EP0490297B1 - Photographische Materialien mit verstärkter Latentbild-Stabilität - Google Patents

Photographische Materialien mit verstärkter Latentbild-Stabilität Download PDF

Info

Publication number
EP0490297B1
EP0490297B1 EP19910120993 EP91120993A EP0490297B1 EP 0490297 B1 EP0490297 B1 EP 0490297B1 EP 19910120993 EP19910120993 EP 19910120993 EP 91120993 A EP91120993 A EP 91120993A EP 0490297 B1 EP0490297 B1 EP 0490297B1
Authority
EP
European Patent Office
Prior art keywords
recording material
silver halide
photographic
latent image
carbon atoms
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
EP19910120993
Other languages
English (en)
French (fr)
Other versions
EP0490297A1 (de
Inventor
George Lee c/o EASTMAN KODAK COMPANY Bonheyo
Ronald Edmund C/O Eastman Kodak Company Leone
Roger C/O Eastman Kodak Company Lok
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.)
Eastman Kodak Co
Original Assignee
Eastman Kodak Co
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 Eastman Kodak Co filed Critical Eastman Kodak Co
Publication of EP0490297A1 publication Critical patent/EP0490297A1/de
Application granted granted Critical
Publication of EP0490297B1 publication Critical patent/EP0490297B1/de
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

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
    • 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
    • G03C1/34—Fog-inhibitors; Stabilisers; Agents inhibiting latent image regression
    • G03C1/346—Organic derivatives of bivalent sulfur, selenium or tellurium

