EP0770908B1 - Compositions durcissantes stabilisées au vinyl sulphone utilisables dans la fabrication photographique - Google Patents

Compositions durcissantes stabilisées au vinyl sulphone utilisables dans la fabrication photographique Download PDF

Info

Publication number
EP0770908B1
EP0770908B1 EP19960202868 EP96202868A EP0770908B1 EP 0770908 B1 EP0770908 B1 EP 0770908B1 EP 19960202868 EP19960202868 EP 19960202868 EP 96202868 A EP96202868 A EP 96202868A EP 0770908 B1 EP0770908 B1 EP 0770908B1
Authority
EP
European Patent Office
Prior art keywords
hardening
vinyl sulfone
stabilizer
citric acid
composition
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
EP19960202868
Other languages
German (de)
English (en)
Other versions
EP0770908A1 (fr
Inventor
Mary Jane Eastman Kodak Company Griggs
Lewis Robert Eastman Kodak Company Hamilton
Peter Anthony Eastman Kodak Company Marr
Philip Raymond Eastman Kodak Company Martell
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Eastman Kodak Co
Original Assignee
Eastman Kodak Co
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Priority claimed from US08/576,144 external-priority patent/US5658721A/en
Application filed by Eastman Kodak Co filed Critical Eastman Kodak Co
Publication of EP0770908A1 publication Critical patent/EP0770908A1/fr
Application granted granted Critical
Publication of EP0770908B1 publication Critical patent/EP0770908B1/fr
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

Links

Classifications

    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03C—PHOTOSENSITIVE MATERIALS FOR PHOTOGRAPHIC PURPOSES; PHOTOGRAPHIC PROCESSES, e.g. CINE, X-RAY, COLOUR, STEREO-PHOTOGRAPHIC PROCESSES; AUXILIARY PROCESSES IN PHOTOGRAPHY
    • G03C1/00—Photosensitive materials
    • G03C1/005—Silver halide emulsions; Preparation thereof; Physical treatment thereof; Incorporation of additives therein
    • G03C1/06—Silver halide emulsions; Preparation thereof; Physical treatment thereof; Incorporation of additives therein with non-macromolecular additives
    • G03C1/30—Hardeners

