EP0242768B1 - Stabilisation d'une image préparée d'argent photographique - Google Patents

Stabilisation d'une image préparée d'argent photographique Download PDF

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Publication number
EP0242768B1
EP0242768B1 EP87105465A EP87105465A EP0242768B1 EP 0242768 B1 EP0242768 B1 EP 0242768B1 EP 87105465 A EP87105465 A EP 87105465A EP 87105465 A EP87105465 A EP 87105465A EP 0242768 B1 EP0242768 B1 EP 0242768B1
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EP
European Patent Office
Prior art keywords
amino
silver
alkyl
aryl
triazole
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
EP87105465A
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German (de)
English (en)
Other versions
EP0242768A2 (fr
EP0242768A3 (en
Inventor
Werner Dr. Berthold
Günther Dr. Mahlberg
Paul Dr. Marx
Hans Dr. Öhlschläger
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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
    • G03C5/00—Photographic processes or agents therefor; Regeneration of such processing agents
    • G03C5/26—Processes using silver-salt-containing photosensitive materials or agents therefor
    • G03C5/38—Fixing; Developing-fixing; Hardening-fixing
    • G03C5/39—Stabilising, i.e. fixing without washing out
    • 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
    • Y10S430/166—Toner containing

Definitions

  • the invention relates to a method for producing a photographic silver image by exposing a silver halide material, developing, fixing, washing and aftertreatment with an aqueous aftertreatment bath.
  • the image tone may shift completely or in areas from black to brown or yellow in the course of time.
  • This change in image tone can be due to a conversion of the silver image to silver sulfide, e.g. in the case of insufficient washing out after fixation with sodium thiosulfate.
  • a similar disturbing image tone shift occurs when oxidizing gases are exposed to silver photographic images.
  • the oxidation of the image silver creates water-soluble silver salts that can diffuse in the material.
  • the photolysis of these soluble silver salts produces finely divided yellow to red-brown colored colloidal silver, or brown-colored silver compounds are formed. In many cases, such disturbing changes occur in the finished photographic silver image in the form of so-called microspot defects.
  • Microspot defects are understood to mean defects of microscopic size which occur in photographic black-and-white silver halide recording materials, which are characteristically round and generally have a yellow to reddish-brown appearance. These "microspot defects” are also known in the field of silver halide photographic materials as so-called “red spots”, “microscopic spots”, “drying or aging defects” or “microscopic defects or stains”.
  • microspots are described in more detail, for example, in a work by RW Henn and DG Wiest with the title “Microscopic Spots in Processed Microfilm: Their Nature and Prevention”, published in the journal “Photographic Science and Engineering, 1963, page 257; furthermore in one work by RW Henn, DG Wiest and BD Mack with the title “Microscopic Spots in Processed Microfilm: The Effect of lodide”, published in the journal “Photographic Science and Engineering", 1965, page 167 and in a work by CI Pope with the title “Blemish Formation in Processed Microfilm,” published in "Journal of Research of the National Bureau. of Standards A. Physics and Chemistry ", volume 72A; 1965; pages 251 to 259.
  • the microspot defects often occur in the form of concentric rings of different sizes, which are particularly noticeable in the semitones of the silver images.
  • stabilization is to be distinguished from the processing step referred to as “stabilization”, in which silver halides remaining in the material are not dissolved (fixed) and watered out, but are converted with complexing agents into light-sensitive complexes which remain in the material (EP-A- 189 603, GB-A-1 139 063, FR-A-2 147 272.
  • an alkyl group represented by R 1 or R 2 can be straight-chain or branched and preferably contain 1 to 4 carbon atoms. Examples are methyl, ethyl, isopropyl. Such an alkyl group can also be substituted, for example by hydroxyl, alkoxy, alkylthio, carboxyl, carbalkoxy or amino.
  • An alkenyl group is, for example, vinyl or allyl.
  • a cycloalkyl group is, for example, cyclohexyl.
  • An aryl group is, for example, phenyl, which can optionally be substituted, for example with halogen, alkoxy, alkylthio, acylamino or nitro.
  • the alkoxy, alkylthio or alkylsulfonyl groups represented by R 1 or R 2 preferably contain alkyl radicals having up to 4 carbon atoms; preferred examples are methoxy, methylthio, methylsulfonyl.
  • a sulfamoyl group is, for example, N, N-dimethylsulfamoyl.
  • An acyl radical is preferably derived from an aliphatic carboxylic acid with up to 4 carbon atoms; Acetyl is an example of this.
  • a heterocyclic group represented by R 1 or R 2 is in particular a furyl or pyridyl group.
  • AT amino-1,2,4-triazoles
  • amino-1,2,4-triazoles used according to the invention are known. A summary of their manufacture, physical properties, tautomerism ratios can be found in The Chemistry of Heterocyclic Compounds, John Wiley & Sons, New York, Volume 37, 1981.
