US3558313A - Water wash for stabilized silver halide photographic materials - Google Patents

Water wash for stabilized silver halide photographic materials Download PDF

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Publication number
US3558313A
US3558313A US529696A US3558313DA US3558313A US 3558313 A US3558313 A US 3558313A US 529696 A US529696 A US 529696A US 3558313D A US3558313D A US 3558313DA US 3558313 A US3558313 A US 3558313A
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US
United States
Prior art keywords
silver halide
washing
photographic
halide photographic
image
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
US529696A
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English (en)
Inventor
Shunichiro Tsuchida
Tomiaki Miyata
Michihiko Takahashi
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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.)
Filing date
Publication date
Application filed by Fuji Photo Film Co Ltd filed Critical Fuji Photo Film Co Ltd
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Publication of US3558313A publication Critical patent/US3558313A/en
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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
    • G03C5/268—Processing baths not provided for elsewhere, e.g. pre-treatment, stop, intermediate or rinse baths
    • 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
    • G03C5/38—Fixing; Developing-fixing; Hardening-fixing
    • G03C5/39—Stabilising, i.e. fixing without washing out

Definitions

  • the present invention relates to a process for further increasing the stability of photographic images of silver halide photographic materials which have been developed and subjected to a so-called stabilizing treatment.
  • the developed silver halide photographic material is fixed and the remaining silver halide is converted into a light-unstable silver complex salt, which is then removed from the photographic material by water-washing.
  • the photographic material is subjected to a stabilizing treatment requiring no water-washing treatment to convert the unexposed silver halide into a light-stable silver complex salt, which is left in the thus stabilized silver halide photographic emulsion without being removed by water-washing.
  • the treatment can be done quickly, but, in general, the qualities of the image are accompanied with many faults.
  • the silver complex salt-forming agent is used in considerable excess of a theoretical amount to assure the stability of images to light, the hygroscopic property of the agent impedes the drying procedure and makes sticky the surface of the stabilized photographic material to be preserved. Further, there is a tendency in this case for the metallic silver composing the image to be gradually oxidized by the silver complex salt-forming agent into a silver complex salt, which reduces the photographic density of the image. That is, when the thus stabilized silver halide photographic material is preserved in the air, the color of the image of the photographic material is converted from black to brown or yellow owing to the reduction in photographic density and in an excessive case, the image tends to disappear. Such a phenom- 3,558,313 Patented Jan. 26, 1971 enon is liable to occur when the stabilized silver halide photographic material is preserved at high temperature and at high humidity.
  • water-washing has been considered to be undesirable in the case of applying stabilizing treatment, because (1) the silver complex salt formed by the conventional stabilizing treatment is stable in the state that the silver complex salt-forming is present in an excessive amount, and (2) because, even though the silver complex salt and the silver complex salt-forming agent are washed out by water, a slight amount of silver complex salt remains in the photographic material, in the case of using as a stabilizing agent thiocyanates or thiourea, which is very unstable and reduces markedly the image.
  • a stabilized silver halide photographic material is subjected to washing with water or an aqueous solution for a period of time to secure the stability of the silver complex salt, that is, for a period shorter than 60 seconds, whereby the reduction of the photographic density of the image, the discoloration of the photographic, and the formation of sticky surface of the photographic material are prevented.
  • the application of ferrotype drying to the stabilized silver halide photographic material is possible.
  • the washing bath in this invention may be used until the concentration of the silver complex salt-forming agent in the bath reaches 3%.
  • a fluorescent bleaching agent such as Whitex BH (made by Sumitomo Kagaku K.K.) and Kayaphor S (Nihou Kayaku K.K.) to increase the whiteness.
  • an ultraviolet absorbing agent such as, HPT (made by Dupont Company) and UV400 (made by Gen- 1eral Aniline & Film Corp.) to increase the stability of ight.
  • a photo-wetting agent such as, Dry Well (made by Fuji Photo-Film Co.), Konidux (made by Konishi Roku-Shashin Kogyo K.K.), and other surface active agents.
  • a hardening agent to reduce the stickiness of the surface of the emulsion layer of the photographic material, such as, potassium alum, chromium alum, acetic acid, formaline, etc.