Definitions

  • This invention relates in general to the hardening of hydrophilic colloids utilized in photographic elements and in particular to the hardening of such colloids using a hardening composition containing, as a hardening agent, a compound comprising two or more vinyl sulfonyl groups. More specifically, this invention relates to improved hardening compositions containing the aforesaid hardening agent and a stabilizing agent which inhibits homopolymerization of such hardening agent.
  • hydrophilic colloids typically refined gelatin
  • layers such as radiation-sensitive layers (e.g., silver halide emulsion layers), interlayers, subbing layers and overcoat layers.
  • Various addenda are conventionally incorporated in the layers, including addenda to alter the properties of the hydrophilic colloids present therein.
  • hydrophilic colloids such as gelatin are easily abraded and ingest large quantities of water when brought into contact with aqueous solutions, thereby causing an undesirable amount of swelling.
  • unmodified colloid coatings tend to melt at relatively low temperatures, thereby limiting their temperature range of utility.
  • hardeners are incorporated into hydrophilic colloids intended to be used in forming photographic element layers. Both inorganic and organic hardeners are known. A summary of hardeners is presented in Research Disclosure , Item 36544, September, 1994.
  • the terms “forehardened” and “forehardener” are employed when the hardener is associated with hydrophilic colloid in the course of manufacturing a photographic element.
  • the terms “prehardened” and “prehardener” are employed when the hardener is associated with a hydrophilic colloid layer of a photographic element in a processing solution preceding the developer bath for the element.
  • hardeners of the active olefin type a preferred class of hardeners particularly useful as forehardeners are compounds comprising two or more vinyl sulfonyl groups. These compounds are hereinafter referred to as "vinyl sulfones.” Compounds of this type are described in numerous patents including, for example, U.S. Patents 3,490,911, 3,642,486, 3,841,872 and 4,171,976. Vinyl sulfone hardeners are believed to be effective as hardeners as a result of their ability to crosslink polymers making up the colloid.
  • a conductivity marker i.e., a material that is added to the relatively non-conductive hardening solution to assist with identification by rendering it feasible to monitor electrical conductivity and thereby ensure delivery of the correct hardener solution to the coating station.
  • a desirable conductivity for a BVSM solution is 2.6 to 3.0 mhos/cm.
  • the conductivity marker should not adversely affect the quality or handling of the hardening solution.
  • a compound that has been commonly used as a conductivity marker in photographic hardening compositions is potassium nitrate.
  • potassium nitrate is disadvantageous in that it contributes to and accelerates the formation of homopolymer in vinyl sulfone hardening solutions when ferric ion is present in levels of only a few parts per million.
  • levels of ferric ion are commonly encountered, with a major source being the iron oxides formed on the surfaces of iron pipes and other equipment used to convey the hardening solution and a minor source being iron present in the vinyl sulfone monomer from its synthesis.
  • potassium nitrate as a conductivity marker, it is difficult to meet required quality specifications and the homopolymerization which occurs results in clogged delivery lines and frequent interruptions in the photographic manufacturing process.
  • citric acid and salts thereof are highly effective inhibitors of homopolymerization in vinyl sulfone hardening compositions.
  • Useful salts for this purpose include ammonium salts of citric acid, alkali metal salts of citric acid such as lithium, sodium or potassium salts, and alkaline earth metal salts of citric acid such as magnesium salts.
  • alkali metal salts is preferred and the use of the trisodium salt of citric acid is particularly preferred.
  • citric stabilizer is used hereinafter to refer to citric acid or an ammonium, alkali metal or alkaline earth metal salt thereof.
  • vinyl sulfone hardeners are inhibited against homopolymerization without interfering with their utility as hardeners, i.e., hydrophilic colloid crosslinking agents, by combining with the hardener a homopolymerization-inhibiting amount of a citric stabilizer.
  • this invention is directed to a hardening composition that is useful in hardening a hydrophilic colloid which is incorporated in a layer of a photographic element, said hardening composition comprising a vinyl sulfone hardening agent and a sufficient amount of a stabilizer to inhibit homopolymerization of the vinyl sulfone hardening agent, wherein the stabilizer is a citric stabilizer, as hereinbefore defined.
  • the composition comprises a citric stabilizer in an amount sufficient to inhibit homopolymerization of the hardener.
  • this invention therefore is directed to a process of hardening an aqueous coating composition useful as a layer of a photographic element comprising adding a vinyl sulfone hardener to a hydrophilic colloid.
  • the improvement comprises inhibiting homopolymerization of the hardener with a citric stabilizer.
