EP0309873B1 - Stabilisation of a photographic picture produced with silver - Google Patents
Stabilisation of a photographic picture produced with silver Download PDFInfo
- Publication number
- EP0309873B1 EP0309873B1 EP88115431A EP88115431A EP0309873B1 EP 0309873 B1 EP0309873 B1 EP 0309873B1 EP 88115431 A EP88115431 A EP 88115431A EP 88115431 A EP88115431 A EP 88115431A EP 0309873 B1 EP0309873 B1 EP 0309873B1
- Authority
- EP
- European Patent Office
- Prior art keywords
- silver
- image
- stabilizing
- photographic
- silver halide
- 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
Links
- 229910052709 silver Inorganic materials 0.000 title claims description 53
- 239000004332 silver Substances 0.000 title claims description 53
- 230000006641 stabilisation Effects 0.000 title description 7
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims description 33
- 238000000034 method Methods 0.000 claims description 17
- 230000000087 stabilizing effect Effects 0.000 claims description 17
- 125000001931 aliphatic group Chemical group 0.000 claims description 5
- ULRPISSMEBPJLN-UHFFFAOYSA-N 2h-tetrazol-5-amine Chemical compound NC1=NN=NN1 ULRPISSMEBPJLN-UHFFFAOYSA-N 0.000 claims description 4
- TZUIXDKNPBARSI-UHFFFAOYSA-N 3-sulfanyl-2,6-dihydro-1h-triazine Chemical compound SN1NNCC=C1 TZUIXDKNPBARSI-UHFFFAOYSA-N 0.000 claims description 4
- 125000003118 aryl group Chemical group 0.000 claims description 4
- 125000004432 carbon atom Chemical group C* 0.000 claims description 4
- 229910052739 hydrogen Inorganic materials 0.000 claims description 4
- 239000001257 hydrogen Substances 0.000 claims description 4
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 4
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 4
- 229920006395 saturated elastomer Chemical group 0.000 claims description 4
- 125000003545 alkoxy group Chemical group 0.000 claims description 2
- 229910052736 halogen Inorganic materials 0.000 claims description 2
- 150000002367 halogens Chemical group 0.000 claims description 2
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 claims description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims 1
- -1 silver halide Chemical class 0.000 description 28
- 239000000463 material Substances 0.000 description 17
- 150000001875 compounds Chemical class 0.000 description 10
- 239000000839 emulsion Substances 0.000 description 9
- 239000010410 layer Substances 0.000 description 9
- 239000011521 glass Substances 0.000 description 6
- 239000000243 solution Substances 0.000 description 6
- 238000011105 stabilization Methods 0.000 description 6
- 238000012545 processing Methods 0.000 description 5
- 239000003381 stabilizer Substances 0.000 description 5
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 4
- 238000011161 development Methods 0.000 description 4
- 238000002845 discoloration Methods 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 description 2
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 2
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 229910052783 alkali metal Inorganic materials 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 2
- 239000011230 binding agent Substances 0.000 description 2
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 238000009792 diffusion process Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 150000004820 halides Chemical class 0.000 description 2
- XMBWDFGMSWQBCA-UHFFFAOYSA-N hydrogen iodide Chemical compound I XMBWDFGMSWQBCA-UHFFFAOYSA-N 0.000 description 2
- 238000010348 incorporation Methods 0.000 description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- 230000001590 oxidative effect Effects 0.000 description 2
- 229920002006 poly(N-vinylimidazole) polymer Polymers 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 150000003378 silver Chemical class 0.000 description 2
- 229940100890 silver compound Drugs 0.000 description 2
- 150000003379 silver compounds Chemical class 0.000 description 2
- GGCZERPQGJTIQP-UHFFFAOYSA-N sodium;9,10-dioxoanthracene-2-sulfonic acid Chemical compound [Na+].C1=CC=C2C(=O)C3=CC(S(=O)(=O)O)=CC=C3C(=O)C2=C1 GGCZERPQGJTIQP-UHFFFAOYSA-N 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- 239000000080 wetting agent Substances 0.000 description 2
- 150000005208 1,4-dihydroxybenzenes Chemical class 0.000 description 1
- 125000000022 2-aminoethyl group Chemical group [H]C([*])([H])C([H])([H])N([H])[H] 0.000 description 1
- CDAWCLOXVUBKRW-UHFFFAOYSA-N 2-aminophenol Chemical compound NC1=CC=CC=C1O CDAWCLOXVUBKRW-UHFFFAOYSA-N 0.000 description 1
- 125000001340 2-chloroethyl group Chemical group [H]C([H])(Cl)C([H])([H])* 0.000 description 1
- 125000004200 2-methoxyethyl group Chemical group [H]C([H])([H])OC([H])([H])C([H])([H])* 0.000 description 1
- 108010010803 Gelatin Proteins 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 1
- 241001061127 Thione Species 0.000 description 1
- 229910052946 acanthite Inorganic materials 0.000 description 1
- XYXNTHIYBIDHGM-UHFFFAOYSA-N ammonium thiosulfate Chemical compound [NH4+].[NH4+].[O-]S([O-])(=O)=S XYXNTHIYBIDHGM-UHFFFAOYSA-N 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 238000005266 casting Methods 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000000084 colloidal system Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- VTIIJXUACCWYHX-UHFFFAOYSA-L disodium;carboxylatooxy carbonate Chemical compound [Na+].[Na+].[O-]C(=O)OOC([O-])=O VTIIJXUACCWYHX-UHFFFAOYSA-L 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 238000005562 fading Methods 0.000 description 1
- 229920000159 gelatin Polymers 0.000 description 1
- 239000008273 gelatin Substances 0.000 description 1
- 235000019322 gelatine Nutrition 0.000 description 1
- 235000011852 gelatine desserts Nutrition 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 125000004356 hydroxy functional group Chemical group O* 0.000 description 1
- 150000002443 hydroxylamines Chemical class 0.000 description 1
- 125000004029 hydroxymethyl group Chemical group [H]OC([H])([H])* 0.000 description 1
- 150000002541 isothioureas Chemical class 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 125000000286 phenylethyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])C([H])([H])* 0.000 description 1
- 238000006303 photolysis reaction Methods 0.000 description 1
- 230000015843 photosynthesis, light reaction Effects 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 239000004848 polyfunctional curative Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 239000011241 protective layer Substances 0.000 description 1
- 108090000623 proteins and genes Proteins 0.000 description 1
