US3817751A - Color forming agents for the peroxide color intensifying process - Google Patents

Color forming agents for the peroxide color intensifying process Download PDF

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Publication number
US3817751A
US3817751A US00246387A US24638772A US3817751A US 3817751 A US3817751 A US 3817751A US 00246387 A US00246387 A US 00246387A US 24638772 A US24638772 A US 24638772A US 3817751 A US3817751 A US 3817751A
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United States
Prior art keywords
compounds
peroxide
color
substituted
color forming
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Expired - Lifetime
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US00246387A
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English (en)
Inventor
R Matejec
W Puschel
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Agfa Gevaert AG
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Agfa Gevaert AG
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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
    • G03C1/00—Photosensitive materials
    • G03C1/64—Compositions containing iron compounds as photosensitive substances
    • 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
    • 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
    • G03C5/56—Processes using photosensitive compositions covered by the groups G03C1/64 - G03C1/72 or agents therefor
    • 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
    • Y10S430/144—Hydrogen peroxide treatment

Definitions

  • the invention relates to a process for the production of photographic images by imagewise decomposition of peroxide compounds in the presence of compounds for a color forming oxidation reaction.
  • catalytic decomposition is meant here the catalytic activation of the peroxide which is required for the color forming oxidation reaction.
  • a light-sensitive layer is exposed imagewise to produce in imagewise distribution nuclei of noble metals of Groups Ib and/or VIII of The Periodic Table.
  • the layer containing the nuclei is then treated with peroxide compounds which decompose cataltyically at the nuclei in the image areas in the presence of reactants for a color forming oxidation reaction.
  • the layers used for the above mentioned process for the production of photographic images may contain substances which yield other peroxidase active catalyst on exposure. Suitable for this process are, for example, certain complex compounds of heavy metals of Groups VIb, VIIb and VIH of The Periodic Table with a monobasic or polybasic carboxylic acid or other ligands. Compounds which split off iodine ions on exposure to light I have the same effect.
  • the process may also be carried out with light-sensitive photographic materials which contain, uniformly distributed, catalase active enzymes such as catalase, peroxidase, haemoglobin or haemin which are inactivated in the image areas when exposed to actinic light. Direct positive images are obtained with these materials.
  • catalase active enzymes such as catalase, peroxidase, haemoglobin or haemin which are inactivated in the image areas when exposed to actinic light. Direct positive images are obtained with these materials.
  • R hydrogen, alkyl having up to 18, preferably up to 5 carbon atoms which may contain additional substituents, e.g. carboxyl or hydroxyl or aryl, in particular phenyl in which the phenyl ring may contain the substituents listed under R R and K, have the same meaning as R R has the same meaning as R or alternatively R and R and/or R and R may also denote the ring members required to complete a heterocyclic saturated or unsaturated S-membered or 6-membered ring which contains nitrogen.
  • the nitrogen atom of the CN-bond in the above formulae may be present in quaternized form.
  • Some of the above compounds are already known as photographic developing agents. Of course one can only use compounds as photographic developing agents which have a suitable redox potential in the required pH region, i.e. which are capable of reducing silver halides to metallic silver.
  • these substances are used as reactants for a color forming coupling reaction which requires the decomposition of the peroxide compound as oxidizing agent.
  • the oxidative coupling reaction has nothing whatever to do with the photographic devolopment of exposed silver halide. Consequently, when these substances are used in accordance with this invention, they are not required to satisfy any conditions as regards their activity within certain, relatively narrow pH ranges.
  • the color forming agents must also satisfy certain requirements as regards their electrochemical properties. Thus, they should have an auodic redox potential which is more negative at the pH values employed than the cathodic redox potential of the peroxide compound used, with the additional requirement that the difference between these two redox potentials must not exceed the value which corresponds to the activation energy required for the (non-catalytic) decomposition of the peroxy compound.
  • these activation energies are very high and furthermore it is possible by suitable choice of various inorganic and/or organic peroxy compounds to cover an almost unlimited range of potentials. Hence even those compounds of structural formulae (I) and (II) which are not operative as photographic developers are suitable for use as color forming agents for the catalytic dye formation.
