochloride, 4-di-n-propylamino 2,3,6 trimethyl phenol sulfate, and 4-di-n-butylamino 2,3,6 trimethyl phenol hydrochloride.
  • a photographic material having at least one lightsensitive silver halide emulsion layer, which contains hydroquinone and a derivative of p-aminophenol having the general formula:
  • each of R R X, Y and Z is an alkyl group containing 1 to 4 carbon atoms.

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  • Physics & Mathematics (AREA)
  • General Physics & Mathematics (AREA)
  • Chemical & Material Sciences (AREA)
  • Spectroscopy & Molecular Physics (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Silver Salt Photography Or Processing Solution Therefor (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
US00206820A 1970-12-10 1971-12-10 Method of developing silver halide photosensitive material Expired - Lifetime US3794489A (en)

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
JP45109869A JPS491211B1 (enExample) 1970-12-10 1970-12-10

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US3794489A true US3794489A (en) 1974-02-26

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US (1) US3794489A (enExample)
JP (1) JPS491211B1 (enExample)
DE (1) DE2161431A1 (enExample)
FR (1) FR2117536A5 (enExample)
GB (1) GB1355721A (enExample)

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DE2161431A1 (de) 1972-06-29
GB1355721A (en) 1974-06-05
JPS491211B1 (enExample) 1974-01-12
FR2117536A5 (enExample) 1972-07-21

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