EP0561860B1 - Procede de developpement de materiaux couleur a base d'halogenure d'argent et utilisation de pyrazolidones - Google Patents

Procede de developpement de materiaux couleur a base d'halogenure d'argent et utilisation de pyrazolidones Download PDF

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Publication number
EP0561860B1
EP0561860B1 EP92900247A EP92900247A EP0561860B1 EP 0561860 B1 EP0561860 B1 EP 0561860B1 EP 92900247 A EP92900247 A EP 92900247A EP 92900247 A EP92900247 A EP 92900247A EP 0561860 B1 EP0561860 B1 EP 0561860B1
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Prior art keywords
colour
carbon atoms
silver halide
hydrogen
development
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EP92900247A
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German (de)
English (en)
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EP0561860A1 (fr
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Peter Jeffery C/O Kodak Limited Twist
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Kodak Ltd
Eastman Kodak Co
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Kodak Ltd
Eastman Kodak Co
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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
    • G03C7/00—Multicolour photographic processes or agents therefor; Regeneration of such processing agents; Photosensitive materials for multicolour processes
    • G03C7/30—Colour processes using colour-coupling substances; Materials therefor; Preparing or processing such materials
    • G03C7/407—Development processes or agents therefor
    • G03C7/413—Developers
    • 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
    • G03C7/00—Multicolour photographic processes or agents therefor; Regeneration of such processing agents; Photosensitive materials for multicolour processes
    • G03C7/30—Colour processes using colour-coupling substances; Materials therefor; Preparing or processing such materials
    • G03C7/392—Additives
    • G03C7/39208—Organic compounds
    • G03C7/3924—Heterocyclic
    • G03C7/39244—Heterocyclic the nucleus containing only nitrogen as hetero atoms
    • G03C7/39252—Heterocyclic the nucleus containing only nitrogen as hetero atoms two nitrogen atoms