  • substances which cannot be used as photographic developers yield, for example, brownish black to black dyes by catalytic dye formation on the image silver by decomposition of the peroxy compound, in particular H 0
  • the substances for use according to the invention may also be used in admixture with other reactants, e.g. pyrocatechol, resorcinol, orthoand para-phenylene diamines, diamine, N-allyland N,N-dialkyl-phenylenediamine. Further improvement in dye formation can thereby be obtained.
  • reactants e.g. pyrocatechol, resorcinol, orthoand para-phenylene diamines, diamine, N-allyland N,N-dialkyl-phenylenediamine.
  • Production of the photographic images may be carried out in various ways by known methods. It is practically immaterial which peroxides active catalysts distributed in accordance with the image are used for the imagewise activation of the peroxide compound. It is preferred to use layers which upon exposure produce imagewise nuclei of noble metals of the Groups IB and/or VIII of The Periodic Table which in turn catalytically accelerate the decomposition of the peroxide compound. Photographic materials of this kind have been described in the above British Patent Specification.
  • Patent Applications relate to a light-sensitive material which contains compounds which on exposure to light form catalase active and/or peroxidase active catalysts. These are complex compounds of metals of Groups VIB, VIIB or VIII of The Periodic Table of Elements.
  • the light-sensitive layer contains a compound which splits oft catalase active or peroxidase active iodine ions on exposure to light.
  • the material described there enables direct positive images to be produced.
  • the light-sensitive layer contains catalase active and/or peroxidase active enzymes which are inactivated on exposure to light. The material is then treated with hydrogen peroxide, decomposition then taking place only in the areas which have not been struck by light.
  • Suitable peroxide compounds are e.g. inorganic peroxide compounds such as perborates, percarbonates, persilicates, perphosphates or persulfates.
  • Organic peroxide compounds may also be used, e.g. benzoyl peroxide.
  • Hydrogen peroxide is particularly suitable owing to its efiicient action and the ease with which it can be handled in the form of aqueous solutions.
  • addition compounds v of hydrogen peroxide with organic compounds especially urea, acid amides, polyhydroxyl compounds or amines.
  • EXAMPLE 1 5 litres of an 8% aqueous gelatin solution are added to 1 litre of a highly sensitive silver iodobromide gelatin emulsion (4.5 mol-percent/Agl). The mixture is adjusted to pH 5.5. 200 g. of compound 44 are then suspended in this mixture which is then cast on a support of poly- Bath I:
  • a black dye image (negative of the exposure original) is produced catalytically on the image silver with the aid of the peroxide introduced into the layer.
  • the layer is finally stabilized and fixed by introducing it for seconds into a solution of the following composition at 35 C.:
  • This bath HI stabilizes the dye image to such an extent that subsequent washing is not absolutely necessary.
  • a brief final washing e.g. 10 seconds is recommended only if the images are to be stored for a long time (e.g. longer than 2 months).
  • the color density of the dye image can be increased by briefly heating the layer between bath H and bath III (e.g. by infra-red radiation for 10 seconds at about 80 C.).
  • water 5 g. of K Fe(CN) are dissolved in 50 cc. of water 1 g. of citric acid is dissolved in 10 cc. of water 12 g. of gelatin are dissolved in 200 cc. of water.
  • the above solutions are mixed together in red darkroom light and the mixture is cast on a support of cellulose triacetate.
  • the thickness of the dried layer is about 10 to 20,.
  • the layer is hardened in the usual manner, by addition of a 2 ml. of a 30% aqueous solution of formalin or mucochloric acid.
  • the dried layer is exposed imagewise behind a grey step in a conventional sensitometer (100 watt lamp, exposure time 10 seconds). It is then exposed to a water vapour atmosphere at about 80 C. for about 10 to 20 seconds and then hardened for 30 seconds by spraying water on it.
  • a black negative image of the original is obtained.
  • EXAMPLE 3 A transparent support of cellulose triacetate is coated with a solution containing 6 ml. of a 10% aqueous solution of polyvinyl alcohol and 2 g. of TiO: reduced to a particle size of 0.3 to 0.4 pm. and 0.1 mg. of erythrosine as spectral sensitizer in 400 cc. of water. The layer is then dried.
  • the dried layer is exposed imagewise and then treated for 30 seconds in the following bath at 20 C.:
  • Bath I 2% aqueous NaPd(C O solution.
  • the layer is then introduced for 30 seconds into a bath of the following composition at 20 C. to effect catalytic dye formation:
  • the improvement comprises the color forming compound is an organic compound having an anodic redox potential more negative than the cathodic redox potential of the 11 12 peroxy compound and containing a CN single or double 2.
  • R Rifi R1 mil-1 km
  • R -J: 5 References Cited (I) n UNITED STATES PATENTS wherein 3,674,490 7/1972 Metejec 96 48 PD 3 503 744 3/1970
  • Itano 96-48 R R aryl substituted with hydroxyl and/0r ammo groups
  • R2 hydmgen, alkyl or and 10 3,697,275 10/1972 Hayakawa et al 9648 R 11: and ⁇ ; have the same meimng as R RONALD H. SMITH, Primary Examiner as esame meamn as ()1? alternatively g 1 I. L. GOODROW, Assistant Examiner R and R and/or R and R may also denote the ring members required to complete a heterocyclic saturated 15 9688 90 R Us or unsaturated S-membered or 6-membered ring.