- 102000004169 proteins and genes Human genes 0.000 description 1
- NDGRWYRVNANFNB-UHFFFAOYSA-N pyrazolidin-3-one Chemical compound O=C1CCNN1 NDGRWYRVNANFNB-UHFFFAOYSA-N 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 230000001235 sensitizing effect Effects 0.000 description 1
- 229940056910 silver sulfide Drugs 0.000 description 1
- XUARKZBEFFVFRG-UHFFFAOYSA-N silver sulfide Chemical compound [S-2].[Ag+].[Ag+] XUARKZBEFFVFRG-UHFFFAOYSA-N 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 235000017550 sodium carbonate Nutrition 0.000 description 1
- 229940045872 sodium percarbonate Drugs 0.000 description 1
- AKHNMLFCWUSKQB-UHFFFAOYSA-L sodium thiosulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=S AKHNMLFCWUSKQB-UHFFFAOYSA-L 0.000 description 1
- 235000019345 sodium thiosulphate Nutrition 0.000 description 1
- MWNQXXOSWHCCOZ-UHFFFAOYSA-L sodium;oxido carbonate Chemical compound [Na+].[O-]OC([O-])=O MWNQXXOSWHCCOZ-UHFFFAOYSA-L 0.000 description 1
- 239000011877 solvent mixture Substances 0.000 description 1
- 230000003595 spectral effect Effects 0.000 description 1
- 235000011149 sulphuric acid Nutrition 0.000 description 1
- 150000005326 tetrahydropyrimidines Chemical class 0.000 description 1
- 150000004905 tetrazines Chemical class 0.000 description 1
- 150000004897 thiazines Chemical class 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 229910052724 xenon Inorganic materials 0.000 description 1
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 1
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
-
- 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 stabilizing photographic silver images by treatment with an aftertreatment bath.
- photographic silver images which have been produced by developing and fixing exposed silver halide emulsion layers, it is possible that the image tone shifts in whole or in part from black to brown or yellow in the course of time.
- This change in the image tone can be based on a conversion of the silver image into silver sulfide, which can occur, for example, if the washout is insufficient 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.
- This soluble silver salts finely divided yellow to red-brown colored colloidal silver is formed, or brown colored silver compounds are formed.
- such disturbing changes occur in the finished photographic silver image in the form of so-called microspot defects.
- the invention thus relates to a process for stabilizing a photographically produced silver image by treating the finished silver image with an aftertreatment bath, which is characterized in that the aftertreatment bath contains aminotetrazole of the formula I. or a mercaptotetrahydrotriazine of the formula II wherein
- R1, R3 and R4 independently of one another hydrogen, saturated or unsaturated, optionally e.g. phenyl-substituted aliphatic groups with up to 6 carbon atoms, such as methyl, ethyl, propyl, butyl, allyl, benzyl or phenylethyl, or aryl groups, in particular phenyl; and
- R2 is hydrogen, saturated or unsaturated aliphatic groups with up to 6 carbon atoms, such as methyl, ethyl, butyl or allyl, it being possible for the aliphatic groups to be substituted by hydroxy, alkoxy, amino, halogen or phenyl, such as hydroxymethyl, 2-hydroxypropyl, 2-methoxyethyl, 2-aminoethyl, 3-dimethylaminopropyl, 2-chloroethyl, 3-chloropropyl or benzyl or aryl groups, in particular phenyl,
- the aminotetrazole used in the invention is known. It was already used in the EP-A-0 242 768 to be considered in accordance with Article 54 (3) EPC in a 1% by weight solution as an image silver stabilizer. The preparation of the mercaptotetrahydrotriazines is described in US-A-3,712,818.
- the aftertreatment bath to be used in the stabilization 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 pH of the solution can be raised or lowered, e.g. with KOH or with H2SO4.
- the method according to the invention can be used in the broadest way for photographic silver images, regardless of the special way in which they are produced.
- silver images can be made using conventional methods by developing and fixing an exposed photographic Materials were manufactured to be stabilized. These can be conventional halftone images, office copies or microfilms.
- the method according to the invention can also be used to stabilize copies which have been produced by the silver salt diffusion method.
- Finished silver images are subjected to the stabilization process according to the invention, i.e. Silver images obtained by photographic processing by developing an imagewise exposed photographic material containing silver halide, and the processing procedure after the development step may include a stabilizing treatment step in which the unexposed silver halide is completely or partially removed or converted to a non-photosensitive form .
- Such a stabilizing treatment step can consist, for example, of subjecting the developed photographic recording material, which already contains the silver image but also residual silver halide, to a conventional fixing treatment, for example in a processing bath which contains an alkali metal thiosulfate or ammonium thiosulfate, the silver halide being soluble Siberian complex salt is extracted from the recording material.
- a "stable" silver image is produced, the stability of which is based on the fact that essentially no light-sensitive silver halide is present in the unexposed areas, and which is referred to in the present context as a finished silver image.
- the stabilizing method according to the invention is to be distinguished from the stabilizing treatment stage mentioned, for which compounds of the formula II have already been proposed (DE-A-1 772 734). While the latter serves to remove or convert any remaining silver halide, the stabilization process according to the invention is only used when the silver image produced contains essentially no more photosensitive silver halide.
- the finished silver image which is subjected to the stabilization process according to the invention can, as already mentioned, also be a silver image which has been produced by the silver salt diffusion process. Such a silver image can have been produced in a separate image-receiving layer which may contain silver precipitation nuclei but no silver halide.
- the aftertreatment bath according to the invention therefore does not need to contain any substances which serve to remove residual silver halide.
- the aftertreatment bath according to the invention can contain further additives such as wetting agents, pH-modifying agents and antioxidants, e.g. contain an alkali metal sulfite or a hydroxylamine salt.
