EP0720049B1 - Composition de traitement photographique et méthode de traitement l'utilisant - Google Patents

Composition de traitement photographique et méthode de traitement l'utilisant Download PDF

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Publication number
EP0720049B1
EP0720049B1 EP96103402A EP96103402A EP0720049B1 EP 0720049 B1 EP0720049 B1 EP 0720049B1 EP 96103402 A EP96103402 A EP 96103402A EP 96103402 A EP96103402 A EP 96103402A EP 0720049 B1 EP0720049 B1 EP 0720049B1
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Prior art keywords
processing
solution
group
iii
layer
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Expired - Lifetime
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EP96103402A
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German (de)
English (en)
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EP0720049A3 (fr
EP0720049A2 (fr
Inventor
Hisashi Okada
Shigeru Nakamura
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Fujifilm Holdings Corp
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Fuji Photo Film Co Ltd
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Priority claimed from JP12858890A external-priority patent/JPH0422948A/ja
Priority claimed from JP17502690A external-priority patent/JP2654714B2/ja
Application filed by Fuji Photo Film Co Ltd filed Critical Fuji Photo Film Co Ltd
Publication of EP0720049A2 publication Critical patent/EP0720049A2/fr
Publication of EP0720049A3 publication Critical patent/EP0720049A3/fr
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Publication of EP0720049B1 publication Critical patent/EP0720049B1/fr
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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
    • 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
    • G03C5/00—Photographic processes or agents therefor; Regeneration of such processing agents
    • G03C5/26—Processes using silver-salt-containing photosensitive materials or agents therefor
    • G03C5/29—Development processes or agents therefor
    • G03C5/305—Additives other than 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
    • G03C5/00—Photographic processes or agents therefor; Regeneration of such processing agents
    • G03C5/26—Processes using silver-salt-containing photosensitive materials or agents therefor
    • G03C5/29—Development processes or agents therefor
    • G03C5/305—Additives other than developers
    • G03C5/3053—Tensio-active agents or sequestering agents, e.g. water-softening or wetting agents
    • 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
    • G03C7/42—Bleach-fixing or agents therefor ; Desilvering processes