  • the aftertreatment bath to be used in the process according to the invention consists of a solution of the stabilizing compounds.
  • Aqueous solutions are preferred, but solutions in organic solvents or in solvent mixtures of water and organic solvents, such as aliphatic alcohols, dimethylformamide or the like, can also be used.
  • the concentration of the stabilizing compounds in the aftertreatment bath can vary within wide limits. It depends on the effectiveness of the amino-1,2,4-triazole used, the material to be stabilized or the desired effect. In general, amounts between 0.5 and 50 g per liter have been found to be suitable. The optimum concentration in the individual case can easily be determined by the expert through routine tests.
  • the aftertreatment bath according to the invention may, however, contain other additives in addition to the aminotriazole compounds, such as wetting agents, pH-modifying agents and antioxidants, e.g. an alkali metal sulfite or a hydroxylamine salt.
  • the aftertreatment bath according to the invention stabilizes the silver image produced by any method by photographic means, so that it is less sensitive to external influences during subsequent storage or storage, in particular to the effects of oxidizing gases.
  • the occurrence of this stabilizing effect is also largely independent of the special type of photographic material used to produce the silver image, as long as it contains at least one photosensitive silver halide emulsion layer and is developed by any black and white development process.
  • the light-sensitive silver halide emulsions used in the recording material can contain chloride, bromide and iodide or mixtures thereof as the halide.
  • the halide content of at least one layer consists of 0 to 12 mol% of iodide, 0 to 50 mol% of chloride and 50 to 100 mol% of bromide.
  • the crystals are predominantly compact, e.g. are cubic or octahedral or have transitional forms. They can be characterized in that they essentially have a thickness of more than 0.2 pm.
  • the average ratio of diameter to thickness is preferably less than 8: 1, it being true that the diameter of a grain is defined as the diameter of a circle with a circle content corresponding to the projected area of the grain.
  • all or individual emulsions can also have essentially tabular silver halide crystals in which the ratio of diameter to thickness is greater than 8: 1.
  • the emulsions can be monodisperse or heterodisperse emulsions, which preferably have an average grain size of 0.3 pm to 1.2 pm.
  • the silver halide grains can have a layered grain structure.
  • hydrophilic film-forming agents are suitable as protective colloid or binder for the layers of the recording material, e.g. Proteins, especially gelatin. However, this can be replaced in whole or in part by other natural or synthetic binders. Casting aids and plasticizers can be used. Reference is made to Research Disclosure 17 643 (December 1978), in particular chapters IX, XI and XII.
  • the emulsions can be chemically and / or spectrally sensitized in the usual way; they can contain silver halide stabilizers, and the emulsion layers, as well as other non-photosensitive layers, can be hardened in the usual manner with known hardening agents.
  • Suitable chemical sensitizers, spectral sensitizing dyes, stabilizers and curing agents are described, for example, in Research Disclosure 17643; Reference is made in particular to chapters 111, IV, VI and X.
  • the recording materials subjected to the process according to the invention are exposed imagewise, it being possible to use ultraviolet, visible or infrared light or else high-energy radiation for the exposure.
  • This is followed by conventional processing to convert the exposed silver halide to image silver, to which end the recording material in the presence of a silver halide developer compound present in one of the layers of the recording material or can be contained in an aqueous treatment bath, is usually treated in an alkaline medium.
  • Inorganic or organic developer compounds can be used. Examples of this are hydroquinone, 3-pyrazolidone, aminophenol and their derivatives.
  • the development is followed by a fixing bath treatment, as a result of which the unexposed and undeveloped silver halide is released from the recording material. The material is then watered.
  • a useful test procedure is that the aftertreated dried black and white materials are exposed to a very dilute hydrogen peroxide atmosphere at a set relative air humidity of 84%.
  • This hydrogen peroxide atmosphere is produced by hydrolysis of sodium percarbonate Na 2 C0 3 -3H 2 0 2 at 84% relative air humidity and room temperature (22-24 ° C).
  • the rel. A humidity of 84% is set by a saturated KBr solution.
  • the exposed and processed paper strips are suspended vertically in a rectangular glass vessel of approximately 20 l. The glass vessel is in a tempered water bath to set the temperature of 22-24 ° inside the vessel.
  • Amino compounds of other heterocycles such as e.g. the compounds V-3, V-4, V-5, V-6 and V-8 have no stabilizing effect.