- the aftertreatment bath according to the invention stabilizes the silver image produced by any method by photography, 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 The stabilizing effect is also largely independent of the special type of photographic recording material used to produce the silver image, as long as it contains at least one light-sensitive 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.
- these are predominantly compact crystals that are, for example, cubic or octahedral or have transitional forms. They can be characterized in that they essentially have a thickness of more than 0.2 ⁇ m.
- 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 ⁇ m up to 1.2 ⁇ m.
- 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 hardeners.
- 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 III, IV, VI and X.
- the recording materials subjected to the stabilization process according to the invention are exposed imagewise, it being possible to use ultraviolet, visible or intra-red light or else high-energy radiation for the exposure.
- This is followed by conventional processing to convert the exposed silver halide to image silver, for which purpose the recording material in the presence of a silver halide developer compound, which can be contained in one of the layers of the recording material or 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.
- Resarch Disclosure 17 643, Chapter XX As a rule, 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 stabilizing method according to the invention can be used at any time after the development and generation of the finished silver image, it is most effective when it is used as the last treatment step before the black and white image is dried. This also means that preferably no further liquid treatment, in particular no washing, follows the stabilizing bath according to the invention. Rather, the stabilizing bath according to the invention is used as an aftertreatment or final bath.
- the soluble and colorless silver compounds which form when the silver image is destroyed are rendered insoluble by the stabilizer bath according to the invention. As can be seen from the table, it was surprisingly found that the claimed compounds have an excellent action.
Landscapes
- Physics & Mathematics (AREA)
- General Physics & Mathematics (AREA)
- Silver Salt Photography Or Processing Solution Therefor (AREA)
- Non-Silver Salt Photosensitive Materials And Non-Silver Salt Photography (AREA)
Description
Die Erfindung betrifft ein Verfahren zur Stabilisierung von fotografischen Silberbildern durch Behandlung mit einem Nachbehandlungsbad.The invention relates to a method for stabilizing photographic silver images by treatment with an aftertreatment bath.
Bei fotografischen Silberbildernm, die durch Entwicklung und Fixierung belichteter Silberhalogenidemulsionschichten hergestellt worden sind, kommt es vor, daß sich der Bildton im Laufe der Zeit ganz oder flächenweise von schwarz nach braun oder gelb verschiebt.In photographic silver images, which have been produced by developing and fixing exposed silver halide emulsion layers, it is possible that the image tone shifts in whole or in part from black to brown or yellow in the course of time.
Diese Änderung des Bildtons kann auf einer Umwandlung des Silberbildes in Silbersulfid beruhen, die z.B. bei ungenügendem Auswaschen nach der Fixierung mit Natriumthiosulfat auftreten kann. Eine ähnliche störende Bildtonverschiebung tritt bei Einwirkung oxidierender Gase auf fotografische Silberbilder auf. Durch die Oxidation des Bildsilbers entstehen wasserlösliche Silbersalze, die im Material diffundieren können. Durch Photolyse dieser löslichen Silbersalze entsteht feinverteiltes gelb bis rotbraun gefärbtes kolloidales Silber, oder es entstehen braungefärbte Silberverbindungen. Vielfach treten derartige störende Veränderungen in dem fertigen fotografischen Silberbild punktförmig auf in Form sogenannter Mikrospot-Defekte.This change in the image tone can be based on a conversion of the silver image into silver sulfide, which can occur, for example, if the washout is insufficient 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. By photolysis this soluble silver salts, finely divided yellow to red-brown colored colloidal silver is formed, 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.
Es hat nicht an Versuchen gefehlt, diese störenden nachträglichen Veränderungen der auf fotografischem Weg hergestellten Silberbilder zu vermeiden oder zu reduzieren, z.B. dadurch, daß die für die Verarbeitung der bildmäßig belichteten fotografischen Aufzeichnungsmaterialien benötigten Chemikalien gründlicher ausgewässert werden, oder dadurch, daß die verarbeiteten Aufzeichnungsmaterialien, d.h. die fertigen Silberbilder unter standartisierten atmosphärischen Bedingungen aufbewahrt werden.There has been no lack of attempts to avoid or reduce these troublesome subsequent changes in the silver images produced by photography, e.g. in that the chemicals required for the processing of the imagewise exposed photographic recording materials are more thoroughly leached out, or in that the processed recording materials, i.e. The finished silver pictures are kept under standardized atmospheric conditions.
Desweiteren sind bereits verschiedene Verbindungsklassen für die Stabilisierung fertiger Silberbilder beschrieben worden.Furthermore, various classes of compounds for stabilizing finished silver images have already been described.
Erwähnt seien nichtcyclische oder cyclische Thiosemicarbazide (DE-A-20 00 622), heterocyclische Mercapto- oder Thionverbindungen aus der Reihe der Tetrahydropyrimidine, Thiazine oder Tetrazine (DE-A-20 13 423), organische und anorganische Rhodanide (DE-A-22 18 387) und Isothioharnstoffe (US-A-4 500 632). Diese Substanzen befriedigen jedoch die Ansprüche der Praxis nicht, da ihre Stabilisierwirkung nicht ausreicht bzw. die fotografischen Eigenschaften der Schichten in unerwünschter Weise beeinflußt werden.Mention should be made of non-cyclic or cyclic thiosemicarbazides (DE-A-20 00 622), heterocyclic mercapto or thione compounds from the series of tetrahydropyrimidines, thiazines or tetrazines (DE-A-20 13 423), organic and inorganic rhodanides (DE-A-22 18,387) and isothioureas (US-A-4,500,632). However, these substances do not meet the requirements in practice because their stabilizing effect is insufficient and the photographic properties of the layers are influenced in an undesirable manner.