Definitions

  • the present invention relates to a processing composition for processing an imagewise exposed silver halide photographic material.
  • the present invention also relates to a method for processing imagewise exposed silver halide photographic materials using this composition.
  • chelating agents for sequestering the metal ions.
  • the chelating agents conventionally used include amino polycarboxylic acids (e.g., ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid, etc.) as described in JP-B-48-30496 (the term “JP-B” as used herein means an "examined Japanese patent publication") and JP-B-44-30232, organic phosphonic acids as described in JP-A-56-97347 (the term “JP-A” as used herein means an "unexamined published Japanese patent application"), JP-B-56-39359 and West German Patent 2,227,639, phosphonocarboxylic acids as described in JP-A-52-102726, JP-A-53-42730, JP-A-54-121127, JP-A-55-126241 and JP-A-55-65956, and the compounds described
  • the iron(III) complex salt of ethylenediaminetetraacetic acid conventionally used has a fundamental disadvantage in that the oxidizing power thereof is low.
  • Bleaching accelerators e.g., mercapto compounds described in U.S. Patent 1,138,842
  • rapid bleaching cannot be achieved.
  • processing solution having a bleaching ability (bleaching solution and bleach-fixing solution are generally called processing solution having a bleaching ability herein) is illustrated below.
  • the bleach-fixing solution containing this metal chelate compound contains a fixing agent (described hereinafter) and optionally the re-halogenating agent in addition to the metal chelate compound.
  • a fixing agent described hereinafter
  • the re-halogenating agent is used in the bleach-fixing solution, the re-halogenating agent is used in an amount of from 0.001 to 2.0 mol/l, preferably from 0.01 to 1.0 mol/l.
  • the bleaching or bleach-fixing step can be carried out at a temperature of from 30 to 50°C, preferably from 35 to 45°C.
  • the time of the bleaching step and/or the bleach-fixing step is generally 10 seconds to 5 minutes, preferably 10 to 60 seconds in the case of a photographic material for photographing.
  • the time is generally from 5 to 70 seconds, preferably from 5 to 60 seconds, more preferably from 5 to 30 seconds in the case of a print photographic material. Good results can be obtained under these preferred processing conditions under which processing is rapid and staining is not increased.
  • thiosulfates particularly ammonium thiosulfate are preferred when rapid fixing is desired. More rapid fixing can be conducted by using two or more fixing agents in combination. For example, it is preferred that ammonium thiosulfate is used in combination with ammonium thiocyanate, imidazole, thiourea, thioether, etc. In this case, the second fixing agent is used in an amount of preferably 0.01 to 100 mol% based on the amount of ammonium thiosulfate.
  • the desilverization step is carried out by a combination of a bleaching step and/or a bleach-fixing step. Typical examples of such combinations include the following.
  • the present invention can be applied to the desilverization treatment by means of a stop bath, rinse bath, etc. after color development.
  • Examples of methods for vigorously stirring include a method wherein a jet stream of the processing solution is directed to the emulsion surface of the light-sensitive material as described in JP-A-62-183460 and JP-A-62-183461; a method wherein a stirring effect is improved by using a rotating means as described in JP-A-62-183461; a method wherein the light-sensitive material is transferred while a wire blade provided in the solution is brought into contact with the emulsion surface to cause a turbulent flow on the emulsion surface, whereby stirring is improved; and a method wherein the circulating flow rate of the entire processing solution is increased.
  • Such methods for improving stirring can be effectively applied to any of the bleaching solution, the bleach-fixing solution and the fixing solution. It is considered that the transport of the bleaching agent and the fixing agent into the emulsion layer is expedited by vigorous stirring, and as a result, the desilverization rate is increased.
  • various chelating agents can be added to the color developing solution in such an amount that the chelating agents do not diminish the effect of the present invention, or otherwise interfere with the compounds used in the present invention.
  • JP-A-48-83820 can be used.
  • the same preservatives contained in the fixing solution and the bleach-fixing solution are also preferably contained in the rinsing water.
  • the amount of the replenisher of the fixing solution is from 300 to 3000 ml, preferably, from 300 to 1000 ml per m 2 of the photographic material in the case of a photographic material for photographing.
  • the amount of the replenisher is from 20 to 300 ml, preferably from 50 to 200 ml in the case of a photographic print material.
  • the replenishment rate of rinsing water or the stabilizing solution per unit area is 1 to 50 times, preferably 2 to 30 times, more preferably 2 to 15 times the amount carried over from the prebath.
  • the photographic materials for processing in accordance with the present invention may have various layer structures (e.g., red-sensitive, green-sensitive and blue-sensitive silver halide emulsion layers, undercoat layer, antihalation layer, filter layer, interlayer, surface protective layer) on one side or both sides of the support according to the intended purpose.
  • layer structures e.g., red-sensitive, green-sensitive and blue-sensitive silver halide emulsion layers, undercoat layer, antihalation layer, filter layer, interlayer, surface protective layer
  • the arrangement of the layers is not particularly limited.