Definitions

  • This invention relates to photographic silver halide processing solutions and particularly to colour developing solutions.
  • US Patent 4 465 762 discloses silver halide colour materials containing a pyrazolidinone of formula (I).
  • the present pyrazolidinones can only be derived by selecting substituents from two separate lists. No specific such compounds are described.
  • US Patent 4 266 002 describes the use of pyrazolidinones as an electron transfer agent in a dye diffusion transfer element. No chromogenic dye development is described.
  • US Patent 4 483 919 describes a photographic colour material containing a compound that releases a pyrazolidinone upon development. The release is therefore imagewise.
  • US Patent 4 155 763 describes colour developing solutions comprising an aromatic amine colour developing agent and a 1-aryl-pyrazolidone having two substituents at the 4-position of the pyrazolidone.
  • the advantages are said to include faster image dye formation and a more stable colour developing solution.
  • the English language abstract of Japanese application 62/178251 describes a colour developing solution comprising a para-phenylenediamine colour developing agent and an auxiliary developing agent including, inter alia , 1-phenyl-pyrazolidone. Image formation is described as “highly sensitive” and forming “excellent gradation”. It is also said to be “free from the influence of agitation.
  • the present invention provides a method of developing an imagewise exposed silver halide colour material to provide sensitometric results of reduced variability which comprises carrying out colour development in an aqueous colour developing solution containing a colour developing agent in the presence of one or a combination of the pyrazolidinone silver halide developing agents of the general formula: wherein R1 and R2 are each hydrogen or an alkoxy group having 1-4 carbon atoms, and R3 and R4 are each hydrogen or an alkyl group having 1-10 carbon atoms, with the proviso that either one of R1 or R2 is an alkoxy group or either one of R3 or R4 is an alkyl group of 3-7 carbon atoms, incorporated in said silver halide colour material in an inactive form from which the active form is released in the alkaline developer solution, characterised in that the nature of the pyrazolidinone silver halide developing agent(s) is such that in low activity conditions development is accelerated while in high activity conditions development is decelerated thus reducing the variability in the density versus
  • the pyrazolidinone developing agent may also be present in the colour developer solution.
  • a useful group of Type (1) ETA's of formula (I) are those in which at least one of R1 and/or R2 is an alkoxy group of 1-4 carbon atoms, eg -OCH3, R3 is hydrogen or an alkyl group of 1-4 carbon atoms, eg - CH3 and R4 is hydrogen or a hydroxyalkyl group of 1-4 carbon atoms, eg -CH2OH.
  • a useful group of Type (2) ETA's of formula (I) are those in which R1, R2 and R3 are hydrogen and R4 is an alkyl group of 3-7 atoms, eg -C5H11
  • the preferred black-and-white developers are: 1-(4-methoxyphenyl)-3-pyrazolidone, 1-(3,4-dimethoxyphenyl)-3-pyrazolidone, and 1-phenyl-4-n-pentylpyrazolidone.
  • the black-and-white developing agent may be present in the developer solution at a concentration up to 5 g/l preferably in the range 0.05 to 0.5 g/l.
  • concentration up to 5 g/l preferably in the range 0.05 to 0.5 g/l.
  • incorporated in the photographic material it may be present in one or more layers thereof. Instead of incorporating them per se in the photographic material they are, as indicated above, in the form of a compound that releases them as a function of the pH of the processing solution.
  • the presence of the black-and-white developing agent improves variability caused by variations in time and temperature of development, pH, bromide ion concentration and colour developing agent (eg CD4) concentration in the colour developer solution.
  • the reduced risk of sensitometric variations further means that replenishment rates can be reduced thus resulting in less overflow and effluent.
  • the sometimes needed bromide ion removal from the developer solution may also be avoidable.
  • the present invention is particularly applicable to the processing of colour negative film but is also applicable to other processes, eg colour paper.
  • the material to be processed comprises a support bearing at least one silver halide emulsion layer having a colour coupler associated therewith.
  • the term "associated therewith” here takes its normal meaning in art.
  • the coupler may be incorporated in the emulsion layer or in a layer adjacent thereto.
  • the preferred colour materials comprise three dye image forming units each containing one or more emulsion layers having couplers associated therewith and each sensitised to a different region of the spectrum.
  • a typical colour material would contain such units sensitised to blue, green and red light and capable of forming yellow, magenta and cyan image dyes respectively.
  • a single layer coating of a silver bromoiodide emulsion comprising tabular grains having a mean grain area of 1.05 m ⁇ 2 containing a colour coupler (A) of the formula: dissolved in di-tert-butylphthalate (coupler to solvent ratio of 1:0.5) was coated at 1.0 g/m2 (as silver) and 0.6 g/m2 of coupler.
  • Table 1 below gives process details of concentration of 1-(4-methoxyphenyl)-3-pyrazolidone and development time at 37.8°C.
  • Example 2 A single layer coating of a silver bromoiodide emulsion as described in Example 1 was tested by the procedure of Example 1 was followed except that the time of development was kept constant at 2.5 minutes while varying the CD4 and ETA concentrations as set out in Table 2 below.

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  • Physics & Mathematics (AREA)
  • General Physics & Mathematics (AREA)
  • Spectroscopy & Molecular Physics (AREA)
  • Silver Salt Photography Or Processing Solution Therefor (AREA)

Abstract

Procédé de développement d'un matériau en couleurs à base d'halogénure d'argent comportant une image latente, afin d'obtenir des résultats sensitométriques acceptables à variabilité réduite. Ledit procédé consiste à réaliser un développement en couleurs en présence d'un agent de développement réversal en noir et blanc, ou d'une combinaison de ces agents, ce qui réduit la variabilité des résultats sensitométriques due aux modifications des variables du processus. Il s'agit de préférence du 1-(4-méthoxyphényl)-3-pyrazolidone, du 1-(3,4-diméthoxy-phényl)-3-pyrazolidone, ou du 1-phényl-4-n-pentyl-pyrazolidone.