Desweiteren sind Verfahren bekannt, bei denen die stabilisierenden Zusätze direkt in das fotografische Silberhalogenidmaterial eingelagert werden. So wird in DE-A-31 51 182 (GB-A-2 090 991) die Einlagerung von Polyvinylimidazol und in GB-A-1 156 167 die Einlagerung von sulfoalkysubstituieten Hydrochinonen berchrieben.Furthermore, methods are known in which the stabilizing additives are incorporated directly into the silver halide photographic material. DE-A-31 51 182 (GB-A-2 090 991) describes the incorporation of polyvinylimidazole and GB-A-1 156 167 describes the incorporation of sulfoalkysubstituted hydroquinones.
Für eine ausreichende Stabilisierung müssen hierbei jedoch relativ hohe Konzentrationen von 0,5 g/m² eingesetzt werden. Die Verträglichkeit des Polyvinylimidazols selbst mit Silberhalogenidemulsionen, mit Netzmitteln, Stabilisatoren, Entwicklern, sowie Hilfosentwicklern ist äußerst kritisch. Hohe Konzentrationen in der Schutzschicht führen darüberhinaus zu einen Glanzverlust.For sufficient stabilization, however, relatively high concentrations of 0.5 g / m² must be used. The compatibility of the polyvinylimidazole even with silver halide emulsions, with wetting agents, stabilizers, developers and auxiliary developers is extremely critical. High concentrations in the protective layer also lead to a loss of gloss.
Es wurde nun ein Verfahren zur Stabiliserung fotografisch hergestellter Silberbilder gefunden, das die obengenannten Nachteile ausschließt, wobei ein Nachbehandlungsbad verwendet wird, das als stabilisierende Verbindung Aminotetrazol oder ein Mercaptotetrahydrotriazin in bestimmter Menge enthält.We have now found a process for stabilizing photographically produced silver images which eliminates the disadvantages mentioned above, using an aftertreatment bath which contains aminotetrazole or a mercaptotetrahydrotriazine in a certain amount as the stabilizing compound.
Gegenstand der Erfindung ist somit ein Verfahren zur Stabilisierung eines fotografisch hergestellten Silberbildes durch Behandlung des fertigen Silberbildes mit eineim Nachbehandlungsbad, das dadurch gekennzeichnet ist, daß das Nachbehandlungsbad Aminotetrazol der Formel I
oder ein Mercaptotetrahydrotriazin der Formel II
worinThe invention thus relates to a process for stabilizing a photographically produced silver image by treating the finished silver image with an aftertreatment bath, which is characterized in that the aftertreatment bath contains aminotetrazole of the formula I.
or a mercaptotetrahydrotriazine of the formula II
wherein
R₁, R₃ und R₄ unabhängig voneinander Wasserstoff, gesättigte oder ungesättigte, gegebenfalls z.B. durch Phenyl substituierte aliphatische Gruppen mit bis zu 6 C-Atomen, wie Methyl, Ethyl, Propyl, Butyl, Allyl, Benzyl oder Phenylethyl, oder Arylgruppen insbesondere Phenyl; undR₁, R₃ and R₄ independently of one another hydrogen, saturated or unsaturated, optionally e.g. phenyl-substituted aliphatic groups with up to 6 carbon atoms, such as methyl, ethyl, propyl, butyl, allyl, benzyl or phenylethyl, or aryl groups, in particular phenyl; and
R₂ Wasserstoff, gesättigte oder ungesättigte aliphatische Gruppen mit bis zu 6 C-Atomen, wie Methyl, Ethyl, Butyl oder Allyl, wobei die aliphatischen Gruppen mit Hydroxy, Alkoxy, Amino, Halogen oder Phenyl substituiert sein können, wie Hydroxymethyl, 2-Hydroxypropyl, 2-Methoxyethyl, 2-Aminoethyl, 3-Dimethylaminopropyl, 2-Chlorethyl, 3-Chlorpropyl oder Benzyl oder Arylgruppen, insbesondere Phenyl bedeuten,R₂ is hydrogen, saturated or unsaturated aliphatic groups with up to 6 carbon atoms, such as methyl, ethyl, butyl or allyl, it being possible for the aliphatic groups to be substituted by hydroxy, alkoxy, amino, halogen or phenyl, such as hydroxymethyl, 2-hydroxypropyl, 2-methoxyethyl, 2-aminoethyl, 3-dimethylaminopropyl, 2-chloroethyl, 3-chloropropyl or benzyl or aryl groups, in particular phenyl,
in einer Konzentration von 1,5 bis 4 Gew.-% enthält.contains in a concentration of 1.5 to 4 wt .-%.
Geeignete Beispiele außer der Verbindung I sind:
Das erfindungsgemäß verwendete Aminotetrazol ist bekannt. Es wurde bereits in der nach Artikel 54 (3) EPÜ zu berücksichtigenden EP-A-0 242 768 in 1 gew.-%iger Lösung als Bildsilberstabilisator verwendet. Die Herstellung der Mercaptotetrahydrotriazine ist in US-A-3 712 818 beschrieben.The aminotetrazole used in the invention is known. It was already used in the EP-A-0 242 768 to be considered in accordance with Article 54 (3) EPC in a 1% by weight solution as an image silver stabilizer. The preparation of the mercaptotetrahydrotriazines is described in US-A-3,712,818.
Das im Rahmen des erfindungsgemäßen Stabilisierverfahrens zu verwendende Nachbehandlungsbad besteht im einfachsten Falle aus einer Lösung der stabilisierenden Verbindungen. Bevorzugt sind wäßrige Lösungen, es können jedoch auch Lösungen in organischen Lösungsmitteln oder in Lösungsmittelgemischen aus Wasser und organischen Lösungsmitteln, wie aliphatischen Alkoholen, Dimethylformamid oder ähnlichen, verwendet werden. Zur Löslichkeitsverbesserung wäßriger Lösungen kann der pH-Wert der Lösung angehoben oder erniedrigt werden, z.B. mit KOH oder mit H₂SO₄.In the simplest case, the aftertreatment bath to be used in the stabilization 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. To improve the solubility of aqueous solutions, the pH of the solution can be raised or lowered, e.g. with KOH or with H₂SO₄.
