EP0586749A1 - Colorants qui absorbent la lumière dans la région de l'extrême rouge et infra-rouge du spectre - Google Patents

Colorants qui absorbent la lumière dans la région de l'extrême rouge et infra-rouge du spectre Download PDF

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Publication number
EP0586749A1
EP0586749A1 EP92202766A EP92202766A EP0586749A1 EP 0586749 A1 EP0586749 A1 EP 0586749A1 EP 92202766 A EP92202766 A EP 92202766A EP 92202766 A EP92202766 A EP 92202766A EP 0586749 A1 EP0586749 A1 EP 0586749A1
Authority
EP
European Patent Office
Prior art keywords
dye
layer
dyes
silver
photographic material
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.)
Withdrawn
Application number
EP92202766A
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German (de)
English (en)
Inventor
Paul Callant
Roland Claes
Rudy Goedeweeck
Eric Kiekens
Raymond Lemahieu
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.)
Agfa Gevaert NV
Original Assignee
Agfa Gevaert NV
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 Agfa Gevaert NV filed Critical Agfa Gevaert NV
Priority to EP92202766A priority Critical patent/EP0586749A1/fr
Publication of EP0586749A1 publication Critical patent/EP0586749A1/fr
Withdrawn legal-status Critical Current

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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
    • G03C5/16—X-ray, infrared, or ultraviolet ray processes
    • G03C5/17—X-ray, infrared, or ultraviolet ray processes using screens to intensify X-ray 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
    • G03C1/00—Photosensitive materials
    • G03C1/76—Photosensitive materials characterised by the base or auxiliary layers
    • G03C1/825—Photosensitive materials characterised by the base or auxiliary layers characterised by antireflection means or visible-light filtering means, e.g. antihalation
    • G03C1/8255—Silver or silver compounds therefor