  • a process of hardening a hydrophilic colloid-containing layer of a photographic element by adding a vinyl sulfone hardener to a coating composition containing the hydrophilic colloid and coating the composition onto a photographic support is also included.
  • the improvement comprises inhibiting homopolymerization of the hardener with a citric stabilizer.
  • a photographic hardener composition which comprises a vinyl sulfone hardener, in an amount sufficient to inhibit homopolymerization of the hardener of a citric stabilizer, may include a sulfate in an amount sufficient to act as a conductivity marker.
  • Useful sulfates for employment as conductivity markers include ammonium sulfate, alkali metal sulfates such as lithium, sodium or potassium sulfate, and alkaline earth metal sulfates such as magnesium sulfate. The use of alkali metal sulfates is preferred and the use of sodium sulfate is particularly preferred.
  • hydrophilic colloid which can be hardened by a vinyl sulfone hardening agent can be employed in the practice of this invention.
  • hydrophilic colloids in photographic elements, including photographic films and photographic papers, is very well known.
  • gelatin gelatin
  • gelatin is a particularly preferred material for use in this invention.
  • Useful gelatins include alkali-treated gelatin (cattle bone or hide gelatin), acid-treated gelatin (pigskin gelatin) and gelatin derivatives such as acetylated gelatin and phthalated gelatin.
  • Other hydrophilic colloids that can be utilized alone or in combination with gelatin include dextran, gum arabic, zein, casein, pectin, collagen derivatives, collodion, agar-agar, arrowroot and albumin.
  • Still other useful hydrophilic colloids are water-soluble polyvinyl compounds such as polyvinyl alcohol, polyacrylamide and poly(vinylpyrrolidone).
  • compositions of the present invention can be simple black-and-white or monochrome elements comprising a support bearing a layer of light-sensitive silver halide emulsion or they can be multilayer and/or multicolor elements.
  • Color photographic elements incorporating compositions of this invention typically contain dye image-forming units sensitive to each of the three primary regions of the spectrum.
  • Each unit can be comprised of a single silver halide emulsion layer or of multiple emulsion layers sensitive to a given region of the spectrum.
  • the layers of the element, including the layers of the image-forming units, can be arranged in various orders as is well known in the art.
  • a preferred photographic element incorporating a composition according to this invention comprises a support bearing at least one blue-sensitive silver halide emulsion layer having associated therewith a yellow image dye-providing material, at least one green-sensitive silver halide emulsion layer having associated therewith a magenta image dye-providing material and at least one red-sensitive silver halide emulsion layer having associated therewith a cyan image dye-providing material, the element containing in at least one layer thereof a hydrophilic colloid that has been hardened with a hardening composition containing a vinyl sulfone hardening agent and a stabilizing amount of a citric stabilizer that inhibits homopolymerization of the vinyl sulfone hardening agent.
  • the elements incorporating compositions of the present invention can contain auxiliary layers conventional in photographic elements, such as overcoat layers, spacer layers, filter layers, interlayers, antihalation layers, pH lowering layers (sometimes referred to as acid layers and neutralizing layers), timing layers, opaque reflecting layers and opaque light-absorbing layers.
  • the support can be any suitable support used with photographic elements. Typical supports include polymeric films, paper (including polymer-coated paper) and glass. Details regarding supports and other layers of the photographic elements of this invention are contained in Research Disclosure , Item 36544, September, 1994.
  • the light-sensitive silver halide emulsions employed in the photographic elements incorporating compositions of this invention can include coarse, regular or fine grain silver halide crystals or mixtures thereof and can be comprised of such silver halides as silver chloride, silver bromide, silver bromoiodide, silver chlorobromide, silver chloroiodide, silver chorobromoiodide, and mixtures thereof.
  • the emulsions can be, for example, tabular grain light-sensitive silver halide emulsions.
  • the emulsions can be negative-working or direct positive emulsions. They can form latent images predominantly on the surface of the silver halide grains or in the interior of the silver halide grains.
  • the emulsions typically will be gelatin emulsions although other hydrophilic colloids can be used in accordance with usual practice. Details regarding the silver halide emulsions are contained in Research Disclosure, Item 36544, September, 1994, and the references listed therein.
  • the photographic silver halide emulsions utilized in this invention can contain other addenda conventional in the photographic art.
  • Useful addenda are described, for example, in Research Disclosure, Item 36544, September, 1994.
