WO1980001962A1 - Protection d'images photographiques contre l'attaque par des peroxydes - Google Patents

Protection d'images photographiques contre l'attaque par des peroxydes Download PDF

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Publication number
WO1980001962A1
WO1980001962A1 PCT/GB1980/000045 GB8000045W WO8001962A1 WO 1980001962 A1 WO1980001962 A1 WO 1980001962A1 GB 8000045 W GB8000045 W GB 8000045W WO 8001962 A1 WO8001962 A1 WO 8001962A1
Authority
WO
WIPO (PCT)
Prior art keywords
catalyst
photographic material
layer
manganese dioxide
solution
Prior art date
Application number
PCT/GB1980/000045
Other languages
English (en)
Inventor
R King
P Bly
Original Assignee
Kodak Ltd
Eastman Kodak Co
R King
P Bly
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 Kodak Ltd, Eastman Kodak Co, R King, P Bly filed Critical Kodak Ltd
Priority to DE8080900467T priority Critical patent/DE3061021D1/de
Publication of WO1980001962A1 publication Critical patent/WO1980001962A1/fr

Links

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
    • G03C5/268—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
    • 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
    • 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
    • G03C11/00—Auxiliary processes in photography
    • G03C11/06—Smoothing; Renovating; Roughening; Matting; Cleaning; Lubricating; Flame-retardant treatments