Das erfindungsgemäße Verfahren ist in breitester Weise für fotografische Silberbilder anwendbar, unabhängig von der speziellen Art ihrer Herstellung. So können z.B. Silberbilder, die nach konventionellen Verfahren durch Entwicklung und Fixierung eines belichteten fotografischen Materials hergestellt wurden, stabilisiert werden. Dabei kann es sich um übliche Halbtonbilder, um Bürokopien oder um Mikrofilme handeln. Nach dem erfindungsgemäßen Verfahren sind auch solche Kopien stabilisierbar, die nach dem Sibersalzdiffusionsverfahren hergestellt wurden.The method according to the invention can be used in the broadest way for photographic silver images, regardless of the special way in which they are produced. For example, silver images can be made using conventional methods by developing and fixing an exposed photographic Materials were manufactured to be stabilized. These can be conventional halftone images, office copies or microfilms. The method according to the invention can also be used to stabilize copies which have been produced by the silver salt diffusion method.
Dem erfindungsgemäßen Stabilisierverfahren werden fertige Silberbilder unterworfen, d.h. Silberbilder, die auf fotografischem Wege durch Entwickeln eines bildmäßig belichteten Silberhalogenid enthaltenden fotografischen Aufzeichnungsmaterials erhalten worden sind, wobei das Verarbeitungsverfahren im Anschluß an den Entwicklungsschritt eine stabilisierende Behandlungsstufe umfassen kann, bei der das nicht belichtete Silberhalogenid vollständig oder teilweise entfernt oder in eine nichtlichtempfindliche Form umgewandelt wird.Finished silver images are subjected to the stabilization process according to the invention, i.e. Silver images obtained by photographic processing by developing an imagewise exposed photographic material containing silver halide, and the processing procedure after the development step may include a stabilizing treatment step in which the unexposed silver halide is completely or partially removed or converted to a non-photosensitive form .
Eine solche stabilisierende Behandlungsstufe kann beispielsweise darin bestehen, daß das entwickelte fotografische Aufzeichnungsmaterial, das bereits das Silberbild, aber daneben noch restliches Silberhalogenid enthält, einer üblichen Fixierbehandlung z.B. in einem Verarbeitungsbad, das ein Alkalithiosulfat oder Ammoniumthiosulfat enthält, unterworfen wird, wobei das Silberhalogenid als lösliches Siberkomplexsalz aus dem Aufzeichnugsmateiral herausgelöst wird. Auf diese Weise wird ein "stabiles" Silberbild erzeugt, dessen Stabilität darauf beruht, daß in den nicht belichteten Bereichen in wesentlichen kein lichtempfindliches Silberhalogenid mehr vorhanden ist, und das im vorliegenden Zusammenhang als fertiges Siberbild bezeichnet wird.Such a stabilizing treatment step can consist, for example, of subjecting the developed photographic recording material, which already contains the silver image but also residual silver halide, to a conventional fixing treatment, for example in a processing bath which contains an alkali metal thiosulfate or ammonium thiosulfate, the silver halide being soluble Siberian complex salt is extracted from the recording material. In this way, a "stable" silver image is produced, the stability of which is based on the fact that essentially no light-sensitive silver halide is present in the unexposed areas, and which is referred to in the present context as a finished silver image.
Das erfindungsgemäße Stabilisierverfahren ist zu unterscheiden von der erwähnten stabilisierenden Behandlungsstufe, für die bereits Verbindungen der Formel II vorgeschlagen wurden (DE-A-1 772 734). Während die letztere der Entfernung bzw. Umwandlung noch vorhandenen restlichen Silberhalogenids dient, kommt das erfindungsgemäße Stabilisierverfahren erst dann zur Anwendung, wenn das erzeugte Silberbild im wesentlichen kein lichtempfindliches Silberhalogenid (mehr) enthält. Das fertige Silberbild, das dem erfindungsgemäßen Stabilisierverfahren unterworfen wird, kann wie bereits erwähnt auch ein Silberbild sein, das nach dem Silbersalzdiffusionsverfahren hergestellt worden ist. Ein solches Silberbild kann in einer separaten Bildempfangsschicht erzeugt worden sein, die gegebenenfalls Silberfällungskeime aber kein Silberhalogenid enthält.The stabilizing method according to the invention is to be distinguished from the stabilizing treatment stage mentioned, for which compounds of the formula II have already been proposed (DE-A-1 772 734). While the latter serves to remove or convert any remaining silver halide, the stabilization process according to the invention is only used when the silver image produced contains essentially no more photosensitive silver halide. The finished silver image which is subjected to the stabilization process according to the invention can, as already mentioned, also be a silver image which has been produced by the silver salt diffusion process. Such a silver image can have been produced in a separate image-receiving layer which may contain silver precipitation nuclei but no silver halide.
Das erfindungsgemäße Nachbehandlungsbad braucht daher keinerlei Substanzen zu enthalten, die der Entfernung restlichen Silberhalogenids dienen.The aftertreatment bath according to the invention therefore does not need to contain any substances which serve to remove residual silver halide.
Das erfindungsgemäße Nachbehandlungsbad kann weitere Zusätze wie Netzmittel, pH-modifizierende Mittel und Oxidationsschutzmittel, z.B. ein Alkalimetallsulfit oder ein Hydroxylaminsalz enthalten.The aftertreatment bath according to the invention can contain further additives such as wetting agents, pH-modifying agents and antioxidants, e.g. contain an alkali metal sulfite or a hydroxylamine salt.
Durch das erfindungsgemäße Nachbehandlungsbad wird das nach irgendeinem Verfahren auf fotografischem Wege erzeugte Silberbild stabilisiert, so daß es gegen äußere Einwirkung bei der nachträglichen Lagerung bzw. Aufbewahrung, insbesondere gegen die Einwirkung oxidierender Gase, weniger empfindlich ist. Das Eintreten dieses stabilisierenden Effektes ist dabei auch weitgehend unahängig von der speziellen Art des zur Herstellung des Silberbildes verwendeten fotografischen Aufzeichnungs- materials, solange dieses mindestens eine lichtempfindliche Siberhalogenidemulsionsschicht enthält und nach einem beliebigen Schwarzweiß-Entwicklungsverfahren entwickelt wird.The aftertreatment bath according to the invention stabilizes the silver image produced by any method by photography, 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 The stabilizing effect is also largely independent of the special type of photographic recording material used to produce the silver image, as long as it contains at least one light-sensitive silver halide emulsion layer and is developed by any black-and-white development process.
