US3822130A - Method for developing silver halide photosensitive material - Google Patents

Method for developing silver halide photosensitive material Download PDF

Info

Publication number
US3822130A
US3822130A US00192953A US19295371A US3822130A US 3822130 A US3822130 A US 3822130A US 00192953 A US00192953 A US 00192953A US 19295371 A US19295371 A US 19295371A US 3822130 A US3822130 A US 3822130A
Authority
US
United States
Prior art keywords
developing
photographic
hydroquinone
emulsion
silver halide
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
US00192953A
Other languages
English (en)
Inventor
A Arai
M Tanaka
Y Tsuchiya
K Ohkubo
T Tajima
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Fujifilm Holdings Corp
Original Assignee
Fuji Photo Film Co Ltd
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Fuji Photo Film Co Ltd filed Critical Fuji Photo Film Co Ltd
Application granted granted Critical
Publication of US3822130A publication Critical patent/US3822130A/en
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

Links

Images

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
    • G03C5/30—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

  • 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-aminophenol having the formula:
  • R is an alkyl group of from 1 to 4 carbon atoms, and n is an integer of from 2 to 5.
  • the present invention relates to a method for developing a silver halide photosensitive material. More particularly, it has as its object the improvement of the developing activity of hydroquinone by the use of hydroquinone in combination with a specific compound as a developing agent.
  • Photosensitive materials have heretofore been prepared by coating a photosensitive silver halide emulsion on a support base, 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 with a developer liquid, which is an alkaline aqueous solution containing a developing agent as its essential ingredient, thereafter it is subjected to the steps of stopping, fixation and various water-rinsing treatments in sequence.
  • a developer liquid which is an alkaline aqueous solution containing a developing agent as its essential ingredient
  • One of the most currently employed methods for shortening the time of development comprises adding a developing agent to a silver halide emulsion layer, then treating the layer with a highly alkaline aqueous solution containing an alkali agent and other photographic additives, such as an antioxidant and a retarder.
  • the advantageous feature of that method resides in making a quick development process possible within a shortened developing reaction time, which is brought forth by the use of a highly increased pH processing liquid. This is only possible when no developing agent is added to the processing liquid employed without causing any degradation on the storability of the liquid.
  • the silver halide photosensitive material to be suitably employed in that method includes a silver chloride emulsion and a silver chlorobromide emulsion having less silver bromide content, which originally has a high rate of developing reaction.
  • each of X and X is, for example, a hydrogen atom, a halogen atom, an alkyl group, an alkyl ammo group, etc., respectively.
  • the primary object of the present invention is to improve the photographic characteristics in a conventional rapid developing process of photographic paper, by adding the above-mentioned compound of formula (III) into the silver halide emulsion layer and/or adjacent layer, such as protective layer or undercoat layer containing a developing agent admixed thereto.
  • the second object of this invention is to employ a compound of the formula (III) as an essential developing agent having super additivity when being combined with hydroquinone for developing monochromic and color photography.
  • the third object of this invention is to accelerate the developing speed of the usual developing treatment by adding the compound of formula (III) into either one of the emulsion layer, protective layer and undercoat layer of a silver halide photosensitive material containing no de' veloping agent added thereto.
  • novel developing agent of the above formula (III) may be usually used in the form of stable salts such as hydrochloride or sulfate rather than in the form of the free amine. More particularly, the compound of formula (III) identified hereinafter have proved to be very suitable for being applied in the process according to the present invention:
  • the development agent to be used in combination with the compounds of formula (III) in accordance with the present invention is not limited to any specific type, and it is possible to use any compound, which is conventionally used as a photographic developing agent having a reducing activity.
  • Such developing agents typically include hydroquinone or its derivatives, catechol or its derivatives, ascorbic acid and like compounds.
  • the support material to be used for carrying the silver halide photosensitive material may be any one of those capable of providing a silver halide emulsion with it, and typically exemplified by paper, glass, and plastic film, which may be further provided with a baryta layer or undercoat layer.
  • the silver halide emulsion to be used is intended to include a silver halide photosensitive material, and may contain gelatin or another synthetic resin such as polyvinyl alcohol, polyvinyl acetal and the like.
  • a mixture comprising 10 g. of the thus prepared 4-ethylamino-2,6-dimethylphenol hydrochloride, 6.5 g. ethylene bromohydrin, 7.1 g. of anhydrous potassium carbonate and ml. of ethanol was heated under reflux for 8 hours in a nitrogen atmosphere. After cooling the reaction product mixture in a nitrogen atmosphere, it was filtered under suction and the residual solid mass on the filter paper was washed twice with ethanol. The filtrate and wash liquid were combined together, and the mixture was distilled under reduced pressure to distill off ethanol to leave a residue, which was impregnated twice with hot ether. After removing the ether by distillation, it was further distilled under a reduced pressure of l mm./Hg.