Definitions

  • This invention relates to the protection of photographic silver images against the action of peroxides. It is known that processed silver halide emulsion photographic materials and especially microfilms are susceptible to the formation of microscopic spot blemishes when stored under adverse conditions. The defect is described in an article entitled 'Microscopic Spots in Processed Microfilm Their Nature and Prevention' published in Photographic Science and Engineering, Vol. 7, No. 5, p. 253, 1963. Oxidationreduction reactions between silver and peroxides are believed to be the cause of the defects.
  • the present invention provides a solution to the problem of peroxide microspots which is simple, of low cost and permanent.
  • a method of protecting silver images formed in a photographic material against attack by peroxides comprising contacting the material with a catalyst for the decomposition of hydrogen peroxide or a precursor of such a catalyst.
  • finely divided, preferably colloidal, particles of the catalyst are incorporated into the photographic material during manufacture in a layer on the same side of the support as a photosensitive silver halide layer.
  • the catalyst may be incorporated in any layer in an amount which does not interfere with the sensitometric properties of the material.
  • the catalyst is incorporated in a layer or layers adjacent the silver halide emulsion layer
  • the catalyst may be incorporated in a sublayer between the emulsion layer and the support and/or in an overlayer on the other side of the emulsion layer.
  • the catalyst may comprise gold, palladium or platinum but is preferably manganese dioxide.
  • Colloidal manganese dioxide may be incorporated into a photographic silver halide material in amounts of from 50 to 500mg/m 2 , preferably from 100 to 300 mg/m 2 . As indicated above it may be located in a sub-layer and/or overlay and the amounts used are preferably from 50 to 250 mg/m 2 in the sublayer and from 5 to 50 mg/m 2 in the overlayer.
  • the preferred catalyst particles are colloidal.
  • the size of colloidal particles may vary widely, e.g. 10 -7 - 10 -3 cm, as is known but sizes up to 500 ⁇ or even 1000 ⁇ are possible with the preferred particles being no larger than 150 ⁇ .
  • the thickness of such layers may vary widely but thicknesses in the range 0.5 to 3.0 ⁇ m for the overlayer and 0.5 to 5.0 ⁇ m for the sub-layer are preferred.
  • the catalyst can be coated in a hydrophilic binder over a layer already containing a silver image.
  • the catalyst is present in a layer containing hydrophilic binder which is preferably gelatin, an acylated gelatin, polyvinyl alcohol or mixtures thereof.
  • Photographic materials containing manganese dioxide catalyst should not be subjected to prolonged contact with acid fixer solutions containing sulphite ions as this can dissolve the catalyst and remove it from the material.
  • acid fixer solutions containing sulphite ions e.g. an alkaline thiosulphate solution is therefore preferred.
  • the silver image is treated with an aqueous solution of a catalyst precursor.
  • the precursor is then converted to the catalyst either by a comparatively slow oxidative process involving atmospheric oxygen and/or peroxides or by a further processing step.
  • the treatment with the catalyst precursor solution may, for example, take place as a final processing step or at any time after processing has otherwise been completed. Since the catalyst precursor is water-soluble any processing after its application to the photographic material will normally be avoided as this would tend to remove it.
  • the preferred catalyst precursor is a watersoluble manganese (II) salt, e.g. manganous sulphate, nitrate or chloride.
  • the solution preferably contains from 0.02 to 0.25, more preferably 0.025 to 0.1, moles manganese (II) salt per litre and optionally contains non-phosphate buffers to maintain the solution between pH 6.5 and 7.5.
  • the time of treatment may vary widely between, for example, 1 second up to several minutes preferably from 5 to 30 seconds.
  • the temperature of the treatment may also vary widely and, apart from its usual relationship with the time of treatment, is not considered critical.
  • the catalyst precursor solution preferably contains a wetting agent to provide an even distribution of catalyst precursor in the photographic material and to avoid the formation of salt spots on drying. Any wetting agent may be used, e.g. an anionic, cationic or non-ionic wetting agent.
  • Water-soluble compounds known to absorb strongly and stabilize filamentary silver images may also be included in the solution, for example nitrogencontaining heterocyclic compounds and thiols, e.g. imidazole and l-phenyl-5-mercaptotetrazole.
  • the present invention further provides a photosensitive photographic material comprising a support bearing at least one silver halide emulsion layer which has incorporated in a layer adjacent thereto finely divided, preferably, colloidal, particles of a catalyst for the decomposition of hydrogen peroxide.
  • the photographic materials protected from peroxide attack by the present invention are preferably microfilm materials but may be any photographic material, for example as described in Research Disclosure, December
  • Example 2 50 mls of the above colloidal manganese dioxide solution were added to 450 mls of a 1096 gelatin solution adjusted to pH 6.5. The gelatin solution was then coated over a silver-containing gelatin layer on a polyethylene terephthalate film at the rate of 1.3 mls/sq.ft to give a MnO 2 laydown of 2.10 mg/m 2 . Acceleration tests using hydrogen peroxide as described in Henn and Wiest - Photographic Science and Engineering, Vol. 7 , Number 5, September - October 1963, page 253j failed to induce spotwise attack on such coati whereas similar control coating without manganese dioxid showed the expected spotwise attack.
  • Example 2 50 mls of the above colloidal manganese dioxide solution were added to 450 mls of a 1096 gelatin solution adjusted to pH 6.5. The gelatin solution was then coated over a silver-containing gelatin layer on a polyethylene terephthalate film at the rate of 1.3 mls/s
  • a photographic microfilm material was prepared by coating on a polyethylene terephthalate film base, a dye-containing anti-halation underlayer containing colloidal manganese dioxide coated at 151 mg/m 2 and gela at 1.90 g/m 2 , a fine grain negative emulsion layer and a gelatin supercoat containing colloidal manganese dioxide coated at 9 mg/m 2 and gelatin at 0.89 g/m 2 .
  • Another photographic microfilm material was prepared by coating on a polyethylene terephthalate film base, a dye-containing anti-halaticn underlayer containing colloidal manganese dioxide coated at 176 mg/m 2 and gelatin at 1.90 g/m 2 , a fine grain negative emulsion layer coated at 1.77 g Ag/m 2 and a gelatin supercoat at 0.89 g/m 2 .
  • the processed films were incubated at 49°C, 8496 RH in an atmosphere containing 150 ppm hydrogen peroxide for 64 hours.
  • control experimental film showed severe microspot attack whilst all samples of the experimental films containing colloidal manganese dioxide in the underlayer and supercoat were unaffected. At higher peroxide concentrations (600 ppm) none of the samples showed microspot attack but the control film showed a significant loss of density after 3 days. The film, containing manganese dioxide was unaffected.