Definitions

  • the present invention relates to silver salts of filter dyes and their use as infrared filter and antihalation dyes in photographic elements.
  • Non-spectrally sensitizing dyes are widely used in photographic elements, particularly in photographic elements of the silver halide type. They may be used in a photosensitive silver halide emulsion layer as screening dyes, in an undercoat adjacent to the photosensitive layer and/or in a backing layer on the side of the support opposite to the photosensitive layer to absorb reflected and scattered light thereby serving as antihalation dye or in an overcoat or interlayer to shield a particular photosensitive layer against undesired exposure being therefore referred to as filter or absorber dye.
  • the dye absorption spectrum should approximately be equal to the sensitivity spectrum of the corresponding silver halide emulsion in the layer of which a sharp image has to be reproduced.
  • filter dyes remain, i.e. that they are non-migratory, in the layer wherein they have been incorporated especially when this layer is in direct contact with the silver halide emulsion layer in order to prevent an undesired desensitizing action on the silver halide.
  • the filter dyes may not stain the photographic material after image processing. Therefore preference is given to filter dyes that decolorize or can be removed from the photographic element in the processing stage. This requirement is nowadays becoming more and more stringent as rapid processing times are of increasing interest.
  • filter dyes characterized by the presence of a 2-pyrazolin-5-one nucleus substituted with a carboxyphenyl group and including a methine group or chain linked to a dialkylamino group are described in US-P 4,857,446.
  • the decolorization of said filter dyes proceeds very rapidly in alkaline aqueous processing baths.
  • the monomethine dyes have an absorption spectrum of which the maximum is in the shorter wavelength range of the visible spectrum so that normally a second filter dye is needed to block or absorb green light and even a third one to absorb radiations of longer wavelengths, e.g. radiations in the red or even in the infrared region.
  • infrared-absorbing antihalation dyes are described in e.g. US-Patent Applications 4,933,269; 4,871,656; 4,876,181 and EP 251,282; 101,646; 329,491 and 341,958.
  • the problem is how to get the filter dye in a coated layer so that all the requirements mentioned previously are met.
  • EP 0,401,709 A2 describes the dissolution of hydrophobic dyes into oil droplets being substantially insoluble in water and the preparation of the corresponding oilformer dispersions or loaded polymer latex dispersions.
  • the dye is often coated with a mordant to bind the dye in the layer in which it is coated as is e.g. illustrated in US-Patent 2,527,583.
  • a mordant to bind the dye in the layer in which it is coated as is e.g. illustrated in US-Patent 2,527,583.
  • dye mordants polymers are often used.
  • Another possibility is offered by adsorption of dyes at the surface of very fine light-insensitive silver halide crystals with the expectable disadvantages of the coating of more silver halide crystals and possibly fixation difficulties.
  • Another object of the invention is to provide photographic materials comprising said dyes.
  • silver salts of pentamethine oxonol dyes are provided, the dyes preferably corresponding to the following general formula (I): wherein each of Z1 and Z2 represents the members necessary to close a five- or six-membered heterocyclic nitrogen containing nucleus, preferably a pyrazolidinone nucleus, each of R1,R2 and R3 independently represents hydrogen, substituted or unsubstituted alkyl, cyclo-alkyl or a bridge-forming alkyl group between (adjacent) C-atoms of the methine chain, substituted or unsubstituted aryl, halogen.
  • NHSO2R4 with R4 being a substituted or unsubstituted alkyl, or a substituted or unsubstituted aryl group.
  • a photographic element comprising a support and at least one extended-red and/or infrared-sensitive, photo-sensitive silver halide emulsion layer, wherein the said element comprises, dispersed in a hydrophilic waterpermeable colloid binder, at least one metal ion salt, preferably a silver salt of a dye according to the above general formula.
  • the filter dyes according to the present invention can be incorporated in aqueous coating compositions in dispersed form by using commercial mixing devices for making colloidal dispersions.
  • said filter dyes are easily solubilized so that they are removed almost completely from a hydrophilic waterpermeable colloid layer of a photographic silver halide emulsion material by its common alkaline aqueous liquid processing and leave almost no residual stain.
  • the presence of sulfite in the processing solution contributes to a more rapid discoloration of the filter dyes.
  • the behaviour of the dyes as a function of pH is quite analogous.
  • dyes for use in salt form in accordance with the present invention are:
  • the silver salts of compounds (II) to (XII) are particularly useful for blocking light in the extended red and infrared spectral regions.
  • filter or antihalation dyes are forming complexes with most of the ions of the transition metals, like iron, gold, chromium, palladium, zinc, manganese, copper, molybdenum, nickel and tellurium
  • silver ions are preferred not only because silver salts react to form a soluble complex with thiosulphate ions during the fixation step, offering the possibility to set the dye free again, but also for ecological reasons.
  • An important advantage of the invention consists in the very simple preparation of the silver salts of mentioned oxonol dyes.
  • a silver salt e.g. silver nitrate
  • dispersed dye e.g. silver nitrate
  • the hydrophilic colloidal layer can be a backing layer, an antihalation undercoating layer, a silver halide emulsion layer, containing silver halide crystals with a diameter of at least 0.1 ⁇ m, a layer containing very fine silver halide particles with a diameter of 10 to 100 nm known as Lippmann emulsions and a protection layer coated as an outermost layer.
  • a silver salt of a dye in a layer, containing already said dye, by wet-coating said layer with an aqueous composition containing a dilute silver nitrate solution so delivering the equivalent amount of silver ions needed to build up the required silver salt complex of said dye.
  • the layers previously mentioned as suitable layers comprising a filter or antihalation silver salt dye may be incorporated in e.g. X-ray materials, graphic materials, diffusion transfer materials, black and white or colour cinematographic materials etc.
  • the silver salt complex of the suitable dye or dyes are incorporated in an antihalation back coating because otherwise when in water permeable relationship with silver halide emulsion layers the silver salt complex(es) may be decomposed due to the interaction of the silver ions of said complex(es) with halide ions from said emulsion layers, said halide ions forming less soluble complexes with these Ag+-ions.
  • said extended red and infrared-light absorbing dyes can be used in an antihalation layer of a photographic silver halide emulsion material in order to improve image sharpness by absorbing exposure light penetrating the emulsion layer(s) into the direction of the support.
  • a specific advantage of this invention consists in the stability of the bathochromically shifted transition metal ion complex of filter dyes, said filter dyes having an absorption maximum in the visible wavelength region before treatment with a transition metal ion solution.
  • Stabilizers capable of forming complexes with silver ions can be incorporated in a hydrophilic colloid layer together with the silver complex dyes in order to improve the stability of the silver salts of the dyes in an atmosphere of high temperature and/or high relative humidity against reduction of free silver ions to fine silver metal clusters which would act as development centre or development nucleus.
  • suitable stabilizers the well-known compounds used to stabilize silver halide crystals in a hydrophilic colloidal silver halide emulsion layer of a photographic material can be used.
  • Suitable examples are i.a. the heterocyclic nitrogen-containing compounds such as benzothiazolium salts, nitroimidazoles, nitrobenzimidazoles, chlorobenzimidazoles, bromobenzimidazoles, mercaptothiazoles, mercaptobenzothiazoles, mercaptobenzimidazoles, mercaptothiadiazoles, aminotriazoles, benzotriazoles (preferably 5-methyl-benzotriazole), nitrobenzotriazoles, mercaptotetrazoles, in particular 1-phenyl-5-mercapto-tetrazole, mercaptopyrimidines, mercaptotriazines, benzothiazoline-2-thione, oxazoline-thione, triazaindenes, tetrazaindenes and pentazaindenes, especially those described by Birr in Z.
  • heterocyclic nitrogen-containing compounds such as benzothiazolium salts, nitroimidazoles,
  • the invention is concerned with the use of the dyes in photographic silver halide materials.
  • the transition metal complex dyes can also be used for other purposes.
  • a hydrophilic colloid layer containing the silver (or any of the previously mentioned transition metal ion) salt of a suitable dye absorbing light in the infrared region of the wavelength spectrum can be used as a particularly sensitive element to detect the presence of halide ions: any contact of this element with halide ions makes the colour of the layer change from colourless to e.g. deep blue, as is the case for dye (II), due to the hypsochromic shift after decomposition of the silver salt complex of the dye.
  • the colloidal liquid as a colourless ink so that the text written with it can be made visible after contacting the dried document with a solution of a halide salt.
  • gelatin An amount of 3 g of gelatin was allowed to swell during 1 hour in a vessel containing 50 ml of demineralized water.
  • the gelatin was of a low viscosity (13.6 mPas for a 10% solution at 40°C measured with a Haake Rotavisco RV2 apparatus).
  • the mixture was heated to a temperature of 38°C.
  • 1 mmole of dye (II) was dissolved in 50 ml of demineralized water; the pH-value was increased with sodium hydroxyde until the dye was completely dissolved and the dye solution added under stirring conditions to the gelatinous mixture described above.
  • Transmission spectrograms of the coated samples were taken versus a reference sample without a dye coating with a Hewlett Packard 8450A UV-VIS spectrophotometer, measuring in the wavelength region from 200 to 800 nm.
  • a reference sample for the tested silver salt dye was made by replacing the diluted silver nitrate solution by an equivalent amount of demineralized water and adjusting the pH to a value of 6.5.
  • a practical infrared absorbing antihalation back coating on a subbed polyethyleneterephtalate support was made after incorporation of the silver salt dye of formula (II).
  • the back coating was formed with two different layers: an antihalation layer containing the silver salt complex of said dye and a protective layer so as to protect the antihalation layer against chemical (e.g. halide ions) and mechanical influences.
  • First layer the antihalation layer.
  • the layer was prepared according to the procedure described in Example 1. Before coating this colloidal solution was containing 47.7 g of gelatin in which 3 mmole of the dye with formula (II) and 3 mmole of a silver nitrate solution were mixed together.
  • pH-value of the coating composition was adjusted to a value of 6.3. With a total volume of 900 ml after the addition of demineralized water, a coating was made with a wet thickness of 50 ⁇ m. This layer formed was quite clear without any turbidity.
  • Second layer the protective layer.
  • the protective coating composition contained 27 g of gelatin, 32 ml (3.2% by weight in a 10% gelatinous aqeous solution) of a matting agent, 5.4 ml (10% by weight) of MOBILCER Q, trademarked product from MOBIL OIL, as a lubrificating agent, 8.1 ml (5% by weight) of C7F15COONH4 (the ammonium salt of perfluorocaprylic acid, trademarked product from 3M) as a surface-active agent and 135 ml (10% by weight) of glutaric dialdehyd as a hardener. Sodium hydroxyde was added to reach a pH value of 6.3 and water added to an amount of 900 ml. The layer had a wet-coated thickness of 17 ⁇ m.