  • the layer thickness is desirably reduced to the extent that the performance of the photographic material is not deteriorated.
  • the lower limit of the dry thickness of the entire constituent layers of the photographic material is 12.0 ⁇ m excluding the support and the undercoat layer of the support.
  • the lower limit of the entire dry thickness of a constituent layer provided between the undercoat layer of the support and the light-sensitive layer nearest the support is 1.0 ⁇ m.
  • the swelling ratio (equilibrium swelling layer thickness in H 2 O at 25°C - overall dry layer thickness at 25°C and 55% RH)/overall dry layer thickness at 25°C and 55% RH ⁇ 100] of the photographic material for processing in accordance with the present invention is preferably 50 to 200%, more preferably 70 to 150%.
  • image quality e.g., desilverization degree
  • layer physical properties such as layer strength are adversely affected.
  • Silver halide grains in the photographic emulsions may have a regular crystal form such as a cube, octahedron or tetradecahedron, an irregular crystal form such as a sphere or tabular form, a crystal form having defect such as twin plane or a composite form thereof.
  • Couplers which release a photographically useful residue upon coupling are preferably used in a photographic material for processing in accordance with the present invention.
  • DIR couplers which release a development restrainer include those described in the patent specifications cited in Research Disclosure (RD) No. 17643, item VII-F, JP-A-57-151944, JP-A-57-154234, JP-A-60-184248, JP-A-63-37346, U.S. Patents 4,248,962 and 4,782,012.
  • Organic solvents having a boiling point of not lower than about 30°C, preferably not lower than 50°C, but not higher than about 160°C can be used as co-solvents.
  • Typical examples of the co-solvents include ethyl acetate, butyl acetate, ethyl propionate, methyl ethyl ketone, cyclohexanone, 2-ethoxyethyl acetate and dimethylformamide.
  • An undercoated cellulose triacetate film support was coated with the following layers having the following compositions to prepare a multi-layer color photographic material s sample 101.
  • Second Layer Antihalation Layer Black colloidal silver 0.2 (as silver) Gelatin 2.2 UV-1 0.1 UV-2 0.2 Cpd-1 0.05 Solv-1 0.01 Solv-2 0.01 Solv-3 0.08
  • Second Layer Interlayer Fine silver bromide grains (grain size: 0.07 ⁇ m in terms of a diameter of a sphere) 0.15 (as silver) Gelatin 1.0 Cpd-2 0.2
  • Third Layer First Red-Sensitive Emulsion Layer Silver iodobromide emulsion (AgI content 10.0 mol%, internal high AgI type, grain size: 0.7 ⁇ m (in terms of a diameter of a sphere), a coefficient of variation in grain size (in terms of a diameter of a sphere): 14%, tetradecahedral grains) 0.26 (as silver) Silver iodobromide emulsion (AgI content 4.0 mol%, internal high AgI type, grain size: 0.4 ⁇ m (in terms of a
  • Example I-2 The sample 311 described in JP-A-2-28637 was processed with the standard bleaching solution used in Example I-1. In the same manner as in Example I-1, bleach fog ⁇ Dmin value was calculated on the basis of the Dmin value obtained on the standard bleaching solution. The Dmin value obtained by using the standard bleaching solution was 0.57. The results are shown in Table I-2.
  • Ion-exchanged water (the concentration of each of calcium ion and magnesium ion being not higher than 3 ppm)
  • Example I-1 The same photographic material as that of Example I-1 was exposed to white light (color temperature of 4800°K) through a wedge and processed in the following processing steps. Processing Step Step Step Processing Time Processing Temperature Replenishment Rate Tank Capacity Color Development 1 min 48°C 10 ml 2 l Bleaching 20 sec 48°C 10 ml 1 l Fixing 40 sec 48°C 30 ml 1 l Rinse 20 sec 40°C 30 ml 1 l Drying 40 sec 60°C Color Developing Solution Mother Solution Replenisher Diethylenetriaminepentaacetic acid 2.2 g 2.2 g 1-Hydroxyethylidene-1,1-diphosphonic acid 3.0 g 3.2 g Sodium sulfite 4.1 g 4.9 g Potassium carbonate 40 g 40 g Potassium bromide 1.4 g 0.4 g Potasium iodide 1.3 mg - 2-Methoxy-4-[N-ethyl-N-( ⁇ -hydroxye
  • the photographic material thus prepared was exposed through an optical wedge and processed in the following steps.
  • the rack of the automatic processor was replaced with a shortened rack such shorter processing times could be selected.
  • Rinse was a countercurrent system of from (2) to (1), and all of the overflow of the rinsing water was introduced into the fixing bath.
  • Replenishment to the bleach-fixing bath was carried out in the following manner.
  • the upper part of the bleaching tank in the automatic processor was connected with the bottom of the bleach-fixing tank by means of a pipe, and the upper part of the fixing tank was connected with the bottom of the bleach-fixing tank by means of a pipe such that all of the overflow produced by the supply of replenisher to the bleaching tank and the fixing tank was allowed to flow into the bleach-fixing bath.
  • Tap water was passed through a mixed bed column packed with H type strongly acidic cation exchange resin (Amberlite IR-120B, a product of Rohm & Haas Co.) and OH type strongly basic anion exchange resin (Amberlite IRA-400) to reduce the concentration of each of calcium ion and magnesium ion to not higher than 3 mg/l. Subsequently, sodium dichloroisocyanurate (20 mg/l) and sodium sulfate (150 mg/l) were added thereto. The pH of the solution was in the range of 6.7 to 7.5.
  • Example I-5 The processed sample was tested under the same conditions as those of Example I-1 to evaluate an increase in stain during the storage of image. The results are shown in Table I-5.
  • Fuji color SUPER HG400 (the manufacturer's serial number 311130) and Fuji color REALA (the manufacturer 5 serial number 861016) were processed by processing Nos. 201 to 211 of Example I-2, similar effects to those of Example I-2 were obtained.