  • Useful addenda include spectral sensitizing dyes, desensitizers, antifoggants, masking couplers, DIR couplers, DIR compounds, antistain agents, image dye stabilizers, absorbing materials such as filter dyes and UV absorbers, light-scattering materials, coating aids, plasticizers and lubricants.
  • the dye-image-providing material employed in the photographic element can be incorporated in the silver halide emulsion layer or in a separate layer associated with the emulsion layer.
  • the dye-image-providing material can be any of a number known in the art, such as dye-forming couplers, bleachable dyes, dye developers and redox dye-releasers, and the particular one employed will depend on the nature of the element, and the type of image desired.
  • Dye-image-providing materials employed with conventional color materials designed for processing with separate solutions are preferably dye-forming couplers; i.e., compounds which couple with oxidized developing agent to form a dye.
  • Preferred couplers which form cyan dye images are phenols and naphthols.
  • Preferred couplers which form magenta dye images are pyrazolones and pyrazolotriazoles.
  • Preferred couplers which form yellow dye images are benzoylacetanilides and pivalylacetanilides.
  • Suitable examples of the organic linking group represented by Z include alkyl, alkylene, aryl, arylene, aralkyl and alkaryl groups.
  • Z can be a heteroatom such as a nitrogen atom or an ether oxygen atom.
  • Z is preferably -A- -A-O-A, -O-A-O- , or -D-
  • A is an alkylene group containing 1 to 8 carbon atoms which may be unsubstituted or substituted and the alkylene chain may be interrupted by one or more hetero atoms or organic groups, or an arylene group, which may be substituted or unsubstituted
  • the aryl moiety of the aralkyl group may be sulfonated.
  • the alkylene group may be interrupted by one or more of the following: oxygen atoms, arylene groups, cycloalkyl groups, -NHCONH-, or -N-R, where R is an alkyl group containing 1 to 8 carbon atoms.
  • the citric stabilizer is associated with the hardener while all or a portion of the hardener remains in its unreacted monomeric form.
  • the citric stabilizer and the hardener can be brought together in any convenient manner.
  • the citric stabilizer can be blended with the hydrophilic colloid to be hardened so that upon addition of the hardener the citric stabilizer is already present. It is generally preferred that the citric stabilizer be blended with the hardener before the hardener is blended with the hydrophilic colloid.
  • the vinyl sulfone hardeners described herein can be used in any effective amount in hardening hydrophilic colloids. Suitable amounts are typically in the range of from 0.5 to 10 percent by weight, based on the weight of hydrophilic colloid, and more preferably in the amount of from 1 to 3 percent by weight.
  • the citric stabilizer can be used as a homopolymerization inhibitor over a wide range of concentrations. Suitable concentrations of the citric stabilizer are typically in the range of from 0.01 to 3 moles per mole of vinyl sulfone hardening agent, more preferably in the range of from 0.05 to 1 moles per mole of vinyl sulfone hardening agent, and most preferably in the range of from 0.1 to 0.5 moles per mole of vinyl sulfone hardening agent.
  • the time required for polymer to form in the hardening composition increases with increase in the molar ratio of citric stabilizer to vinyl sulfone.
  • a sulfate as a conductivity marker in conjunction with the use of the citric stabilizer.
  • the use of the sulfate as a conductivity marker is for the purpose of facilitating identification of the hardening solution. Electrical conductivity is much easier to monitor than other characteristics of such solutions and by using the sulfate in an appropriate concentration, a desired level of electrical conductivity can be readily established. Suitable concentrations of the sulfate are typically in the range of from 0.05 to 0.6 moles per mole of vinyl sulfone hardening agent, and more preferably in the range of from 0.1 to 0.4 moles per mole of vinyl sulfone hardening agent.
  • Vinyl sulfones are usually prepared from the corresponding haloethylsulfonyl compounds by dehydrohalogenation using a strong organic base such as triethylamine.
  • a strong organic base such as triethylamine.
  • One of the problems involved in synthesizing such compounds, particularly the more active ones, such as BVSM, is that they tend to homopolymerize in the presence of the strong base. This problem can be alleviated by combining the citric stabilizer with the haloethylsulfonyl precursor compound. In this way, the citric stabilizer is associated with the vinyl sulfone hardener from its inception.
  • An important feature of the present invention is the ability of the citric stabilizer to protect against homopolymerization in the presence of trace amounts of ferric ion, e.g., 2 to 20 ppm. It is extremely difficult to avoid such levels of iron in production equipment and the invention makes it unnecessary to take special precautions to reduce iron levels. It is believed that the citric stabilizer may interact with ferric ion and effectively "remove” it from the solution and thereby help to inhibit or delay homopolymerization of the vinyl sulfone.
  • Vinyl sulfones are believed to be able to undergo homopolymerization through a number of different mechanisms, e.g., radical ion (either cationic or anionic) as well as base-catalyzed polymerization, with the tendency for homopolymerization to occur being in part dependent on the synthesis procedure.