Claims (7)

  1. Procédé de développement d'un matériau en couleurs aux halogénures d'argent exposé suivant une image pour donner des résultats sensitométriques de variabilité réduite qui comprend
       la mise en oeuvre du développement chromogène dans une solution aqueuse de développement chromogène contenant un agent développateur chromogène en présence d'un ou d'une combinaison d'agents développateurs des halogénures d'argent du type pyrazolidinone de formule générale :
    Figure imgb0013
     dans laquelle
    R¹ et R² sont chacun l'hydrogène ou un groupe alcoxy en C₁-C₄ et
    R³ et R⁴ sont chacun l'hydrogène ou un groupe alkyle en C₁-C₁₀,
    pourvu que l'un ou l'autre de R¹ et R² soit un groupe alcoxy ou que l'un ou l'autre de R³ et R⁴ soit un groupe alkyle en C₃-C₇,
    incorporé dans ledit matériau en couleurs aux halogénures d'argent sous une forme inactive à partir de laquelle la forme active est libérée dans la solution révélatrice alcaline, la nature du ou des agents développateurs des halogénures d'argent du type pyrazolidinone étant telle que, dans des conditions de faible activité, le développement est accéléré, tandis que, dans des conditions d'activité élevée, le développement est ralenti, réduisant ainsi la variabilité de la courbe de densité en fonction de logE (courbe caractéristique) provoquée par des variations de la durée de développement.
  2. Procédé selon la revendication 1, dans lequel l'agent développateur du type pyrazolidinone est également contenu dans la solution de révélateur chromogène.
  3. Procédé selon la revendication 1 ou 2, dans lequel l'un au moins de R¹ et/ou R² est un groupe alcoxy en C₁-C₄, R³ est l'hydrogène ou un groupe alkyle en C₁-C₄ et R⁴ est l'hydrogène ou un groupe hydroxyalkyle en C₁-C₄.
  4. Procédé selon la revendication 1 ou 2, dans lequel R¹, R² et R³ sont des atomes d'hydrogène et R⁴ est un groupe alkyle en C₃-C₇.
  5. Procédé selon l'une quelconque des revendications 1 à 4, dans lequel l'agent développateur du type pyrazolidinone est la 1-(4-méthoxyphényl)-3-pyrazolidone, la 1-(3,4-diméthoxyphényl)-3-pyrazolidone ou la 1-phényl-4-n-pentylpyrazolidone.
  6. Procédé selon l'une quelconque des revendications 2 à 5, dans lequel l'agent développateur du type pyrazolidinone est présent dans la solution de révélateur à une concentration de 0,05 à 0,5 g/l.
  7. Utilisation d'une ou plusieurs pyrazolidinones pour réduire la variabilité sensitométrique des matériaux photographiques en couleurs aux halogénures d'argent traités, dans laquelle les pyrazolidinones répondent à la formule générale (I) :
    Figure imgb0014
     dans laquelle
    R¹ et R² sont chacun l'hydrogène ou un groupe alcoxy en C₁-C₄ et
    R³ et R⁴ sont chacun l'hydrogène ou un groupe alkyle en C₁-C₁₀,
    pourvu que l'un ou l'autre de R¹ et R² soit un groupe alcoxy ou l'un ou l'autre de R³ et R⁴ soit un groupe alkyle en C₃-C₇,
    et dans laquelle la ou les pyrazolidinones sont présentes pendant le développement chromogène mis en oeuvre dans une solution aqueuse de développement chromogène et sont telles que, dans des conditions de faible activité, le développement est accéléré, tandis que, dans des conditions d'activité élevée, le développement est ralenti, réduisant ainsi la variabilité de la courbe de densité en fonction de logE (courbe caractéristique) provoquée par des variations de la durée de développement.
EP92900247A 1990-12-13 1991-12-10 Procede de developpement de materiaux couleur a base d'halogenure d'argent et utilisation de pyrazolidones Expired - Lifetime EP0561860B1 (fr)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
GB9027062 1990-12-13
GB909027062A GB9027062D0 (en) 1990-12-13 1990-12-13 Method of photographic silver halide processing,silver halide materials and solutions therefor
PCT/EP1991/002363 WO1992010789A1 (fr) 1990-12-13 1991-12-10 Procede de developpement photographique renverse, materiaux a base d'halogenure d'argent, et solutions associees

