US3804624A - Method for developing silver halide photosensitive material - Google Patents

Method for developing silver halide photosensitive material Download PDF

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Publication number
US3804624A
US3804624A US00192951A US19295171A US3804624A US 3804624 A US3804624 A US 3804624A US 00192951 A US00192951 A US 00192951A US 19295171 A US19295171 A US 19295171A US 3804624 A US3804624 A US 3804624A
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United States
Prior art keywords
layer
hydroquinone
photographic
process according
derivative
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Expired - Lifetime
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US00192951A
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English (en)
Inventor
T Tajima
M Tanaka
A Arai
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
    • 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
    • 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

Definitions

  • Photosensitive materials have been heretofore prepared by coating a photosensitive silver halide emulsion on a support material such as a glass plate, paper, plastic films, 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 and thereafter sequentially subjected to stopping, fixation and water-rinsing treatments.
  • a developer liquid is an alkaline aqueous solution containing a developing agent as its essential ingredient
  • One of the currently employed methods for shortening the time of development comprises adding a developing agent to 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.
  • the advantageous feature of this method resides in making quick development processing possible with shortened developing time which is brought forth by the use of a highly increased pH of a processing liquid that can be allowed only when no developing agent is contained in the processing liquid thereby not causing any degradation in the storability of the processing liquid.
  • the silver halide photosensitive material to be employed suitably in the above-described method includes silver chloride emulsions and silver chlorobromide emulsions having less silver bromide content, which inherently have a higher rate of developing reaction than is common.
  • halogen atom an alkyl group, an alkoxyl group, an alkylamido group, etc.
  • a primary object of this invention is to improve the photographic characteristics in a conventional rapid developing process of photographic paper, by adding a compound of the general formula (III) shown below into a silver halide emulsion layer and/or adjacent layer such as a protective layer or undercoating layer containing a developing agent admixed therein.
  • each of R and R is an alkyl group containing 1 to 4 carbon atoms.
  • a further object of this invention is to employ a compound of the general formula (III) as an essential developing agent having exceptional additivity when combined with hydroquinone for developing monochromic and color photographs.
  • a still further object of this invention is to accelerate the developing speed of the usual developing treatment by adding the compound of the general formula (III) into the emulsion layer, a protective layer and/or the undercoating layer of silver halide photosensitive materials containing no developing agent added therein.
  • each of R and R is an alkyl group containing 1 to 4 carbon atoms.
  • novel developing agent of the above general formula (Ill) may be usually used in the form of stable salts such as the hydrochloride or sulfate salts rather than in the form of the free amine. More particularly, the compounds of formula (III) identified below have proved to be very suitable for being applied in the process of the present invention:
  • 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 type, and it is possible to use any compounds which are conventionally employed as photographic developing agents having reducing reactivity.
  • Such developing agents typically include hydroquinone or its derivatives, catecohol or its derivatives, ascorbic acid, etc..
  • the support material to be used for supporting the silver halide photosensitive material may be any one of those capable of supporting silver halide emulsions and is typically exemplified by paper and plastic film which may be further provided with baryta layer(s) or undercoating layer(s).
  • 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 polyvinyl alcohol, polyvinyl acetal, etc..
  • EXAMPLE 2 A coating solution was prepared by adding a necessary hardening agent and a coating additive to 400 cc 0 ofa silver halide gelating emulsion containing g gelatin and 20 silver iodobromide in which silver iodide occupied 1.5 mol percent. This coating solution was applied to a photographic baryta paper of 150 g/m.
  • This coated paper was further coated, under the set state, with a coating solution comprising 20g of gelatin, a mixture of 30g of hydroquinone and 1.5g of 4-diethy1amino-2-phenylphenol hydrochloride as an essential developing ingredient, 2g of sodium benzene sulfinate as an antioxidant for the developing agent, 3 cc of 30 percent aqueous formalin solution, 6 cc of 6 percent methanol solution of saponin and one liter of water and thereafter dried.
  • a coating solution comprising 20g of gelatin, a mixture of 30g of hydroquinone and 1.5g of 4-diethy1amino-2-phenylphenol hydrochloride as an essential developing ingredient, 2g of sodium benzene sulfinate as an antioxidant for the developing agent, 3 cc of 30 percent aqueous formalin solution, 6 cc of 6 percent methanol solution of saponin and one liter of water and thereafter dried.