  • SYNTHETIC EXAMPLE 2 4-(N-methyl-N-fi-hydroxyethylamino)-2,6-dimethylphenol hydrochloride This compound was prepared according to a manner similar to that of Example 1, from 10 g. of 4-methylamino-2,6-dimethylphenol hydrochloride, which per se was obtained by using 40 g. of 2,6-dimethyl hydroquinone and 200 g. of 40% aqueous methylamine, 6.95 g. of ethylene bromohydrin, 7.6 g. anhydrous potassium carbonate and 100 ml. of ethanol.
  • Coating solutions were each prepared by adding a requisite hardening agent, a coating adjuvant and each developing agent as shown in Table 1, which follows, to 400 cc. of a silver halide gelatin emulsion containing 50 g. of gelatin and g. of silver chlorobromide having a silver bromide content of 60 mol percent.
  • Each coating solution thus prepared was applied to a photographic baryta paper of 150 g./m.
  • the coated paper was further provided, under a set state before drying of the coated emulsion layer, with a protective coating layer consisting of 20 g. of gelatin, 6 cc. of saponin (as a 6% solution in methanol) and one liter of water, and thereafter dried to give each sample of A-G.
  • the photographic paper thus prepared was exposed to light through an optical wedge (step wedge) and developed with the use of an activated solution having a composition as follows:
  • Composition of activated solution G. Anhydrous sodium sulfite 45 Potassium hydroxide 48 Potassium bromide 1.3
  • 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 50 g. of gelatin and 20 g. of silver iodobromide in which the silver iodide content was 1.5 mol percent.
  • This coating solution was applied to a photographic baryta paper of 150 g./m.
  • the thus coated paper was further provided under a set state before drying of the coated emulsion layer, with a coating solution comprising 20 g. of gelatin, a mixture of g. of hydroquinone with 1.5 g.
  • a comparative sample was similarly prepared, but adding no 4-(methyl-N-[B-hydroxyethylamino)-2,6-dimethylphenol.
  • Example 2 The thus prepared samples were each treated according to a manner similar to Example 1.
  • the sample of this invention exhibited superior values in every sensitivity, maximum density and in gamma to the control sample.
  • EXAMPLE 3 A photographic baryta paper of g./m. was coated with a solution comprising 50 g. of gelatin, 35 g. of hydroquinone, 1.7 g. of 4-(N-ethyl-N-B-hydroxyethylamino)-2,6-dimethylphenol xylenol hydrochloride, 2 g. of sodium benzene sulfinate as an antioxidant for the hydroquinone, 2 cc. of a 30% aqueous formalin solution, 1.0 g. of a fluorescent whitening agent Blankophor BUP (trade name, manufactured by Bayer Co., West Germany) and one liter of water. Onto this there was coated a coating solution comprising 400 cc.
  • a coating solution comprising 400 cc.
  • a silver halide gelatin emulsion containing 20 g. of silver chlorobromide in which the content of silver bromide was 60 mol percent, and other necessary additives, such as a hardening agent and a coating adjuvant.
  • the thus coated paper was further provided, under a set state before drying of the coated emulsion, with a protective layer by coating thereon, a solution comprising 20 g. of gelatin, 6 cc. of a 6% methanol 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 50 g. of gelatin and 20 g. of silver chlorobromide with a silver bromide content of 50 mol percent. The coating solution thus 0 tained was applied to a photographic baryta paper of 150 g./m. to thereby prepare a photographic paper. This paper was developed with the use of a developing liquid having the following composition, and the change in density in relation to the developing period at a constant exposure dosage was plotted on the curves shown in FIG. 1.
  • each curve indicates the following:
  • 'Curve B Hydroquinone was used in combination with 1-' Composition of developing bath: G. Anhydrous sodium sulfite 20 Hydroquinone 3 Anhydrous sodium carbonate 15 Potassium bromide 1 Cooperative developing agent shown in the table above (in the molar ratio of 1/20 to hydroquinone).
  • FIG. 1 illustrates plotted curves showing the relation of density to the developing time of the sample obtained in accordance with an example of this invention and a comparative sample.
  • 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 adding to the activated solution 0.9 g. per liter of the added compound of Synthetic Example 1.
  • Table 2 The results obtained after measuring specific sensitivity, maximum density and gamma are given in Table 2.
  • EXAMPLE 6 A photographic baryta paper of 150 g./m. was coated with an emulsion containing 2.0 g. of the compound of Synthetic Example 2 per one kg. of the silver halide emulsion of Example 5 and other additives, and then dried to give a photographic paper.
  • This photographic paper and another sample of photographic paper prepared by using an emulsion without containing the added compound of Synthetic Example 2 were each exposed to light through a step wedge, then developed for 4 seconds with an activated solution containing 20 g. of hydroquinone per liter of the solution shown in Example 1, and thereafter stabilized with a stabilizer solution containing ammonium rhodanate.
  • the results obtained after measuring the specific sensitivity, maximum density and gamma are given in Table 3.
  • R is an alkyl group of from 1 to 4 carbon atoms, and n is an integer of from 2 to 5.
  • a multi-layer photographic element having at least one light sensitive silver halide emulsion layer, which contains from 0.05 to 50 grams per mole of silver halide of a derivative of p-aminophenol having the formula:
  • An alkaline solution for photographic development which contains from 0.01 to 20 grams per liter of said solution of a derivative of p-aminophenol having the formula:
  • R is an alkyl group having from 1 to 4 carbon atoms, and n is an integer of from 2 to 5, said p-aminophenol derivative exhibiting a super-additive developing effect when used for development in combination with hydroquinone.