  • the polymer formed can be of high molecular weight and can also be highly crosslinked.
  • a heavy precipitate will settle out quite quickly, for example within a few hours. The extent of precipitation is affected by a number of factors such as, for example, the pH of the composition.
  • the sulfate can interact with ferric ion to form a yellow-colored precipitate composed, at least in part, of Fe 3 O 4 and FeO(OH).
  • the amount of such precipitate which is formed is slight and it does not present problems of plugging of delivery lines and other equipment to anywhere near the extent that can result from the homopolymerization of the vinyl sulfone hardener. The formation of such precipitates does not appear to occur to the same extent as a result of interaction of the citric stabilizer with ferric ion.
  • the invention is further illustrated by the following examples of its practice.
  • the solutions were inspected for polymer formation after specified periods of storage. Upon inspection, if the solution was clear, i.e., no observable precipitate, it was rated “CL.” The presence of haze was rated “H” while a solution that was cloudy but with no precipitate was rated “C.” The presence of polymeric precipitate was rated "PPT.”
  • An aqueous solution of BVSME was prepared, maintained at room temperature and inspected for polymer formation after periods of storage ranging from one hour to three months.
  • the solution consisted of 0.0088 moles of BVSME in 100 milliliters of water (2% by weight BVSME). This solution is referred to herein as Control Solution 1.
  • a second solution, referred to as Control Solution 2 was prepared in which the only difference was the addition of ferric ion at a concentration of 20 ppm.
  • a third solution, referred to as Example 1 was the same as Control Solution 2 except that 0.0022 moles of citric acid was added. The results obtained are summarized in Table 1 below.
  • Example 1 In order to determine the effect of concentration of citric acid, Example 1 was repeated at varying levels of citric acid content as summarized in Table 2 below. In each case, ferric ion was present at 20 ppm.
  • citric acid in amounts of 250 parts per million or more protected against precipitate formation for the entire 22-day duration of the test. With an amount of 50 parts per million, precipitate formed after 24 hours. An amount of 10 parts per million was insufficient to provide protection against precipitate formation.
  • citric acid was employed in combination with sodium sulfate.
  • concentration of ferric ion was 20 ppm, the same as in Examples 1 and 2.
  • the levels of citric acid and sodium sulfate employed are summarized in Table 3 below.
  • sodium sulfate can be used as a conductivity marker in the presence of citric acid as a polymerization retardant.
  • Example 1 was repeated except that 0.0022 moles of the trisodium salt of citric acid was used in place of the 0.0022 moles of citric acid employed in Example 1. The results were the same as in Example 1, i.e., there was no precipitation after three months of storage.
  • BVSM 2% by weight solution of BVSM was used in place of the 2% by weight solution of BVSME employed in Example 1.
  • the ferric ion concentration was 20 ppm.
  • Citric acid, sodium sulfate or combinations of citric acid and sodium sulfate were employed as the stabilizer.
  • Table 4 As indicated by the data in Table 4, citric acid is an effective stabilizer for use with BVSM and combinations of citric acid and sodium sulfate are effective to serve as both a stabilizer and conductivity marker.
  • the insoluble and intractable polymers formed as a result of homopolymerization of vinyl sulfone hardener solutions in manufacturing delivery lines are known to induce liquid flow disruptions or flow discontinuities during the coating of photographic products.
  • the flow disruption arises due to partial occlusion of the delivery lines (control valves, strainers and/or pumps), while the flow discontinuities are caused by total occlusion of the delivery lines or delivery line components.
  • This has been a major problem which has long plagued the photographic manufacturing process and solutions to the problem proposed heretofore have been generally ineffective.
  • the nitro-substituted aromatic compounds of U.S. Patent 4,171,976 provide effective protection in the synthesis stage of vinyl sulfone manufacture and use they are not as effective as desired in the stages involved in preparation and coating of gelatin or other hydrophilic colloid compositions.
  • the citric stabilizers have been found to be surprisingly effective as stabilizers which prevent homopolymerization of vinyl sulfone hardeners. By their use, the concentration of vinyl sulfone hardener in solution does not significantly change from the point of manufacture to the point of use. Stringent specifications can thus be maintained for solution concentration. The integrity of the delivery system is not compromised due to plugging by polymer and the burdens of maintenance and cleaning are greatly reduced.
  • the citric stabilizers can be effectively employed in combination with a sulfate which serves as a conductivity marker.