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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)
  • Catalysts (AREA)
  • Silver Salt Photography Or Processing Solution Therefor (AREA)

Abstract

Une methode de protection d'images argentiques formees dans un materiau photographique, specialement un microfilm, contre l'attaque par des peroxydes consiste a mettre en contact le materiau avec un catalyseur pour decomposer l'eau oxygenee ou un precurseur d'un tel catalyseur. La mise en contact peut avoir lieu apres la formation de l'image en utilisant une solution d'un precurseur, par exemple un sel de manganese (II) ou on peut incorporer un catalyseur, par exemple un bioxyde de manganese colloidal pendant la fabrication dans une couche de materiaux adjacente a une couche d'halogenure d'argent.
PCT/GB1980/000045 1979-03-14 1980-03-14 Protection d'images photographiques contre l'attaque par des peroxydes WO1980001962A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
DE8080900467T DE3061021D1 (en) 1979-03-14 1980-03-14 Protecting photographic images against microspot attack

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
GB7908972 1979-03-14
GB7908972 1979-03-14

Publications (1)

Publication Number Publication Date
WO1980001962A1 true WO1980001962A1 (fr) 1980-09-18

Family

ID=10503862

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/GB1980/000045 WO1980001962A1 (fr) 1979-03-14 1980-03-14 Protection d'images photographiques contre l'attaque par des peroxydes

Country Status (3)

Country Link
EP (1) EP0025441B1 (fr)
DE (1) DE3061021D1 (fr)
WO (1) WO1980001962A1 (fr)

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0105004A2 (fr) * 1982-09-29 1984-04-04 EASTMAN KODAK COMPANY (a New Jersey corporation) Utilisation de composés du manganèse pour la stabilisation de la densité de l'image dans un matériau d'enregistrement par transfert
US4471049A (en) * 1983-04-12 1984-09-11 Eastman Kodak Company Dye image-generating photographic elements
WO1990013061A1 (fr) * 1989-04-26 1990-11-01 Kodak Limited Procede de formation d'une image couleur photographique

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2839405A (en) * 1955-03-08 1958-06-17 Eastman Kodak Co Inorganic salt antifoggants for photographic emulsions
GB1138087A (en) * 1966-10-13 1968-12-27 Criterion Plates Papers Films Improvements relating to photographic processes and films

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2839405A (en) * 1955-03-08 1958-06-17 Eastman Kodak Co Inorganic salt antifoggants for photographic emulsions
GB1138087A (en) * 1966-10-13 1968-12-27 Criterion Plates Papers Films Improvements relating to photographic processes and films

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
Photographic Science and Engeneering, Volume 9, No. 6, published November 1965, (Society of Photographic Scientics and Engineers, Washington D.C.20005 US) R.W.Henn and B.D. Mack: " A Gold Protective Treatment for Microfilm", see pages 378-384. *

Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0105004A2 (fr) * 1982-09-29 1984-04-04 EASTMAN KODAK COMPANY (a New Jersey corporation) Utilisation de composés du manganèse pour la stabilisation de la densité de l'image dans un matériau d'enregistrement par transfert
EP0105004A3 (fr) * 1982-09-29 1985-12-18 EASTMAN KODAK COMPANY (a New Jersey corporation) Utilisation de composés du manganèse pour la stabilisation de la densité de l'image dans un matériau d'enregistrement par transfert
US4471049A (en) * 1983-04-12 1984-09-11 Eastman Kodak Company Dye image-generating photographic elements
EP0122142A2 (fr) * 1983-04-12 1984-10-17 EASTMAN KODAK COMPANY (a New Jersey corporation) Eléments photographiques générateurs d'images couleurs et méthodes de formation d'images couleurs utilisant ceux-ci
EP0122142A3 (en) * 1983-04-12 1986-01-29 Eastman Kodak Company Dye image-generating photographic elements and methods of forming dye images therewith
WO1990013061A1 (fr) * 1989-04-26 1990-11-01 Kodak Limited Procede de formation d'une image couleur photographique
US5260184A (en) * 1989-04-26 1993-11-09 Eastman Kodak Company Method of forming a photographic color image

Also Published As

Publication number Publication date
DE3061021D1 (en) 1982-12-09
EP0025441A1 (fr) 1981-03-25
EP0025441B1 (fr) 1982-11-03

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