  • EXAMPLE 1 A silver halide photographic light-sensitive paper and a silver halide photographic light-sensitive film were exposed, developed treated in a stabilizing solution mainly comprising ammonium thiocyanate, and then subjected to water-washing. The results of the procedures are shown in FIG. 1 of the accompanying drawings, in which the graph shows the relation of the photographic density and the washing period. The solid line corresponds to the case of the silver halide photographic paper and the dotted line to the case of the silver halide photographic film.
  • the results show that the water-washing treatment for a period of shorter than 60 seconds is effective for the prevention of reduction of photographic density of the photographic image by heat and humidity while sufficiently securing the light-stability of the image.
  • EXAMPLE 2 Instead of water-bath washing in Example 1, waterspray washing was conducted and the results are shown in FIG. 2 of the accompanying drawing in which the testing procedures are the same as those in the case of FIG. 1 in Example 1, As shown in the graph of FIG. 2, waterspray washing of shorter than 5 seconds is effective for preventing the reduction of photographic density of the photographic images by heat and humidity while securing the stability of the photographic material to light.
  • EXAMPLE 3 A silver halide photographic light-sensitive paper and a silver halide photographic light-sensitive film were exposed, developed, treated in a stabilizing solution mainly comprising thiourea, and then subjected to water-washing. The results are shown in FIG. 3 of the accompanying drawing. The testing procedures are the same as in the case of Example 1.
  • EXAMPLE 4 Into 1 liter of water-washing bath was dissolved 5 g. of a fluorescent bleaching agent, Whitex BH.
  • a stabilized silver halide photographic light-sensitive paper was treated by the bath as in Example 1, the whiteness of the white ground of the photographic paper was increased and the reduction of photographic density of the image was sufficiently prevented.
  • the results of testing preservability of the stabilized silver halide photographic paper subjected to the washing treatment for 2 seconds and a stabilized silver halide photographic paper subjected to no washing treatment (comparative sample) by the deterioration test, in the same manner as in Example 1, are as follows:
  • EXAMPLE 6 A washing bath prepared by dissolving ml. of an ultraviolet absorber HPT in 1 liter of water-washing bath was used. Decoloring of the image was prevented and also the reduction of photographic density of the 4 image was sufficiently prevented.
  • the results of the tests of the preservability of the stabilized silver halide photographic paper subjected to the washing treatment for 2 seconds and a stabilized comparative silver halide photographic paper subjected to no washing treatment are as follows:
  • EXAMPLE 8 A washing bath prepared by dissolving 15 g. of potassium alum and 10 ml. of acetic acid as a hardening agent in 1 liter of water-washing bath was used. By the treatment, the surface of the emulsion layer of a stabilized silver halide photographic material was hardened to reduce the stickiness of the surface and the reduction of the photographic density of the image was sutficiently prevented.
  • the results of the tests of the preservability of the stabilized silver halide photographic paper and silver halide photographic film subjected to the washing treatment for 30 seconds and comparative samples subjected to no washing treatment are as follows:
  • AD +AD Paper Film Paper Film Non-washed image O. 57 1. 00 0. 01 0. 01 Washed image 0. 14 0. 18 O. 02 0. O1
  • EXAMPLE 9 A washing bath prepared by dissolving 15 ml. of Formalin (37%), 0.5 g. of boric acid, and 5.5 g. of sodium carbonate as a hardening agent into 1 liter of a waterwashing bath was used. By the treatment, the surface of the emulsion layer of a silver halide photographic material was hardened to reduce the stickiness and also the reduction of the photographic density of the image was sufficiently prevented.
  • the results of the preservability tests are as follows:
  • said light-sensitive material is a silver halide light-sensitive film.

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  • Physics & Mathematics (AREA)
  • General Physics & Mathematics (AREA)
  • Silver Salt Photography Or Processing Solution Therefor (AREA)
US529696A 1965-02-24 1966-02-24 Water wash for stabilized silver halide photographic materials Expired - Lifetime US3558313A (en)

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
JP1032865 1965-02-24

Publications (1)

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US3558313A true US3558313A (en) 1971-01-26

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US529696A Expired - Lifetime US3558313A (en) 1965-02-24 1966-02-24 Water wash for stabilized silver halide photographic materials

Country Status (5)

Country Link
US (1) US3558313A (instruction)
BE (1) BE676853A (instruction)
CH (1) CH473404A (instruction)
DE (1) DE1547834A1 (instruction)
GB (1) GB1103806A (instruction)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4059446A (en) * 1975-04-30 1977-11-22 Agfa-Gevaert, N.V. Processing of photographic silver halide material

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4059446A (en) * 1975-04-30 1977-11-22 Agfa-Gevaert, N.V. Processing of photographic silver halide material

Also Published As

Publication number Publication date
GB1103806A (en) 1968-02-21
BE676853A (instruction) 1966-07-18
CH473404A (de) 1969-05-31
DE1547834A1 (de) 1969-12-04

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