Landscapes

  • Physics & Mathematics (AREA)
  • Chemical & Material Sciences (AREA)
  • Spectroscopy & Molecular Physics (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • General Physics & Mathematics (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Physical Or Chemical Processes And Apparatus (AREA)
  • Polymerisation Methods In General (AREA)

Claims (13)

  1. Composition tannante utilisée pour tanner un colloïde hydrophile incorporé dans une couche d'un élément photographique, ladite composition tannante comprenant un agent tannant vinylsulfone et une quantité d'un agent stabilisant suffisante pour inhiber l'homopolymérisation dudit agent tannant vinylsulfone, caractérisée en ce que ledit agent stabilisant est choisi parmi le groupe comprenant l'acide citrique et les sels d'ammonium, de métaux alcalins et alcalino-terreux de l'acide citrique.
  2. Composition tannante selon la revendication 1, dans laquelle ledit agent tannant vinylsulfone est représenté par la formule : (H2C=CH-SO2)n - Z où n est un entier de 2 à 6 et Z est un groupe de liaison organique ayant une valence égale à n.
  3. Composition tannante selon la revendication 2, dans laquelle Z est un hétéroatome ou un groupe alkyle, alkylène, aryle, arylène, aralkyle ou alcaryle.
  4. Composition tannante selon la revendication 1, dans laquelle ledit agent tannant vinylsulfone est représenté par la formule : CH2=CH-SO2-(CH2)x-SO2-CH=CH2 où x est un entier d'une valeur de 1 à 3.
  5. Composition tannante selon la revendication 1, dans laquelle ledit agent tannant vinylsulfone est le bis(vinylsulfonyl)méthane.
  6. Composition tannante selon la revendication 1, dans laquelle ledit agent tannant vinylsulfone est le bis(vinylsulfonylméthyl)éther.
  7. Composition tannante selon l'une quelconque des revendications 1 à 6, dans laquelle ledit agent stabilisant est l'acide citrique.
  8. Composition tannante selon l'une quelconque des revendications 1 à 6, dans laquelle ledit agent stabilisant est un sel de métal alcalin de l'acide citrique.
  9. Composition tannante selon l'une quelconque des revendications 1 à 6, dans laquelle ledit agent stabilisant est le sel trisodique de l'acide citrique.
  10. Composition tannante selon l'une quelconque des revendications 1 à 9, dans laquelle on utilise une quantité dudit agent stabilisant comprise entre 0,05 et 1 mole environ par mole d'agent tannant vinylsulfone.
  11. Composition tannante selon l'une quelconque des revendications 1 à 10 contenant en outre une quantité suffisante de sulfate d'ammonium, d'un sulfate de métal alcalin ou d'un sulfate de métal alcalino-terreux qui agit comme un marqueur de conductivité.
  12. Procédé de tannage d'une composition de couchage aqueuse utile pour former une couche d'un élément photographique comprenant les étapes suivantes : ajouter à un colloïde hydrophile un agent tannant vinylsulfone et de l'acide citrique ou un sel d'ammonium, de métal alcalin ou alcalino-terreux de ce dernier, en quantité suffisante pour inhiber l'homopolymérisation dudit agent tannant vinylsulfone.
  13. Procédé selon la revendication 12, dans lequel ledit colloïde hydrophile est la gélatine, ledit agent tannant vinylsulfone est le bis(vinylsulfonylméthyl)éther et ladite homopolymérisation est inhibée par le sel trisodique de l'acide citrique.
EP19960202868 1995-10-19 1996-10-15 Compositions durcissantes stabilisées au vinyl sulphone utilisables dans la fabrication photographique Expired - Lifetime EP0770908B1 (fr)

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
US559795P 1995-10-19 1995-10-19
US5597 1995-10-19
US576144 1995-12-21
US08/576,144 US5658721A (en) 1995-12-21 1995-12-21 Stabilized vinyl sulfone hardening compositions useful in photographic manufacturing

Publications (2)

Publication Number Publication Date
EP0770908A1 EP0770908A1 (fr) 1997-05-02
EP0770908B1 true EP0770908B1 (fr) 1999-08-04

Family

ID=26674523

Family Applications (1)

Application Number Title Priority Date Filing Date
EP19960202868 Expired - Lifetime EP0770908B1 (fr) 1995-10-19 1996-10-15 Compositions durcissantes stabilisées au vinyl sulphone utilisables dans la fabrication photographique

Country Status (3)

Country Link
EP (1) EP0770908B1 (fr)
JP (1) JPH09179234A (fr)
DE (1) DE69603564T2 (fr)

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP4832675B2 (ja) * 2001-07-27 2011-12-07 和光純薬工業株式会社 ビニルスルホンの品質劣化防止方法並びに精製方法

Family Cites Families (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4171976A (en) * 1978-03-10 1979-10-23 Eastman Kodak Company Homopolymerization inhibition of photographic hardeners
JPH0782217B2 (ja) * 1985-03-29 1995-09-06 富士写真フイルム株式会社 ハロゲン化銀写真感光材料及びそれを用いた超硬調ネガ画像形成方法
EP0568285A1 (fr) * 1992-05-01 1993-11-03 Konica Corporation Procédé de traitement de matériau couleur à l'halogénure d'argent sensible à la lumière
EP0640589B1 (fr) * 1993-08-30 1997-03-12 Eastman Kodak Company Procédé pour la fabrication des composés contenant deux ou plusieurs groupements vinylsulfones

