US3762923A - Method for processing black and white photographic silver halidematerial - Google Patents

Method for processing black and white photographic silver halidematerial Download PDF

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Publication number
US3762923A
US3762923A US00124942A US3762923DA US3762923A US 3762923 A US3762923 A US 3762923A US 00124942 A US00124942 A US 00124942A US 3762923D A US3762923D A US 3762923DA US 3762923 A US3762923 A US 3762923A
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US
United States
Prior art keywords
developing
bleaching
seconds
silver
fixing
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
US00124942A
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English (en)
Inventor
Yama M Sug
S Ishiguro
N Sugiyama
H Iwano
Y Iijima
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Fujifilm Holdings Corp
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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.)
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Publication date
Application filed by Fuji Photo Film Co Ltd filed Critical Fuji Photo Film Co Ltd
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Publication of US3762923A publication Critical patent/US3762923A/en
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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
    • 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
    • G03C5/40—Chemically transforming developed images
    • G03C5/44—Bleaching; Bleach-fixing
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10S430/00—Radiation imagery chemistry: process, composition, or product thereof
    • Y10S430/15—Lithographic emulsion

Definitions

  • a high contrast silver halide material generally called lith film
  • the original with continuous gradation is divided into a group of dots arranged in a network. That is to say, the density change is converted into an area change of dots and recorded on the lith film.
  • Division into a dot group of a network is carried out by the use of a glass cross screen or contact screen. An image of the original is printed through such screen on a lith film or plate and then subjected to development, thus obtaining a dotted image.
  • Such dot image consist of image spots having a maximum density andbackground having a minimum density, but formation of intermediate density zones called fringe" around the dots is unavoidable since even a high contrast photographic light-sensitive material has an intermediate density or so-called half tone portion.
  • the fringe tends to degrade the quality of a printed image-and, accordingly, is not preferred in plate making. The less the fringe is, the better the quality of the dot image.
  • Development of a lith film or lith plate is ordinarily carried out with an alkaline developer containing hydroquinone as a developing agent and an aldehyde-alkali metal bisulfite adduct, ascorbic acid and an acetonebisulfite adduct as a preservative.
  • Method I l. lith development 2. stopping 3. bleaching 4. rinse 5. second development 6. stopping 7. fixing 8. water washing Method II lith development bleaching rinse second development stopping fixing water washing Method III lith development bleaching rinse mono both development and fixing water washing Method IV same as Method III except rinse step is omitted.
  • the lith development as the first step is similar to the ordinary lith development (so-called infectious developer), i.e., using a lith developer containing a developing agent, such as hydroquinone, a preservative such as a sodium bisulfite-paraformaldehyde adduct, ascorbic acid or kojic acid, an alkaline agent, such as sodium carbonate or caustic soda, and a fog inhibitor, such as potassium bromide or l-phenyl-5-mercaptotetrazole.
  • a developing agent such as hydroquinone
  • a preservative such as a sodium bisulfite-paraformaldehyde adduct
  • ascorbic acid or kojic acid an alkaline agent
  • an alkaline agent such as sodium carbonate or caustic soda
  • a fog inhibitor such as potassium bromide or l-phenyl-5-mercaptotetrazole.
  • Developer Super Lithodol (trademark, manufactured
  • the lith development can be completely stopped for 10 seconds.
  • the bleaching bath may hold another action asa stopping bath.
  • the bleaching bath contains an oxidizing agent and a halide compound, and if necessary, may contain an acid or an alkali as a pH regulator, another salt having a buffering action and a further salt to raise the ionic strength.
  • the oxidizing agent there are used potassium or sodium bichromate, ferricyanide and sodium or ammonium persulfate, and as the halide compound, there are used sodium, potassium and ammonium chloride, bromide and iodide.
  • an acid such as acetic acid, hydrochloric acid or nitric acid, and a salt, such as sodium acetate or sodium hydrogen phosphate may be added.
  • Bleaching time depending upon the variety of a light-sensitive material as well as the composition of the bath, may range from 5 to 100 seconds, preferably to 30 seconds. In this case, the bleaching solution must have a pH of no less than I to prevent the dissolution of silver.
  • the step of rinsing after the bleaching step may ordinarily be carried out by immersing in water for several seconds to 1 minute. Flowing water may be used or the rinsing step may be omitted as in usual IV without any substantial effects. 1-2 percent aqueous solutions of sodium sulfite may be used as a rinse solution. In any case, a suitable procedure may be taken as the occasion demands since this step serves to prevent the second developer from contamination of the bleaching solution so as to lengthen the effective life thereof.
  • the step of second development following the rinse step is not always carried out by the lith development, but the commonly used black-and-white developer may also be used.
  • commercial developers such as Super Lithodol and other developers such as D-76, D-72, D-8, FD-3, FD-3l, D-85, FD-l85, PM-MK and D-l9 mentioned in "Kaguku Shashin Benran” II Ed., pages 58-67 (published by Maruzen Co.) may be used.
  • developer there may be incorporated one or more developing agents, such as metol(pmethylaminophenol sulfate), hydroquinone, l-phenyl- 3-pyrazolidone, 2,4-diaminophenol hydrochloride and N,N-diethyl-p-phenylenediamine, one or more of alkaline agents, such as sodium carbonate, caustic soda, trisodium phosphate, borax and potassium metaborate, one or more preservatives, such as sodium sulfite, ascorbic acid and hydroxylamine and other developing aids.
  • developing agents such as metol(pmethylaminophenol sulfate), hydroquinone, l-phenyl- 3-pyrazolidone, 2,4-diaminophenol hydrochloride and N,N-diethyl-p-phenylenediamine
  • alkaline agents such as sodium carbonate, caustic soda, trisodium phosphate, borax and potassium metaborate
  • the second developer may be a mono-bath developing and fixing solution as mentioned in Method III.