Definitions

  • the present invention relates to photographic recording materials and more particularly to photographic recording materials having enhanced latent image keeping stability.
  • a visible image is formed in silver halide photographic materials by exposure of the material to actinic radiation to form a record of the exposure. This record, which is invisible to the unaided eye, yields a visible image by photographic processing of the exposed material.
  • the latent image comprises minute specks of metallic silver. These specks form in or on individual silver halide grains by interaction between silver ions and photoelectrons generated by absorption of actinic radiation by the silver halide grains.
  • Processing of most common silver halide photographic materials includes a development step in which the material is contacted with an aqueous alkaline solution of a developing agent.
  • the developing agent which is a reducing agent, selectively reduces to metallic silver those silver halide grains containing a latent image.
  • latent image is not permanent and that, with passage of time, silver halide grains which would be developable immediately after exposure become nondevelopable. This phenomenon is termed latent image fading and manifests itself as a loss in image density in the developed image and a consequent loss in speed in the silver halide photographic material.
  • latent image fading would not be a problem.
  • delays between exposure and processing frequently occur.
  • latent image fading can present a significant problem and compounds are added to photographic materials to prevent or reduce this undesirable effect.
  • These compounds are referred to as latent image stabilizers and prevention or reduction of latent image fading is referred to as latent image stabilization.
  • a photographic recording material comprising a support and a photographic silver halide emulsion which has associated therewith a benzothiazolium or benzoselenazolium salt having the structural formula: wherein: X is sulfur or selenium; R1 is hydrogen, halogen, alkyl containing 1 to 5 carbon atoms, such as methyl, ethyl, propyl n-butyl, t-butyl or pentyl; or alkoxy containing 1 to 5 carbon atoms, such as methoxy, ethoxy, propoxy, n-butoxy, t-butoxy and R2 and R3 individually are hydrogen or alkyl containing 1 to 5 carbon atoms, such as methyl, ethyl, propyl, n-butyl, t-butyl or pentyl; Y is a counterbalancing ion; z is 1 or 2; m is 0 to 4; n is
  • R1 is alkyl or alkoxy
  • the length of the carbon chain is from 1 to 5 carbon atoms, preferably from 1 to about 3 carbon atoms.
  • the alkyl or alkoxy group can be straight or branched chain.
  • R1 is halogen it is preferably chloro.
  • the counterbalancing ion Y can be any anion compatible with the photographic material in which it is coated.
  • Useful ions include inorganic anions such as halides, halophosphates, trifluoromethanesulfonates and the like.
  • n can be an integer as high as 4, the preferred value is from 1 to 3.
  • the carbon chain can be straight or branched chain.
  • alkynyl benzothiazolium and benzoselenazolium compounds as described can be prepared by methods known in the organic compound synthesis art.
  • a typical method of preparation is as follows:
  • the benzothiazolium and benzoselenazolium compounds of this invention can be prepared by the route shown below.
  • Commercially available or synthesized alcohols (I) are commercially available or synthesized alcohols (I)
  • the benzothiazolium and benzoselenazolium salts described herein can be added to a silver halide emulsion at any point subsequent to precipitation of the silver halide grains.
  • the salts are added to an emulsion after chemical and spectral sensitization, but prior to coating.
  • the salts can be present during these sensitization procedures.
  • benzothiazolium or benzoselenazolium salt added to an emulsion will depend upon various factors such as the particular salt employed, the particular silver halide emulsion used or the nature of other components of the emulsion. Useful amounts are within the range of from about 0.002 to about 10 millimoles of salt per mole of silver. Preferably, the salt is incorporated in the emulsion in an amount of from about 0.02 to about 0.5 millimole per mole of silver.
  • the silver halide emulsions as described can be any of the silver halide emulsions known in the art which are desirably protected against latent image instability or fading.
  • the silver halide emulsions can be comprised of silver bromide, silver chloride, silver chlorobromide, silver chloroiodide, silver bromoiodide, silver chlorobromoiodide or mixtures thereof.
  • the emulsions can include coarse, medium or fine grains and can be monodisperse or polydisperse.
  • the silver halide emulsions are preferably surface latent image-forming emulsions. They can be chemically sensitized as illustrated by T. H. James, The Theory of the Photographic Process, 4th Ed., MacMillan, 1977, pp. 67-76, or with sulfur, selenium, tellurium, gold, platinum, palladium, iridium, osmium, rhenium or phosphorus sensitizers, or combinations of these sensitizers, as illustrated by Research Disclosure, Vol. 134, June 1975, Item 13452, or in U. S. Patent Nos.