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

Claims (4)

1. Procédé de stabilisation d'une image argentique produite par photographie,. par traitement de l'image argentique finie avec un bain de post-traitement, caractérisé en ce que le bain de post-traitement contient un amino-1,2,4-triazole.
2. Procédé suivant la revendication 1, caractérisé en ce que l'amino-1,2,4-triazole répond à la formule I suivante
Figure imgb0011
lans laquelle
R1, R2 sont identiques ou différents et représentent H, ―NH2, un groupe alkyle, alcényle, cycloalkyle, aryle, alkoxy, alkylthio, alkylsulfonyle, sulfamoyle, acyle, -SH, ou un groupe hétérocyclique.
3. Procédé suivant la revendication 1, caractérisé en ce que l'amino-1,2,4-triazole répond à l'une des - formules II et III suivantes
Figure imgb0012
Figure imgb0013
où
R3, R4 sont identiques ou différents et représentent H, -NH2, un groupe alkyle, aryle ou alkylthio;
R5 est un reste tel que R4 ou -SH,
R6 représente H, un groupe alkyle, aryle ou ―X―R7;
X représente -CO-, -CS- ou -SO2-;
R7 est un groupe alkyle, alcényle, cycloalkyle, aryle ou un groupe amino.
4. Procédé suivant l'une des revendications 1 à 3, caractérisé en ce que l'amino-1,2,4-triazole est présent dans un bain aqueux de post-traitement en une quantité de 0,5 à 50 g par litre.
EP87105465A 1986-04-23 1987-04-13 Stabilisation d'une image préparée d'argent photographique Expired - Lifetime EP0242768B1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE19863613622 DE3613622A1 (de) 1986-04-23 1986-04-23 Stabilisierung eines fotografisch hergestellten silberbildes
DE3613622 1986-04-23

Publications (3)

Publication Number Publication Date
EP0242768A2 EP0242768A2 (fr) 1987-10-28
EP0242768A3 EP0242768A3 (en) 1988-10-19
EP0242768B1 true EP0242768B1 (fr) 1990-05-23

Family

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Family Applications (1)

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EP87105465A Expired - Lifetime EP0242768B1 (fr) 1986-04-23 1987-04-13 Stabilisation d'une image préparée d'argent photographique

Country Status (4)

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US (1) US4760015A (fr)
EP (1) EP0242768B1 (fr)
JP (1) JPS62257150A (fr)
DE (2) DE3613622A1 (fr)

Families Citing this family (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4960683A (en) * 1987-06-29 1990-10-02 Fuji Photo Film Co., Ltd. Method for processing a black-and-white photosensitive material
DE3733291A1 (de) * 1987-10-02 1989-04-20 Agfa Gevaert Ag Stabilisierung eines fotografisch hergestellten silberbildes
EP0356581B1 (fr) * 1988-08-09 1993-07-14 Agfa-Gevaert N.V. Méthode de traitement d'un matériau photographique à émulsion d'halogénure d'argent
US4987059A (en) * 1988-12-01 1991-01-22 Agfa-Gevaert Aktiengesellschaft Process for stabilizing photographic silver images
JP2981933B2 (ja) * 1991-09-25 1999-11-22 コニカ株式会社 ハロゲン化銀カラー写真感光材料用安定液及び該安定液を用いた処理方法
US6348293B1 (en) * 1999-11-26 2002-02-19 Agfa-Gevaert Radiographic film material exhibiting increased covering power and “colder” blue-black image tone

Family Cites Families (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3577240A (en) * 1965-02-09 1971-05-04 Fuji Photo Film Co Ltd Diffusion transfer photographic materials
GB1139063A (en) * 1965-02-10 1969-01-08 Kodak Ltd Improvements in photographic reproduction processes
DE1930339A1 (de) * 1969-06-14 1970-12-17 Agfa Gevaert Ag Bildempfangsmaterial fuer Silbersalzdiffusionsverfahren
BE785960A (fr) * 1971-07-27 1973-01-08 Agfa Gevaert Nv Stabilisering van ontwikkelde fotografische beelden
US4351896A (en) * 1980-12-12 1982-09-28 Eastman Kodak Company Mesoionic silver halide stabilizer precursor and use in a heat developable and heat stabilizable photographic silver halide material and process
US4404390A (en) * 1980-12-12 1983-09-13 Eastman Kodak Company Mesoionic 1,2,4-triazolium silver halide stabilizer precursors
JPS60122936A (ja) * 1983-12-07 1985-07-01 Fuji Photo Film Co Ltd ハロゲン化銀写真感光材料
EP0189603A1 (fr) * 1985-01-29 1986-08-06 Agfa-Gevaert N.V. Procédé pour la production d'une image argentique comprenant un traitement de stabilisation-fixage

Also Published As

Publication number Publication date
EP0242768A2 (fr) 1987-10-28
DE3613622A1 (de) 1987-10-29
JPS62257150A (ja) 1987-11-09
US4760015A (en) 1988-07-26
EP0242768A3 (en) 1988-10-19
DE3762927D1 (de) 1990-06-28

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