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  • Physics & Mathematics (AREA)
  • General Physics & Mathematics (AREA)
  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Silver Salt Photography Or Processing Solution Therefor (AREA)
EP92202766A 1992-09-11 1992-09-11 Colorants qui absorbent la lumière dans la région de l'extrême rouge et infra-rouge du spectre Withdrawn EP0586749A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
EP92202766A EP0586749A1 (fr) 1992-09-11 1992-09-11 Colorants qui absorbent la lumière dans la région de l'extrême rouge et infra-rouge du spectre

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
EP92202766A EP0586749A1 (fr) 1992-09-11 1992-09-11 Colorants qui absorbent la lumière dans la région de l'extrême rouge et infra-rouge du spectre

Publications (1)

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EP0586749A1 true EP0586749A1 (fr) 1994-03-16

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Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB1077049A (en) * 1964-11-03 1967-07-26 Filmfabriken Wolfen Veb Photographic material containing anti-halation and/or filter layers
EP0276566A1 (fr) * 1986-12-23 1988-08-03 EASTMAN KODAK COMPANY (a New Jersey corporation) Elément radiographique à effet interimage réduit
EP0521664A1 (fr) * 1991-07-04 1993-01-07 Konica Corporation Matériau photographique à l'halogénure d'argent sensible à la lumière

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB1077049A (en) * 1964-11-03 1967-07-26 Filmfabriken Wolfen Veb Photographic material containing anti-halation and/or filter layers
EP0276566A1 (fr) * 1986-12-23 1988-08-03 EASTMAN KODAK COMPANY (a New Jersey corporation) Elément radiographique à effet interimage réduit
EP0521664A1 (fr) * 1991-07-04 1993-01-07 Konica Corporation Matériau photographique à l'halogénure d'argent sensible à la lumière

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
CHEMICAL ABSTRACTS, vol. 78, no. 14, 9 April 1973, Columbus, Ohio, US; abstract no. 90981h, B PORTNAYA ET AL 'Photographic material' page 476 ;column 2 ; *

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