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EP0561860A1 EP0561860A1 (fr) 1993-09-29
EP0561860B1 true EP0561860B1 (fr) 1995-11-22

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EP (1) EP0561860B1 (fr)
JP (1) JPH06503183A (fr)
DE (1) DE69114862T2 (fr)
GB (1) GB9027062D0 (fr)
WO (1) WO1992010789A1 (fr)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5994037A (en) * 1998-10-21 1999-11-30 Eastman Kodak Company Method for rapid photographic processing with maintained color balance using diffusible photochemicals
US6020112A (en) * 1998-10-21 2000-02-01 Eastman Kodak Company Method for rapid photographic processing with maintained color balance

Families Citing this family (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0617322B1 (fr) * 1993-03-22 1999-12-01 Eastman Kodak Company Procédé de traitement d'éléments photographiques originaires comprenant des grains tabulaires de chlorure d'argent délimités pas des faces (100)
US5443943A (en) * 1993-03-22 1995-08-22 Eastman Kodak Company Method of processing originating photographic elements containing tabular silver chloride grains bounded by {100} faces
GB9306355D0 (en) * 1993-03-26 1993-05-19 Kodak Ltd Method of processing photographic silver halide materials
GB9408531D0 (en) * 1994-04-29 1994-06-22 Kodak Ltd Photographic silver halide colour materials
GB9408530D0 (en) * 1994-04-29 1994-06-22 Kodak Ltd Photographic silver halide colour material
GB9623709D0 (en) * 1996-11-14 1997-01-08 Kodak Ltd Novel auxiliary developing agents,photographic materials incorporating them and the use thereof
US6087084A (en) * 1997-11-14 2000-07-11 Eastman Kodak Company Auxiliary developing agents, photographic materials incorporating them and the use thereof

Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0347849A2 (fr) * 1988-06-21 1989-12-27 EASTMAN KODAK COMPANY (a New Jersey corporation) Matériau d'enregistrement photographique pour développement accéléré

Family Cites Families (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CA731087A (en) * 1959-09-03 1966-03-29 M. Mader Paul Color development with compositions containing 3-pyrazolidone developing agents
US3902905A (en) * 1972-11-20 1975-09-02 Eastman Kodak Co Photographic elements containing image dye-providing layer units
JPS5943735B2 (ja) * 1976-09-07 1984-10-24 富士写真フイルム株式会社 カラ−写真処理方法
US4266002A (en) * 1978-10-02 1981-05-05 Eastman Kodak Company Substituted 1-phenyl-3-pyrazolidinone electron transfer agents
JPS57144547A (en) * 1981-03-03 1982-09-07 Fuji Photo Film Co Ltd Silver halide color photosensitive material and its processing method
JPS59121328A (ja) * 1982-12-28 1984-07-13 Fuji Photo Film Co Ltd ハロゲン化銀写真感光材料
JPS60162253A (ja) * 1984-02-01 1985-08-24 Konishiroku Photo Ind Co Ltd ハロゲン化銀カラ−写真感光材料の処理方法
JPS62175752A (ja) * 1986-01-29 1987-08-01 Fuji Photo Film Co Ltd ハロゲン化銀カラ−写真感光材料の処理方法

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0347849A2 (fr) * 1988-06-21 1989-12-27 EASTMAN KODAK COMPANY (a New Jersey corporation) Matériau d'enregistrement photographique pour développement accéléré

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5994037A (en) * 1998-10-21 1999-11-30 Eastman Kodak Company Method for rapid photographic processing with maintained color balance using diffusible photochemicals
US6020112A (en) * 1998-10-21 2000-02-01 Eastman Kodak Company Method for rapid photographic processing with maintained color balance

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JPH06503183A (ja) 1994-04-07
WO1992010789A1 (fr) 1992-06-25
DE69114862T2 (de) 1996-09-12
DE69114862D1 (de) 1996-01-04
EP0561860A1 (fr) 1993-09-29
GB9027062D0 (en) 1991-02-06

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