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

Claims (10)

  1. Composition de traitement photographique pour traiter un matériau photographique couleur à l'halogénure d'argent exposé suivant une image, ladite composition de traitement contenant un composé de chélate métallique formé à partir d'un composé représenté par la formule (I) et d'un sel métallique choisi dans le groupe consistant en les sels de Fe(III), Mn(III), Co(III), Rh(II), Rh(III), Au(III), Au(II) et Ce(IV) :
    Figure 01960001
    où R, R1 et R2 représentent chacun un atome d'hydrogène, un groupe alkyle qui peut être substitué ou un groupe aryle qui peut être substitué, et L1 représente un groupe akylène ou un groupe arylène.
  2. Composition de traitement photographique selon la revendication 1, où ladite composition de traitement est une solution de blanchiment ou une solution de blanchiment-fixage contenant ledit composé de chélate métallique en une quantité de 0,05 à 1 mol/l de la composition de traitement.
  3. Composition de traitement photographique selon la revendication 1, où ledit composé de chélate métallique est formé à partir d'un composé représenté par la formule (I) et d'un sel métallique choisi dans le groupe consistant en les sels de Fe(III), Mn(III) et Ce(IV).
  4. Composition de traitement photographique selon la revendication 1, où ledit composé de chélate métallique est formé à partir d'un composé représenté par la formule (I) et d'un sel métallique de Fe(III).
  5. Composition de traitement photographique selon la revendication 1, où ledit composé représenté par la formule (I) est représenté par la formule (II) ou (III) :
    Figure 01960002
    Figure 01970001
    où R, R11, R31 et R32 représentent chacun un atome d'hydrogène, un groupe alkyle qui peut être substitué ou un groupe aryle qui peut être substitué ; L1 représente un groupe alkylène ou un groupe arylène ; L2, L3, L4, L5 et L6 représentent chacun un groupe alkylène ou un groupe arylène ; M représente un atome d'hydrogène, un métal alcalin ou un ammonium ; et W représente un groupe de liaison divalent lié à
    Figure 01970002
    par l'intermédiaire d'un groupe alkylène, tel qu'un groupe cyclohexylène, ou un groupe arylène.
  6. Composition de traitement photographique selon la revendication 5, où ledit composé de chélate métallique est formé à partir d'un composé représenté par la formule (III) et d'un sel métallique de Fe(III).
  7. Composition de traitement photographique selon la revendication 1, où ladite composition de traitement est une solution de blanchiment-fixage contenant ledit composé de chélate métallique et un agent de fixage.
  8. Procédé de traitement d'un matériau photographique couleur à l'halogénure d'argent exposé suivant une image comprenant un support sur lequel est disposée au moins une couche d'émulsion d'halogénure d'argent photosensible, comprenant tout d'abord le traitement du matériau photographique couleur à l'halogénure d'argent dans une solution de développement chromogène puis dans une seconde composition de traitement choisie parmi une solution de blanchiment ou de blanchiment-fixage contenant un composé de chélate métallique formé à partir d'un composé représenté par la formule (I) et d'un sel métallique choisi dans le groupe consistant en les sels de Fe(III), Mn(III), Co(III), Rh(II), Rh(III), Au(III), Au(II) et Ce(IV) en une quantité de 0,05 à 1 mol/l :
    Figure 01980001
    où R, R1 et R2 représentent chacun un atome d'ydrogène, un groupe alkyle qui peut être substitué ou un groupe aryle qui peut être substitué, et L1 représente un groupe akylène ou un groupe arylène.
  9. Procédé de traitement d'un matériau photographique couleur à l'halogénure d'argent selon la revendication 8, où ladite ou lesdites couches d'émulsion d'halogénure d'argent photosensible comprennent une émulsion d'halogénure d'argent ayant une teneur en iodure de 0,1 à 30 mol %, et ledit matériau photographique couleur est traité avec ladite seconde composition de traitement pendant une durée de 10 à 60 s.
  10. Procédé de traitement d'un matériau photographique couleur à l'halogénure d'argent selon la revendication 8, où ladite ou lesdites couches d'émulsion d'halogénure d'argent photosensible comprennent du chlorure d'argent ou du chlorobromure d'argent, et ledit matériau photographique couleur est traité avec ladite seconde composition de traitement pendant une durée de 5 à 30 s.
EP96103402A 1990-05-09 1991-05-07 Composition de traitement photographique et méthode de traitement l'utilisant Expired - Lifetime EP0720049B1 (fr)