Die in dem Aufzeichnungsmaterial verwendeten lichtempfindlichen Silberhalogenidemulsionen können als Halogenid Chlorid, Bromid und Iodid bzw. Mischungen davon enthalten. In einer bevorzugten Ausführungsforn besteht der Halogenidanteil wenigstens einer Schicht zu 0 bis 12 mol-% aus Iodid, zu 0 bis 50 mol-% aus Chlorid und zu 50 bis 100 mol-% aus Bromid. In der Regel handelt es sich um überwiegend kompakte Kristalle, die z.B. kubisch oder oktaedrisch sind oder Übergangsformen aufweisen. Sie lassen sich dadurch kennzeichnen, daß sie in wesentlichen eine Dicke von mehr als 0,2 µm aufweisen. Das durchschnittliche Verhältnis von Durchmesser zu Dicke ist bevorzugt kleiner als 8: 1, wobei gilt, daß der Durchmesser eines Kornes definiert ist als der Durchmesser eines Kreises mit einen Kreisinhalt entsprechend der projizierten Fläche des Kornes. In einer anderen bevorzugten Ausführungsform können alle oder einzelne Emulsionen aber auch im wesentlichen tafelförmige Silberhalogenidkristalle aufweisen, bei denen das Verhältnis von Durchmesser zu Dicke größer als 8: 1 ist. Bei den Emulsionen kann es sich um monodisperse oder auch heterodisperse Emulasionen handeln, welche bevorzugt eine mittlere Korngröße von 0,3 µm bis 1,2 µm aufweisen. Die Silberhalogenidkörner können einen geschichteten Kornaufbau aufweisen.The light-sensitive silver halide emulsions used in the recording material can contain chloride, bromide and iodide or mixtures thereof as the halide. In a preferred embodiment, 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. As a rule, these are predominantly compact crystals that are, for example, cubic or octahedral or have transitional forms. They can be characterized in that they essentially have a thickness of more than 0.2 µm. 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. In another preferred embodiment, 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 μm up to 1.2 µm. The silver halide grains can have a layered grain structure.
Als Schutzkolloid bzw. Bindemittel für die Schichten des Aufzeichnungsmaterials sind die üblichen hydrophilon filmbildenden Mittel geeignet, z.B. Proteine, insbesondere Gelatine. Diese kann jedoch ganz oder teilweise durch andere natürliche oder synthetische Bindemittel ersetzt werden. Begußhilfsmittel und Weichmacher können verwendet werden. Verwiesen wird auf Research Disclosure 17 643 (Dezember 1978), insbesondere Kapitel IX, XI und XII.The usual 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.
Die Emulsionen können in der üblichen Weise chemisch und/oder spektral sensibilisiert sein; sie können Silberhalogenidstabilisierungsmittel enthalten, und die Emulsions-schichten wie auch andere nicht-lichtempfindliche Schichten können in der üblichen Weise mit bekannten Härtungsmitteln gehärtet sein. Geeignete chemische Sensibilisatoren, spektrale Sensibilisierungsfarbstoffe, Stabilisatoren und Härtungsmittel sind beispielsweise in Research Disclosure 17643, beschrieben; verwiesen wird insbesondere auf die Kapitel III, IV, VI und X.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 hardeners. 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 III, IV, VI and X.
Die dem erfindungsgemäßen Stabilisierverfahren unterworfenen Aufzeichnungsmaterialien werden bildmäßig belichtet, wobei zur Belichtung ultraviolettes, sichtbares oder intrarotes Licht oder auch eine hochenergetische Strahlung verwendet werden kann. Es schließt sich eine übliche Verarbeitung an, um das belichtete Silberhalogenid in Bildsilber zu übertführen, wozu das Aufzeichnungsmaterial in Gegenwart einer Silberhalogenidentwicklerverbindung, die in einer der Schichten des Aufzeichnungsmaterials oder ein einem wäßrigen Behandlungsbad enthalten sein kann, in der Regel im alkalischen Medium behandelt wird. Es können anorganische oder organische Entwicklerverbindungen verwendet werden. Beispiele hierfür sind Hydrochinon, 3-Pyrazolidon, Aminophenol und deren Derivate. Verwiesen wird auf Resarch Disclosure 17 643, Kapitel XX. In der Regel schließt sich an die Entwicklung eine Fixierbadbehandlung an, wodurch das nicht belichtete und nicht entwickelte Silberhalogenid aus dem Aufzeichnungsmaterial herausgelöst wird.The recording materials subjected to the stabilization process according to the invention are exposed imagewise, it being possible to use ultraviolet, visible or intra-red light or else high-energy radiation for the exposure. This is followed by conventional processing to convert the exposed silver halide to image silver, for which purpose the recording material in the presence of a silver halide developer compound, which can be contained in one of the layers of the recording material or 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. Reference is made to Resarch Disclosure 17 643, Chapter XX. As a rule, 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.
Obwohl das erfindungsgemäße Stabilisierverfahren zu jedem beliebigen Zeitpunkt nach der Entwicklung und Erzeugung des fertigen Silberbildes angewendet werden kann, entfaltet es seine größte Wirksamkeit, wenn es als letzter Behandlungsschritt vor dem Trocknen des Schwarzweißbildes angewendet wird. Dies bedeutet auch, daß sich vorzugsweise an das erfindungsgemäße Stabilisierbad keine weitere Flüssigbehandlung, insbesondere keine Wässerung anschließt. Vielmehr wird das erfindungsgemäße Stabilisierbad als Nachbehandlungs- oder Schlußbad verwendet.Although the stabilizing method according to the invention can be used at any time after the development and generation of the finished silver image, it is most effective when it is used as the last treatment step before the black and white image is dried. This also means that preferably no further liquid treatment, in particular no washing, follows the stabilizing bath according to the invention. Rather, the stabilizing bath according to the invention is used as an aftertreatment or final bath.