  • Chemical sensitization can optionally be conducted in the presence of thiocyanate derivatives, as described in U. S. Patent Nos. 2,222,264 and 2,642,361; thioether compounds, as disclosed in U. S. Patent Nos. 2,521,926; 3,021,215 and 4,054,457; or azaindenes, azapyridazines and azapyrimidines, as described in U. S. Patent Nos. 3,411,914; 3,554,757; 3,565,631 and 3,901,714.
  • the emulsions can be reduction sensitized e.g., with hydrogen, as illustrated by U.S. Patent Nos.
  • the silver halide emulsions can be spectrally sensitized with dyes from a variety of classes, including the polymethine dye class, which includes the cyanines, merocyanines, complex cyanines and merocyanines (i.e., tri-, tetra-, and poly-nuclear cyanines and merocyanines), oxonols, hemioxonols, styryls, merostyryls and streptocyanines.
  • Particularly useful dyes are benzoxazole, benzimidazole and benzothiazole carbocyanine dyes.
  • the photographic silver halide emulsions can contain various colloids alone or in combination as vehicles. Suitable hydrophilic materials as well as hardeners therefore, are described in Research Disclosure, December 1989, Item 308119, Sections IX and X.
  • the photographic silver halide emulsions and elements employing the stabilizing agents of this invention can contain other addenda conventional in the photographic art.
  • Useful addenda are described, for example, in Research Disclosure, December 1989, Item 308119 and include antifoggants, couplers (such as dye forming couplers, masking couplers, DIR and DIAR couplers), anti-stain agents, image dye stabilizers, absorbing materials such as filter dyes and UV absorbers, light scattering materials, coating aids, plasticizers and lubricants.
  • the photographic recording materials described herein can be black-and-white or monochrome materials or they can be multilayer and/or multicolor elements comprising a support bearing one or more layers of a silver halide emulsion. These materials can be designed for processing in conventional developer solutions.
  • Multicolor elements can contain dye image forming units sensitive to each of the three primary regions of the spectrum. Each unit can be comprised of a single emulsion layer or of multiple emulsion layers sensitive to a given region of the spectrum.
  • the layers of the element, including the layers of the image-forming units, can be arranged in various orders as known in the art.
  • the emulsion or emulsions can be disposed as one or more segmented layers.
  • a preferred color photographic recording material comprises a support bearing at least one blue-sensitive silver halide emulsion layer having associated therewith a yellow dye-forming coupler, at least one green-sensitive silver halide emulsion layer having associated therewith a magenta dye-forming coupler and at least one red-sensitive silver halide emulsion layer having associated therewith a cyan dye-forming coupler, at least one of the silver halide emulsion layers containing a latent image stabilizing compound of this invention.
  • the stabilizing compound is contained in a yellow dye-forming blue-sensitive silver halide emulsion.
  • the photographic recording materials of the present invention can contain additional layers conventional in photographic elements, such as overcoat layers, spacer layers, filter layers, antihalation layers, scavenger layers and the like.
  • the support can be any suitable support used with photographic elements. Typical supports include polymeric films, paper (including polymer-coated paper), glass and the like. Details regarding supports and other layers of the photographic elements of this invention are contained in Research Disclosure, December 1989, Item 308119, referred to above.
  • the term "associated therewith” signifies that the stabilizing compound is in a silver halide emulsion layer or in an adjacent layer so that the materials contained therein are accessible to one another.
  • Benzothiazolium salts as latent image keeping agents were evaluated in a color negative test.
  • the Emulsion I used was a 1.6 micrometer equivalent circular diameter, .12 micrometer thick tabular silver bromoiodide emulsion containing 6 mol % iodide.
  • the emulsion was sulfur and gold sensitized with a yellow optical sensitizing dye.
  • This emulsion was coated in a two layer monochrome with a protective overcoat over the image layer.
  • the image layer contained the emulsion, a yellow dye forming coupler, and the latent image keeping agents coated both at .02 and .10 mmole/mole Ag.
  • the melt pH was 5.9 and the melt pAg was 7.9.
  • the latent image keeping coatings were exposed for 1/100 second and were incubated at 25°C, 50% RH for four weeks.
  • the check coatings were stored at -18°C and then were exposed. Both coatings were processed in a C-41 process with a commercial bleach (C-41 is a tradename and available from Eastman Kodak Company, U.S.A.). The processed coatings were read with status M densitometry. Results are reported in Table 1.
  • the compounds A, B and C are as follows:

Landscapes

  • Physics & Mathematics (AREA)
  • Chemical & Material Sciences (AREA)
  • Spectroscopy & Molecular Physics (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • General Physics & Mathematics (AREA)
  • Silver Salt Photography Or Processing Solution Therefor (AREA)
  • Plural Heterocyclic Compounds (AREA)

Claims (10)

  1. Photographisches Aufzeichnungsmaterial mit einem Träger und einer photographischen Silberhalogenidemulsion, der ein Benzothiazolium- oder Benzoselenazoliumsalz der folgenden Strukturformel:
    Figure imgb0024
     zugeordnet ist, worin bedeuten:
    X ein Schwefel- oder Selenatom;
    R¹ Wasserstoff, Halogen, Alkyl mit 1 bis 5 Kohlenstoffatomen oder Alkoxy mit 1 bis 5 Kohlenstoffatomen;
    R² und R³ einzeln Wasserstoff oder Alkyl mit 1 bis 5 Kohlenstoffatomen;
    Y ein ausgleichendes Gegenion;
    z gleich 1 oder 2;
    m gleich 0 bis 4;
    n gleich 1 bis 4; und
    R⁴ unsubstituiertes oder substituiertes Alkyl oder Aryl.
  2. Aufzeichnungsmaterial nach Anspruch 1, mit einem Salz der angegebenen Formel, in der R¹ für Wasserstoff steht.
  3. Aufzeichnungsmaterial nach einem der Ansprüche 1 bis 2 mit einem Salz der angegebenen Formel, in der R¹ für Chlor steht.
  4. Aufzeichnungsmaterial nach einem der Ansprüche 1 bis 3 mit einem Salz der angegebenen Formel, worin R¹ für Alkyl oder Alkoxy mit 1 bis 5 Kohlenstoffatomen steht.
  5. Aufzeichnungsmaterial nach einem der Ansprüche 1 bis 4 mit einem Salz der angegebenen Formel, in der R⁴ für Alkyl mit 1 bis 3 Kohlenstoffatomen steht, R¹, R² und R³ für Wasserstoffatome stehen und n gleich 1 und z gleich 1 ist.
  6. Aufzeichnungsmaterial nach einem der Ansprüche 1 bis 5, in dem das Salz in einer Menge von 0,002 bis etwa 10 Millimolen pro Mol Silber vorliegt.
  7. Aufzeichnungsmaterial nach einem der Ansprüche 1 bis 6, in dem das Salz in einer Menge von 0,02 bis etwa 0,5 Millimolen pro Mol Silber vorliegt.
  8. Aufzeichnungsmaterial nach einem der Ansprüche 1 bis 7, bei dem es sich um ein farbphotographisches Aufzeichnungsmaterial handelt.
  9. Aufzeichnungsmaterial nach einem der Ansprüche 1 bis 8, in dem das Salz der folgenden Strukturformel entspricht:
    Figure imgb0025
  10. Aufzeichnungsmaterial nach einem der Ansprüche 1 bis 9, in dem die photographische Silberhalogenidemulsion eine photographische Silberhalogenidemulsion mit tafelförmigen Körnern ist.
EP19910120993 1990-12-10 1991-12-06 Photographische Materialien mit verstärkter Latentbild-Stabilität Expired - Lifetime EP0490297B1 (de)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US62526390A 1990-12-10 1990-12-10
US625263 1990-12-10

Publications (2)

Publication Number Publication Date
EP0490297A1 EP0490297A1 (de) 1992-06-17
EP0490297B1 true EP0490297B1 (de) 1993-09-29

Family

ID=24505273

Family Applications (1)

Application Number Title Priority Date Filing Date
EP19910120993 Expired - Lifetime EP0490297B1 (de) 1990-12-10 1991-12-06 Photographische Materialien mit verstärkter Latentbild-Stabilität

Country Status (3)

Country Link
EP (1) EP0490297B1 (de)
JP (1) JPH04269742A (de)
DE (1) DE69100442T2 (de)

Family Cites Families (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS5814665B2 (ja) * 1975-12-09 1983-03-22 富士写真フイルム株式会社 チヨクセツポジハロゲンカギンカンコウザイリヨウ
US4375508A (en) * 1981-10-15 1983-03-01 Eastman Kodak Company Photographic compositions and elements spectrally sensitized with new methine dyes
EP0377889B1 (de) * 1989-01-07 1994-05-18 Agfa-Gevaert AG Silberhalogenidaufzeichnungsmaterial

Also Published As

Publication number Publication date
DE69100442T2 (de) 1994-05-05
JPH04269742A (ja) 1992-09-25
DE69100442D1 (de) 1993-11-04
EP0490297A1 (de) 1992-06-17