  • a comparative sample was similarly prepared but adding no 4-diethy1amino-2-phen1y1phenol hydrochloride.
  • Example 2 Thus prepared samples were treated according to the manner similar to Example 1.
  • the sample of this invention exhibits superior values in sensitivity, maximum density and in gamma to the control sample.
  • Photographic baryta paper of 150 g/m was coated with a solution comprising 50g of gelatin, 35g of hydroquinone, 1.8g of 4-dimethylamino-2-phenylphenol hydrochloride, 2g of sodium benzene sulfinate as an antioxidant for hydroquinone, 2 cc of 30 percent aqueous formalin solution, 1.0g of a fluorescent whitening agent, Blankopher BUP" (manufactured by Bayer Co., West Germany) and one liter of water.
  • a solution comprising 50g of gelatin, 35g of hydroquinone, 1.8g of 4-dimethylamino-2-phenylphenol hydrochloride, 2g of sodium benzene sulfinate as an antioxidant for hydroquinone, 2 cc of 30 percent aqueous formalin solution, 1.0g of a fluorescent whitening agent, Blankopher BUP" (manufactured by Bayer Co., West Germany) and one liter of water.
  • a coating solution comprising 400 cc of silver halide gelatin emulsion containing 20g of silver chlorobromide in which the content of silver bromide was mol percent, and other necessary additives such as a hardening agent and a coating additive were coated thereon.
  • the coated paper was further provided while under the set state, with a protective layer by coating thereon a solution comprising 20g of gelatin, 6 cc of 6 percent methanol, a solution of saponin and one liter of water.
  • EXAMPLE 4 A coating solution was prepared by adding a necessary hardening agent and a coating additive to 400 cc of a silver halide gelatin emulsion containing 50g of gelatin and g of silver chlorobromide with a silver bromide content of 50 mol percent. The coating solution was applied to photographic baryta paper of 150 g/cm to thereby prepare a photographic paper. This apper was developed with the use of the developing liquid having the following composition, and the change in density in relation to the developing period at a constant exposure dosage is illustrated in FIG. 1.
  • Photographic baryta paper of 150 g/m was coated with a coating solution prepared by adding 30 g hydroquinone and other necessary additives to every one Kg of a silver halide emulsion containing 40 g of silver chlorobromide (60 mol percent silver bromide) per 125 g of gelatin and then dried.
  • the thus prepared photographic paper was exposed to light through a step wedge, then developed for 4 seconds with the activated solution used in Example 1 and thereafter stabilized with a stabilizer solution containing ammonium thiocyanate.
  • the same treatment was repeated but using as the activated solution a solution containing 0.9 g per liter added compound of Synthetic Example 1.
  • Table 2 The results obtained after measuring specific sensitivity, maximum density and gamma are given in Table 2.
  • Photographic baryta paper of g/m was coated with an emulsion containing 2.2g of the compound of Synthetic Example (1 per one Kg. of the silver halide emulsion of Example 5 and other additives, then dried to give a photographic paper.
  • This photographic paper and another photographic paper prepared by using an emulsion containing the compound of Synthetic Example (1) were each exposed to light through a step wedge, then developed for 4 seconds with an activated solution containing 20g of hydroquinone per liter of the solution shown in Example 1, and thereafter stabilized with a stabilizer solution containing ammonium rhodanate.
  • the results obtained by measuring the specific sensitivity, maximum density and gamma are given in Table 3.
  • the present invention is not only adaptable for a silver halide photosensitive material containing a developing agent in the emulsion layer thereof, but also quite similarly applicable with excellent results to conventionally used silver halide photosensitive materials for photographic or copying purposes containing no developing agent in the emulsion layer thereof.
  • a photographic developing process which comprises developing an exposed light-sensitive silver halide emulsion layer of a multilayer photographic element with an alkaline solution hydroquinone and a derivative of p-aminophenol having the general formula:
  • a photographic developing process wherein said hydroquinone is incorporated in said layer, in an adjacent layer to said emulsion layer or in said layer and in an adjacent layer to said emulsion layer, and said derivative is incorporated in said alkaline solution.
  • a photographic developing process wherein said hydroquinone and said derivative are incorporated in said layer, in an adjacent layer to said emulsion layer or in said layer and in an adjacent layer to said emulsion layer.
  • a photographic developing process wherein the amount of said hydroquinone is from 5 to 500 grams per mole of light-sensitive silver halide.
  • a photographic developing process according to claim 4, wherein the amount of said derivative is from 0.05 to 50 grams per mole of light-sensitive silver halide.
  • each of said R and R is an alkyl group having 1 to 4 carbon atoms said derivative showing a superadditive effect in combination with hydroquinone when said photographic material is developed in said derivative and hydroquinone.