Verschiedene Proben eines belichteten, entwickelten, fixierten und gut gewässerten fotografischen Schwarz-Weiß-Materials, zweckmäßigerweise "Stufenkeile", wurden nach dem Wässern 3 min in einer Lösung einer der in der folgenden Tabelle angegebenen Vorbindungen gebadet und getrocknet. Die nachbehandelten getrockneten Schwarz-Weiß-Materialien wurden bei einer eingestellten relativen Luftfeuchtigkeit von 84% einer sehr verdünnten Wasserstoffperoxid-Atmosphäre aussetzt. Diese Wasserstoffperoxid-Atmophäre wurde durch Hydrolyse von Natriumpercarbonat Na₂CO₃· 3H₂O₂ bei 84%iger relativer Luftfeuchtigkeit und Zimmeretemperatur (22-24°C) hergestellt. Die rel. Luftfeuchtigkeit von 84% wurde durch eine gesättigte KBr-Lösung eingestellt. Die belichteten und verarbeiteten Papierstreifen wurden senkrecht in ein rechteckiges Gläsgefäß von etwa 20 l eingehängt. Das Glasgefäß befand sich in einem temperierten Wasserbad zur Einstellung der Temperatur von 22-24°C im Innern des Gefäßes. Es wurde mit einer opaken Glasplatte verschlossen. Die zu untersuchenden Proben wurden durch diese Glasplatte von einer fluoreszierenden Lampe (Xenonlampe 22 Watt) in einem AbstAnd von ca. 20 cm bestrahlt. Auf den Boden des Glasgefäßes wurden gleichmäßig etwa 50 g Percarbonat gegeben. Die getrockneten Prüflinge wurden in jedem Test solange in dem Glasgefäß belassen, bis mindestens einer von ihnen schwer angegriffen worden war, wobei folgender Bewertungsmaßstab zugrundegelegt wurde:
- kein Angriff:
- Keine erkennbaren Verfärbungen
- geringer Angriff:
- geringe Verfärbungen überwiegend bei niedriger Dichte
- mäßiger Angriff:
- Mäßige Verfärbungen bei niedriger oder hoher Dichte
- schwerer Angriff:
- Starke Verfärbungen bei niedriger und hoher Dichte bis zur Ausbleichung
Various samples of an exposed, developed, fixed and well-watered black and white photographic material, advantageously "step wedges", were bathed and dried for 3 minutes in a solution of one of the prebindings given in the table below. The aftertreated dried black and white materials were exposed to a very dilute hydrogen peroxide atmosphere at a set relative air humidity of 84%. This hydrogen peroxide atmosphere was produced by hydrolysis of sodium percarbonate Na₂CO₃ · 3H₂O₂ at 84% relative humidity and room temperature (22-24 ° C). The rel. Air humidity of 84% was adjusted using a saturated KBr solution. The exposed and processed paper strips were suspended vertically in a rectangular glass jar of about 20 l. The glass vessel was in a tempered water bath to set the temperature of 22-24 ° C inside the vessel. It was closed with an opaque glass plate. The samples to be examined were irradiated through this glass plate by a fluorescent lamp (xenon lamp 22 watts) at a distance of approx. 20 cm. About 50 g of percarbonate were evenly added to the bottom of the glass jar. In each test, the dried test specimens were left in the glass jar until at least one of them had been severely attacked, using the following evaluation criteria:
- no attack:
- No discernible discoloration
- minor attack:
- minor discoloration predominantly at low density
- moderate attack:
- Moderate discoloration with low or high density
- severe attack:
- Severe discoloration at low and high density until fading
In der nachfolgenden Tabelle sind die Ergebnisse und Effekte der einzelnen Verbindungen zusammengefaßt.The results and effects of the individual compounds are summarized in the table below.
Durch das erfindungsgemäße Stabilisatorbad werden die bei der Zerstörung des Silberbildes sich bildenden löslichen und farblosen Silberverbindungen unlöslich gemacht. Wie aus der Tabelle ersichtlich wurde über raschend gefunden, daß die beanspruchten Verbindungen eine ausgezeichnete Wirkung haben.
Claims (1)
R₁, R₃ and R₄ independently of one another represent hydrogen, saturated or unsaturated, optionally substituted aliphatic groups containing up to 6 C atoms or aryl groups and
R₂ represents hydrogen or saturated or unsaturated aliphatic groups containing up to 6 C atoms, which may be substituted by hydroxy, alkoxy, amino, halogen or phenyl, or aryl groups, in a concentration of 1.5 to 4% by weight.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE3733291 | 1987-10-02 | ||
| DE19873733291 DE3733291A1 (en) | 1987-10-02 | 1987-10-02 | STABILIZATION OF A PHOTOGRAPHIC SILVER IMAGE |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| EP0309873A1 EP0309873A1 (en) | 1989-04-05 |
| EP0309873B1 true EP0309873B1 (en) | 1991-03-27 |
Family
ID=6337442
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| EP88115431A Expired - Lifetime EP0309873B1 (en) | 1987-10-02 | 1988-09-21 | Stabilisation of a photographic picture produced with silver |
Country Status (4)
| Country | Link |
|---|---|
| US (1) | US4886737A (en) |
| EP (1) | EP0309873B1 (en) |
| JP (1) | JP2634646B2 (en) |
| DE (2) | DE3733291A1 (en) |
Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4987059A (en) * | 1988-12-01 | 1991-01-22 | Agfa-Gevaert Aktiengesellschaft | Process for stabilizing photographic silver images |
| EP0589460B1 (en) | 1992-09-24 | 2000-08-09 | Fuji Photo Film Co., Ltd. | Method for processing a black & white silver halide light-sensitive material |
| US8034542B2 (en) | 2006-03-28 | 2011-10-11 | Fujifilm Corporation | Conductive film and manufacturing method thereof, and transparent electromagnetic shielding film |
| JP5588597B2 (en) | 2007-03-23 | 2014-09-10 | 富士フイルム株式会社 | Manufacturing method and manufacturing apparatus of conductive material |