Also Published As

Publication number Publication date
DE69603564T2 (de) 2000-01-27
JPH09179234A (ja) 1997-07-11
EP0770908A1 (fr) 1997-05-02
DE69603564D1 (de) 1999-09-09

Similar Documents

Publication Publication Date Title
US3719492A (en) Complexed p-phenylenediamine containing photographic element and development process therefor
EP0193389B1 (fr) Utilisation d'un coupleur comprenant un groupe liberant un groupe accélérant le blanchiment
US3220839A (en) Photographic emulsions containing isothiourea derivatives
US3708303A (en) Photographic elements and processes lithographic silver halide element containing a 1-(amidophenyl)-5-mercaptotetrazole sensitizing agent and development process of using same
US4055429A (en) Inhibitor barrier layers for photographic materials
EP0517889B1 (fr) Stabilisateurs au thiosulfonate-sulfinate pour emulsions photosensibles
US4917994A (en) Color photographic reflection print material with improved keeping properties
EP0742476B1 (fr) Compositions durcissantes stabilisées au vinyl sulphone utilisables dans la fabrication photographique
EP0084290B1 (fr) Matériau photographique à base d'halogénures d'argent contenant des hydroquinones substituées
EP0770908B1 (fr) Compositions durcissantes stabilisées au vinyl sulphone utilisables dans la fabrication photographique
US4175970A (en) Process for sensitizing photographic silver halide emulsions
US5658721A (en) Stabilized vinyl sulfone hardening compositions useful in photographic manufacturing
EP0285308B2 (fr) Matériaux photographiques à contraste élevé
US5041367A (en) Photographic recording material
US4088495A (en) Silver halide photographic element containing a gelatinous layer hardened with an aliphatic hydrocarbon having at least three vinylsulfonyl groups
US3342596A (en) Benzothiazolium compounds for controlling overdevelopment
US4346154A (en) Antistain agent or antistain agent precursor in photographic silver halide element
EP0352618B1 (fr) Matériau d'enregistrement photograhique stabilisé
JP3597624B2 (ja) 写真要素および写真要素の生成方法
US4710454A (en) Photographic recording material and a process for the production of photographic images
US6740479B2 (en) Silver halide photographic processing solution
US3811896A (en) Silver halide emulsion stabilized with isoselenoureas or ketoselenozolidines
US4316953A (en) Photographic emulsion containing a stabilizer, a process for its production and photographic materials
EP0745896A1 (fr) Supports de films antistatiques et éléments photographiques contenant les dits supports de films antistatiques
US3677761A (en) Development process

Legal Events

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

Free format text: ORIGINAL CODE: 0009012

AK Designated contracting states

Kind code of ref document: A1

Designated state(s): DE FR GB

17P Request for examination filed

Effective date: 19971006

17Q First examination report despatched

Effective date: 19980623

GRAG Despatch of communication of intention to grant

Free format text: ORIGINAL CODE: EPIDOS AGRA

GRAG Despatch of communication of intention to grant

Free format text: ORIGINAL CODE: EPIDOS AGRA

GRAH Despatch of communication of intention to grant a patent

Free format text: ORIGINAL CODE: EPIDOS IGRA

GRAH Despatch of communication of intention to grant a patent

Free format text: ORIGINAL CODE: EPIDOS IGRA

GRAA (expected) grant

Free format text: ORIGINAL CODE: 0009210

AK Designated contracting states

Kind code of ref document: B1

Designated state(s): DE FR GB

REF Corresponds to:

Ref document number: 69603564

Country of ref document: DE

Date of ref document: 19990909

ET Fr: translation filed
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
REG Reference to a national code

Ref country code: GB

Ref legal event code: IF02

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

Ref country code: GB

Payment date: 20040915

Year of fee payment: 9

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

Ref country code: FR

Payment date: 20041004

Year of fee payment: 9

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

Ref country code: DE

Payment date: 20041029

Year of fee payment: 9

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: 20051015

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: 20060503

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

Effective date: 20051015

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: 20060630

REG Reference to a national code

Ref country code: FR

Ref legal event code: ST

Effective date: 20060630