Applications Claiming Priority (10)

Application Number Priority Date Filing Date Title
JP11925090 1990-05-09
JP11925090 1990-05-09
JP119250/90 1990-05-09
JP12858890A JPH0422948A (ja) 1990-05-18 1990-05-18 写真用処理組成物及び処理方法
JP128588/90 1990-05-18
JP12858890 1990-05-18
JP17502690 1990-07-02
JP175026/90 1990-07-02
JP17502690A JP2654714B2 (ja) 1990-05-09 1990-07-02 ハロゲン化銀カラー写真感光材料用の処理組成物及び処理方法
EP19910107440 EP0458131B1 (fr) 1990-05-09 1991-05-07 Composition de traitement photographique et méthode de traitement l'utilisant

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EP91107440.9 Division 1991-05-07
EP19910107440 Division EP0458131B1 (fr) 1990-05-09 1991-05-07 Composition de traitement photographique et méthode de traitement l'utilisant

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EP0720049A2 EP0720049A2 (fr) 1996-07-03
EP0720049A3 EP0720049A3 (fr) 1997-02-26
EP0720049B1 true EP0720049B1 (fr) 1999-08-04

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AU2007248656B2 (en) 2006-05-03 2013-04-04 Dana-Farber Cancer Institute, Inc. Histone deacetylase and tubulin deacetylase inhibitors
RU2515611C2 (ru) 2008-07-23 2014-05-20 Президент Энд Феллоуз Оф Гарвард Колледж Ингибиторы деацетилазы и их применение
WO2011019393A2 (fr) 2009-08-11 2011-02-17 President And Fellows Of Harvard College Inhibiteurs de hdac classe- et isoforme-spécifiques et utilisations de ceux-ci
CN116943871B (zh) * 2023-05-17 2024-04-26 江西理工大学 一种高效捕收剂及其制备方法和在高钙萤石矿中浮选萤石的应用

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DE69127130D1 (de) 1997-09-11
DE69131509T2 (de) 1999-11-25
EP0720049A3 (fr) 1997-02-26
EP0458131B1 (fr) 1997-08-06
DE69131509D1 (de) 1999-09-09
EP0458131A1 (fr) 1991-11-27
DE69127130T2 (de) 1997-12-11
EP0720049A2 (fr) 1996-07-03

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