Similar Documents

Publication Publication Date Title
EP0026520B1 (de) Entwicklung photographischer Silberhalogenidemulsionen in Anwesenheit von Thioätherentwicklungsaktivatoren; Verfahren, Entwickler und photographisches Element
US5219721A (en) Silver halide photographic emulsions sensitized in the presence of organic dichalcogenides
US5049484A (en) Photographic silver halide material and process
EP0059144B1 (de) Silberhalogenidemulsion, enthaltend einen Stabilisator für das latente Bild, und fotografisches Element
EP0317950B1 (de) Photographische Elemente, die einen Bleich-Beschleuniger-Vorläufer enthalten
US4604339A (en) Method of developing silver halide photographic light-sensitive material
US4423140A (en) Silver halide emulsions containing aromatic latent image stabilizing compounds
EP0195622B1 (de) Hydrolisierte Azolium-Wirkstoffe zur Erhöhung der Empfindlichkeit und Schleierhemmung für Silberhalogenidphotographie
JPH0635147A (ja) カラー写真材料
EP0599383B1 (de) Photographische Silberhalogenidmaterialien enthaltend furan- oder pyrolsubstituierte Farbstoffverbindungen
US5413905A (en) Photographic sensitivity increasing alkynylamine compounds and photographic elements
US4281059A (en) Photographic material
EP0490297B1 (de) Photographische Materialien mit verstärkter Latentbild-Stabilität
US4366231A (en) Photographic material containing a stabilizer, a process for its production, a development process, new pyrazoles, a process for their production and intermediate products
EP0488030B1 (de) Photographische Materialien mit erhöhter Latentbildstabilität
US5500333A (en) Class of compounds which increases and stabilizes photographic speed
US4849327A (en) Silver halide light-sensitive material comprising benzo-bis-thiazole quaternary salts as antifogging agents
US4948721A (en) Photographic recording materials with enhanced latent image stability
USRE32195E (en) Silver halide emulsions containing aromatic latent image stabilizing compounds
EP0809138B1 (de) Xanthatsalze als chemische Silberhalogenidsensibilisatoren
EP0410753A1 (de) Photographische Aufzeichnungsmaterialien mit Latentbildstabilität
EP0061446B1 (de) Chemisch sensibilisierte, photographische silberhalid-emulsionen sowie diese enthaltende farbphotographische elemente
US5429919A (en) Silver halide photographic elements with increased contrast
EP0116346A2 (de) Photographische Silberhalogenidemulsion
EP0192464A2 (de) Telluriumsalz-Antischleier für Silberhalogenidphotographie

Legal Events

Date Code Title Description
PUAI Public reference made under article 153(3) epc to a published international application that has entered the european phase

Free format text: ORIGINAL CODE: 0009012

AK Designated contracting states

Kind code of ref document: A1

Designated state(s): AT BE CH DE DK ES FR GB GR IT LI LU MC NL SE

17P Request for examination filed

Effective date: 19920526

17Q First examination report despatched

Effective date: 19921216

RBV Designated contracting states (corrected)

Designated state(s): BE CH DE FR GB IT LI NL

GRAA (expected) grant

Free format text: ORIGINAL CODE: 0009210

AK Designated contracting states

Kind code of ref document: B1

Designated state(s): BE CH DE FR GB IT LI NL

REF Corresponds to:

Ref document number: 69100442

Country of ref document: DE

Date of ref document: 19931104

ET Fr: translation filed
PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: CH

Payment date: 19931215

Year of fee payment: 3

ITF It: translation for a ep patent filed

Owner name: MODIANO & ASSOCIATI S.R

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: NL

Payment date: 19931231

Year of fee payment: 3

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: BE

Payment date: 19940127

Year of fee payment: 3

PLBE No opposition filed within time limit

Free format text: ORIGINAL CODE: 0009261

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: NO OPPOSITION FILED WITHIN TIME LIMIT

26N No opposition filed
PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: LI

Effective date: 19941231

Ref country code: CH

Effective date: 19941231

Ref country code: BE

Effective date: 19941231

BERE Be: lapsed

Owner name: EASTMAN KODAK CY

Effective date: 19941231

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: NL

Effective date: 19950701

REG Reference to a national code

Ref country code: CH

Ref legal event code: PL

NLV4 Nl: lapsed or anulled due to non-payment of the annual fee

Effective date: 19950701

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: GB

Payment date: 19981110

Year of fee payment: 8

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: FR

Payment date: 19981203

Year of fee payment: 8

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: DE

Payment date: 19981230

Year of fee payment: 8

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: GB

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 19991206

GBPC Gb: european patent ceased through non-payment of renewal fee

Effective date: 19991206

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: FR

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20000831

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: DE

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20001003

REG Reference to a national code

Ref country code: FR

Ref legal event code: ST

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: IT

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES;WARNING: LAPSES OF ITALIAN PATENTS WITH EFFECTIVE DATE BEFORE 2007 MAY HAVE OCCURRED AT ANY TIME BEFORE 2007. THE CORRECT EFFECTIVE DATE MAY BE DIFFERENT FROM THE ONE RECORDED.

Effective date: 20051206