Landscapes

  • 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)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Silver Salt Photography Or Processing Solution Therefor (AREA)
US00192953A 1970-10-27 1971-10-27 Method for developing silver halide photosensitive material Expired - Lifetime US3822130A (en)

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
JP45094869A JPS4843814B1 (Direct) 1970-10-27 1970-10-27

Publications (1)

Publication Number Publication Date
US3822130A true US3822130A (en) 1974-07-02

Family

ID=14122039

Family Applications (1)

Application Number Title Priority Date Filing Date
US00192953A Expired - Lifetime US3822130A (en) 1970-10-27 1971-10-27 Method for developing silver halide photosensitive material

Country Status (5)

Country Link
US (1) US3822130A (Direct)
JP (1) JPS4843814B1 (Direct)
DE (1) DE2153632A1 (Direct)
FR (1) FR2113245A5 (Direct)
GB (1) GB1344897A (Direct)

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS54142112U (Direct) * 1978-03-25 1979-10-02

Also Published As

Publication number Publication date
GB1344897A (en) 1974-01-23
DE2153632A1 (de) 1972-05-04
JPS4843814B1 (Direct) 1973-12-20
FR2113245A5 (Direct) 1972-06-23

Similar Documents

Publication Publication Date Title
US3221023A (en) (2-hydroxymethyl-3-pyrazolidones)
US3269840A (en) Method and material for surface brightening layers containing gelatin as the binding agent using anionic water-soluble diaminostilbene fluorescent compounds
US3447925A (en) Anti-fogging and anti-plumming disulfide compound for use in silver halide photographs
CA1060697A (en) Processing solution for use as photographic developer bath and replenisher therefor
US2214446A (en) Photographic development of silver halide layers
US4810623A (en) Development of photographic silver halide emulsion materials
US4330617A (en) Photographic elements containing novel developing agent precursors
US3822130A (en) Method for developing silver halide photosensitive material
US2339309A (en) Photographic reducing composition and process
US3804624A (en) Method for developing silver halide photosensitive material
US3712818A (en) Photographic stabilising or fixing bath
US3801323A (en) Method of developing silver halide photosensitive material
US3615607A (en) Method of desensitizing light-sensitive silver halide photographic materials with cycloheptimidazole derivatives
US3162534A (en) Photographic developer
US3169863A (en) Pentaerythritol phosphoric acid ester sensitizers for photographic emulsions
US3794489A (en) Method of developing silver halide photosensitive material
US3396022A (en) Quinone stabilizers and antifoggants for silver halide emulsions
US3782946A (en) Photographic development
US3873315A (en) Method of developing silver halide photosensitive material
US3600181A (en) Fog reduction of photographic silver halide emulsions by incorporation of a nitrocinnamic acid,or cinnamaldehyde in a contiguous layer
US3969117A (en) Lithographic developing process utilizing a silver halide photographic material containing hydroimidazo-s-triazine and polyalkylene oxide derivative
US3687669A (en) Process for low contrast development
EP0446457B1 (en) Alkaline black-and-white photographic developer
DE1622270A1 (de) Verfahren zum Stabilisieren von photographischem Material und photographisches Material zur Durchfuehrung des Verfahrens
US3725077A (en) Silver halide emulsions stabilized with nitroso derivatives of phenols