| US8426749B2 (en) | 2007-05-09 | 2013-04-23 | Fujifilm Corporation | Electromagnetic shielding film and optical filter |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE1772734A1 (en) * | 1968-06-27 | 1970-05-14 | Agfa Gevaert Ag | Photographic stabilizing or fixing bath |
| DE3613622A1 (en) * | 1986-04-23 | 1987-10-29 | Agfa Gevaert Ag | STABILIZING A PHOTOGRAPHICALLY MADE SILVER IMAGE |
-
1987
- 1987-10-02 DE DE19873733291 patent/DE3733291A1/en not_active Withdrawn
-
1988
- 1988-09-19 US US07/245,558 patent/US4886737A/en not_active Expired - Fee Related
- 1988-09-21 EP EP88115431A patent/EP0309873B1/en not_active Expired - Lifetime
- 1988-09-21 DE DE8888115431T patent/DE3862184D1/en not_active Expired - Fee Related
- 1988-09-28 JP JP63241166A patent/JP2634646B2/en not_active Expired - Lifetime
Also Published As
| Publication number | Publication date |
|---|---|
| JPH01102553A (en) | 1989-04-20 |
| EP0309873A1 (en) | 1989-04-05 |
| DE3862184D1 (en) | 1991-05-02 |
| US4886737A (en) | 1989-12-12 |
| JP2634646B2 (en) | 1997-07-30 |
| DE3733291A1 (en) | 1989-04-20 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| DE2811025A1 (en) | SILVER SALTS OF 3-AMINO-1,2,4-MERCAPTOTRIAZOL DERIVATIVES | |
| DE1281845B (en) | Silver halide photographic emulsion | |
| DE2303204A1 (en) | COLOR PHOTOGRAPHIC SILVER HALOGENIDE RECORDING MATERIAL | |
| DE1929223A1 (en) | Developer-precursor compounds and their uses in photography | |
| DE2034064B2 (en) | Color photographic recording material | |
| DE3029209A1 (en) | LIGHT SENSITIVE PHOTOGRAPHIC RECORDING MATERIAL AND THEIR USE FOR PRODUCING PHOTOGRAPHIC IMAGES | |
| DE69007286T2 (en) | METHOD FOR PHOTOGRAPHIC METHOD. | |
| EP0309873B1 (en) | Stabilisation of a photographic picture produced with silver | |
| DE2218189A1 (en) | Bleaching processes for photographically processed silver and bleaching baths suitable for carrying out this process | |
| DE1772026A1 (en) | Photographic recording material | |
| EP0242768B1 (en) | Stabilization of a photographically prepared silver image | |
| DE2053714C2 (en) | Photographic material and method for preventing fogging | |
| DE2850612A1 (en) | PHOTOMATERIAL AND PHOTOGRAPHICAL DEVELOPER | |
| DE2733950A1 (en) | METHOD OF MANUFACTURING PHOTOGRAPHIC SILVER HALOGENIDE MATERIAL | |
| EP0371359A1 (en) | Method of stabilising silver images | |
| EP0044813A2 (en) | Process for the formation of negative colour images according to the silver dye-bleaching process, and the silver dye-bleaching material used in this process | |
| DE1793289C2 (en) | Hydroxyaminobenzyl derivatives, processes for the preparation and use as developer-coupler compounds in developer solutions and photographic light-sensitive material | |
| DE2212550A1 (en) | Use of azotriazoles and azotetrazoles as antifoggants and antispot agents and selective desensitizers in photographic silver halide emulsions and in photographic baths, and photographic recording material containing these compounds | |
| DE2112728C3 (en) | Color photographic recording material | |
| EP0001415B1 (en) | Photographic inversion process with chemical fogging, chemical fogging baths therefor, and their use in the production of photographic images | |
| DE2711942C2 (en) | ||
| DE1912332A1 (en) | Photographic recording material | |
| DE69024215T2 (en) | Photographic direct positive silver halide material that can be handled in room lighting | |
| DE2931690A1 (en) | PHOTOGRAPHIC EMULSION, METHOD FOR THE PRODUCTION AND PHOTOGRAPHIC MATERIALS | |
| DE1949331A1 (en) | Photographic developer |
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 |
|
| 17P | Request for examination filed |
Effective date: 19880921 |
|
| AK | Designated contracting states |
Kind code of ref document: A1 Designated state(s): BE DE FR GB IT NL |
|
| 17Q | First examination report despatched |
Effective date: 19900726 |
|
| GRAA | (expected) grant |
Free format text: ORIGINAL CODE: 0009210 |
|
| AK | Designated contracting states |
Kind code of ref document: B1 Designated state(s): BE DE FR GB IT NL |
|
| ET | Fr: translation filed | ||
| REF | Corresponds to: |
Ref document number: 3862184 Country of ref document: DE Date of ref document: 19910502 |
|
| ITF | It: translation for a ep patent filed | ||
| GBT | Gb: translation of ep patent filed (gb section 77(6)(a)/1977) | ||
| 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 | ||
| PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: DE Payment date: 19970811 Year of fee payment: 10 |
|
| PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: BE Payment date: 19970910 Year of fee payment: 10 |
|
| PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: GB Payment date: 19970912 Year of fee payment: 10 |
|
| PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: FR Payment date: 19970924 Year of fee payment: 10 |
|
| PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: NL Payment date: 19970930 Year of fee payment: 10 |
|
| 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: 19980921 |
|
| PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: BE Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 19980930 |
|
| BERE | Be: lapsed |
Owner name: AGFA-GEVAERT A.G. Effective date: 19980930 |
|
| PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: NL Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 19990401 |
|
| GBPC | Gb: european patent ceased through non-payment of renewal fee |
Effective date: 19980921 |
|
| 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: 19990531 |
|
| NLV4 | Nl: lapsed or anulled due to non-payment of the annual fee |
Effective date: 19990401 |
|
| 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: 19990701 |
|
| 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: 20050921 |