  • the one-bath developing and fixing solution may be prepared by adding to the above-mentioned black-and-white developer one or more silver halide dissolving agents, such as sodium thiosulfate, potassium thiocyanate, ammonium thiosulfate, sodium thiocyanate and thioglycollic acid and adjusting suitably the pH and concentrations of the chemicals.
  • the basic consideration of the composition thereof is disclosed by A. A. Newman in the British Journal of Photography 106, 4448, 56, 66-68 (1959).
  • the period of time for the second development is about 10 to 200 seconds, preferably 30-80 seconds in respect of the workability.
  • the method of this invention is apparently similar to the method of treating a black-and-white reversal film, but in practice they are essentially different.
  • the steps of bleaching and second development are also carried out following the developing step. In this case, however, I
  • the bleaching solution used is a sulfuric and acetic acid acidic solution of potassium bichromate (pH: less than l) which is much stronger than the bleaching solution of this invention and capable of oxidizing and dissolving the developed silver completely.
  • the bleaching solution of this invention holds the developed silver forming a dot image as it is in the film.
  • the radiation of white light is not carried out and, therefore, the unexposed area is not developed even in the second development; only the dot area is developed. This is a negative development.
  • dot etching which is often carried out after development to improve the dot quality of screened negatives, is not required according to the method of the invention.
  • Another advantage of this invention is that it is possible to make thinner the thickness of an emulsion on a lith film or lith plate, thus saving the emulsion.
  • the lith film or lith plate has an emulsion layer containing a relatively large amount of silver halide in order to raise sufficiently the blackened density of a dot image and to make the fringe as little as possible. Therefore, it is relatively expensive.
  • the method of the invention can give such an excellent dot image quality that saving of silver halide is possible by thinning the emulsion layer or by decreasing the content of silver halide in the emulsion layer.
  • the method of this invention is applicable to treatment of any lith film or lith plate. It is applicable to any of silver chloride, silver bromide, silver chlorobromide and silver chloroiodobromide. Furthermore, it may be used irrespective of color sensitization, chemical sensitization and addition of a sensitizer, such as polyethylene glycol, or fog inhibitor, such as tetrazaindene and other additives.
  • a sensitizer such as polyethylene glycol
  • fog inhibitor such as tetrazaindene and other additives.
  • the foregoing illustration is based on only a dot image photographic material, but the method of the invention is applicable to processing of X-ray photographic materials, facsimile films and photographic plates for making an integrated circuit, and other black-and-white negative photographic materials.
  • the resulting image is hardened and highly densed.
  • development may be carried out with an ordinary developer.
  • EXAMPLE 1 A commercial lith film was subjected to stepwise dot image exposure through a magenta contact screen of I33 lines and step wedge for sensitometry and then subjected to the following two developments for comparison:
  • Dot Area Ratio means a ratio of the blackened parts of dots to a sample area
  • Extension of Fringe means a value of the size of a dot at a trace image density of 0.3 (diameter) minus the size at a density of 2.5.
  • a commercial lith film was exposed in a similar manner to that of Example I and then subjected to the following treatment:
  • Bleaching solution VI potassium bichromate 20 g 3% aqueous solution of hydrochloric acid I50 ml water to I000 ml Second developer II The following compounds are added per 1000 ml of Developer I: addition salt of formaldehyde.
  • Second developer in Improved treatment H is substituted by the following Second developer III Second Developer Ill Potassium thiocyanate of Second developer II is converted into 70 g/l of sodium thiosulfate As is evident from the results shown in Table 3, the effects of the invention can be attained even if the processings after the second development are simplified by a one-bath developing and fixing solution.
  • EXAMPLE 4 A support member was coated with each of silver chloride, silver bromide and silver chlorobromide (silver chloride 70 mol percent) to prepare a photographic film, which was then subjected to dot image photographing in a similar manner to that of Example I and Standard treatment of the prior art and Improved treatment K.
  • a coated silver amount 51 mg Ag/dm B coated silver amount 42 mg Ag/dm C coated silver amount 32 mg Ag/dm Sample A has a coated silver amount necessary for the ordinary lith film but the coated silver amount of Samples B and C is not sufficient to give a dot image quality by the known lith developing method.
  • EXAMPLE 8 A film base was coated with a silver iodobromide gelatin emulsion (silver iodide 5 mol percent) so as to give a coated silver amount of 40 mg/dm to thus obtain a light-sensitive material for X-rays, which was then subjected to sensitometric exposure and to the following treatment:
  • Prior art method of invention development 34 C 60 seconds same as prior art rinse 34 C 30 seconds same as prior art fixing 34 C seconds water washing 34 C 60 seconds bleaching 34 C 40 seconds rinse 34 C 10 seconds redevelopment 34 C I50 seconds caustic soda 32 g sodium sulfite 83 g I-phenyl-S-pyrazolidone 6.7 g hydroquinone 58 g sodium thiosulfate 92 g potassium iodide 03 g water to I000 ml
  • the sample treated by the method of this invention gave an increase of 50 percent to the sensitivity represented by the reciprocal of exposure quantity giving a density of above 0.2 fog, as compared with that treated by the prior art method.
  • the gamma was increased by 0.3.
  • increase of fog could be suppressed to 0.03 as compared with 0.09 of the prior art method.
  • EXAMPLE 9 A superfine grain and high resolving power dry plate of silver chlorobromide was subjected to sensitometric exposure and to the following treatment:
  • said developer further contains at least one member selected from the group consisting of ascorbic acid and sodium sulfite.
  • a method for treating an exposed black-and-white negative photographic material to obtain a high contrast silver image, wherein the chloride content of said silver halide material is present in an amount of at least mol percent which comprises the steps of:
  • step (c) 14. The method of claim 1, further comprising a fixing step, which step takes place either during or after step (c).