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  • Physics & Mathematics (AREA)
  • Chemical & Material Sciences (AREA)
  • General Physics & Mathematics (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)
US00192951A 1970-10-27 1971-10-27 Method for developing silver halide photosensitive material Expired - Lifetime US3804624A (en)

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
JP45094868A JPS4943333B1 (de) 1970-10-27 1970-10-27

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US3804624A true US3804624A (en) 1974-04-16

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US00192951A Expired - Lifetime US3804624A (en) 1970-10-27 1971-10-27 Method for developing silver halide photosensitive material

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US (1) US3804624A (de)
JP (1) JPS4943333B1 (de)
DE (1) DE2153633A1 (de)
FR (1) FR2113247A5 (de)
GB (1) GB1344690A (de)

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4465762A (en) * 1981-03-03 1984-08-14 Fuji Photo Film Co., Ltd. Method for color developing color photographic silver halide light-sensitive material
US5484690A (en) * 1990-09-13 1996-01-16 Fuji Photo Film Co., Ltd. Silver halide photographic material
US20090029125A1 (en) * 2005-02-15 2009-01-29 Fujifilm Corporation Photosensitive material for forming conductive film, conductive film, light transmitting electromagnetic wave shielding film and method for manufacturing the same

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS63171330U (de) * 1987-04-30 1988-11-08

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3108001A (en) * 1959-08-17 1963-10-22 Polaroid Corp Novel photographic products, processes, and compositions
US3134673A (en) * 1960-02-19 1964-05-26 Ilford Ltd Photographic developers
US3257207A (en) * 1963-08-30 1966-06-21 Polaroid Corp Photographic products, processes and compositions
US3265499A (en) * 1961-07-10 1966-08-09 Gevaert Photo Prod Nv Photographic developing compositions
US3600176A (en) * 1968-11-29 1971-08-17 Eastman Kodak Co Photographic elements,compositions and processes

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3108001A (en) * 1959-08-17 1963-10-22 Polaroid Corp Novel photographic products, processes, and compositions
US3134673A (en) * 1960-02-19 1964-05-26 Ilford Ltd Photographic developers
US3265499A (en) * 1961-07-10 1966-08-09 Gevaert Photo Prod Nv Photographic developing compositions
US3257207A (en) * 1963-08-30 1966-06-21 Polaroid Corp Photographic products, processes and compositions
US3600176A (en) * 1968-11-29 1971-08-17 Eastman Kodak Co Photographic elements,compositions and processes

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
PSA Journal, Section B, Nov. 1953, Henn, pp. 149 150. *

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4465762A (en) * 1981-03-03 1984-08-14 Fuji Photo Film Co., Ltd. Method for color developing color photographic silver halide light-sensitive material
US5484690A (en) * 1990-09-13 1996-01-16 Fuji Photo Film Co., Ltd. Silver halide photographic material
US20090029125A1 (en) * 2005-02-15 2009-01-29 Fujifilm Corporation Photosensitive material for forming conductive film, conductive film, light transmitting electromagnetic wave shielding film and method for manufacturing the same

Also Published As

Publication number Publication date
JPS4943333B1 (de) 1974-11-20
FR2113247A5 (de) 1972-06-23
GB1344690A (en) 1974-01-23
DE2153633A1 (de) 1972-05-04

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