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  • Physics & Mathematics (AREA)
  • General Physics & Mathematics (AREA)
  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Pyridine Compounds (AREA)
  • Non-Silver Salt Photosensitive Materials And Non-Silver Salt Photography (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
US00246387A 1971-04-24 1972-04-21 Color forming agents for the peroxide color intensifying process Expired - Lifetime US3817751A (en)

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
DE19712120091 DE2120091A1 (de) 1971-04-24 1971-04-24 Farbbildner für das Peroxid-Farbverstärkungs-Verfahren

Publications (1)

Publication Number Publication Date
US3817751A true US3817751A (en) 1974-06-18

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US00246387A Expired - Lifetime US3817751A (en) 1971-04-24 1972-04-21 Color forming agents for the peroxide color intensifying process

Country Status (8)

Country Link
US (1) US3817751A (enExample)
BE (1) BE782088A (enExample)
CA (1) CA998870A (enExample)
CH (1) CH573610A5 (enExample)
DE (1) DE2120091A1 (enExample)
FR (1) FR2134460A1 (enExample)
GB (1) GB1393727A (enExample)
IT (1) IT960332B (enExample)

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5641615A (en) * 1994-04-20 1997-06-24 Eastman Kodak Company Processing silver halide photographic elements with a non-rehalogenating peroxide bleaching composition
US5641616A (en) * 1994-04-20 1997-06-24 Eastman Kodak Company Non-rehalogenating bleaching composition and its use to process silver halide photographic elements
US5686229A (en) * 1995-09-15 1997-11-11 Eastman Kodak Company Method of processing a color photographic silver halide material

Families Citing this family (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR2691145A1 (fr) * 1992-05-18 1993-11-19 Inst Nat Sante Rech Med Nouveaux dérivés de la dihydroxybenzylamine, leur préparation et les compositions pharmaceutiques qui les contiennent.
TW502026B (en) * 1995-06-20 2002-09-11 Zeneca Ltd Aromatic compounds useful as antagonists of e-type prostaglandins, processes for the preparation thereof, pharmaceutical compositions comprising the compounds, and intermediates
FR2766177B1 (fr) * 1997-07-16 2000-04-14 Oreal Nouvelles bases d'oxydation cationiques, leur utilisation pour la teinture d'oxydation des fibres keratiniques, compositions tinctoriales et procedes de teinture

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5641615A (en) * 1994-04-20 1997-06-24 Eastman Kodak Company Processing silver halide photographic elements with a non-rehalogenating peroxide bleaching composition
US5641616A (en) * 1994-04-20 1997-06-24 Eastman Kodak Company Non-rehalogenating bleaching composition and its use to process silver halide photographic elements
US5686229A (en) * 1995-09-15 1997-11-11 Eastman Kodak Company Method of processing a color photographic silver halide material

Also Published As

Publication number Publication date
GB1393727A (en) 1975-05-14
IT960332B (it) 1973-11-20
CH573610A5 (enExample) 1976-03-15
FR2134460A1 (enExample) 1972-12-08
CA998870A (en) 1976-10-26
BE782088A (nl) 1972-10-16
DE2120091A1 (de) 1972-11-09

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