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  • Physics & Mathematics (AREA)
  • General Physics & Mathematics (AREA)
  • Silver Salt Photography Or Processing Solution Therefor (AREA)
US00124942A 1970-03-16 1971-03-16 Method for processing black and white photographic silver halidematerial Expired - Lifetime US3762923A (en)

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
JP45022178A JPS5023615B1 (fr) 1970-03-16 1970-03-16

Publications (1)

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US3762923A true US3762923A (en) 1973-10-02

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Country Status (4)

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US (1) US3762923A (fr)
JP (1) JPS5023615B1 (fr)
FR (1) FR2084666A5 (fr)
GB (1) GB1287547A (fr)

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4113489A (en) * 1972-03-01 1978-09-12 Fuji Photo Film Co., Ltd. Method of forming photographic line and half-tone images
US4172728A (en) * 1977-12-16 1979-10-30 E. I. Du Pont De Nemours And Company High contrast continuous tone developer and process of use
US4191575A (en) * 1972-12-07 1980-03-04 Philip A. Hunt Chemical Corp. Two-step photographic processing of black and white images which enhances the images by controlled bleaching during fixing immediately following development and which produces black and white images with reduced density in low density areas

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH03187155A (ja) * 1989-12-15 1991-08-15 Fuji Elelctrochem Co Ltd スパイラル形非水電解液電池

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4113489A (en) * 1972-03-01 1978-09-12 Fuji Photo Film Co., Ltd. Method of forming photographic line and half-tone images
US4191575A (en) * 1972-12-07 1980-03-04 Philip A. Hunt Chemical Corp. Two-step photographic processing of black and white images which enhances the images by controlled bleaching during fixing immediately following development and which produces black and white images with reduced density in low density areas
US4172728A (en) * 1977-12-16 1979-10-30 E. I. Du Pont De Nemours And Company High contrast continuous tone developer and process of use

Also Published As

Publication number Publication date
GB1287547A (en) 1972-08-31
JPS5023615B1 (fr) 1975-08-08
DE2112530A1 (de) 1971-10-14
DE2112530B2 (de) 1976-02-12
FR2084666A5 (fr) 1971-12-17

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