EP0671655B1 - Durcissement amélioré de colloids hydrophyliques à l'aide de combinaisons imidazolium/triazine - Google Patents

Durcissement amélioré de colloids hydrophyliques à l'aide de combinaisons imidazolium/triazine Download PDF

Info

Publication number
EP0671655B1
EP0671655B1 EP19950103145 EP95103145A EP0671655B1 EP 0671655 B1 EP0671655 B1 EP 0671655B1 EP 19950103145 EP19950103145 EP 19950103145 EP 95103145 A EP95103145 A EP 95103145A EP 0671655 B1 EP0671655 B1 EP 0671655B1
Authority
EP
European Patent Office
Prior art keywords
carbons
substituted
alkyl
aryl
aralkyl
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
EP19950103145
Other languages
German (de)
English (en)
Other versions
EP0671655A2 (fr
EP0671655A3 (fr
Inventor
Ludovic Fodor
Richard R.M. Jones
Reinhold Rueger
Rolf Thomas Weberg
Timothy Donald Weatherill
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.)
Agfa Gevaert NV
Original Assignee
Agfa Gevaert NV
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
Application filed by Agfa Gevaert NV filed Critical Agfa Gevaert NV
Publication of EP0671655A2 publication Critical patent/EP0671655A2/fr
Publication of EP0671655A3 publication Critical patent/EP0671655A3/fr
Application granted granted Critical
Publication of EP0671655B1 publication Critical patent/EP0671655B1/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 is related to improved hardeners for proteinaceous materials. More specifically this invention is related to a combination of imidazolium and triazine hardeners for crosslinking a proteinaceous material in a photographic film.
  • Proteinaceous materials are used for a wide variety of applications.
  • One of the predominant useful properties is their ability to swell in aqueous solutions and yet form a solid matrix which is permeable to aqueous solutions upon drying. These properties have been exploited for many generations in the field of photographic sciences and proteinaceous materials are still widely used as a binder for harbouring silver halide grains in the photosensitive layer of photographic films.
  • Formation of a solid matrix is typically considered to be a result of inter-and intra-molecular hydrogen bonding within both the helical and random regions of proteinaceous materials. If only the natural hydrogen bonding is employed the strength of the matrix is typically insufficient for use in a photographic film. Therefore, it is common practice to add a hardener, also known as crosslinking agent, to a proteinaceous material when used for photographic layers.
  • a hardener also known as crosslinking agent
  • Hardeners are chosen, in part, for their ability to link one group on a proteinaceous molecule with another group on the same, or different, proteinaceous molecule.
  • the linking generates a three dimensional network of proteinaceous material.
  • This three-dimensional network has sufficient strength to safely harbour a silver halide grain.
  • Another important aspect of the three dimensional network is an ability to allow solution to permeate freely during the photographic processing steps of development, fix (or bleach) and wash. It is imperative that the solution which freely permeates the matrix is not strongly absorbed. This is particularly important for photosensitive elements since they must often be capable of transiting the photographic processing steps of development, fix, wash and dry in 20-120 sec.
  • Crosslinking of a binder matrix most often involves the carboxyl groups, amine groups, or combinations thereof.
  • the number of carboxyl groups is substantially larger than the number of amine groups in most commercially available gelatin.
  • Traditional hardeners such as triazines, described, for example, in US-A-3 288 775 or US-A-3 325 287, are widely accepted as capable of combining amine groups and are thus termed amine-amine crosslinkers.
  • Amine-amine crosslinkers provide a very strong matrix yet the carboxyls are largely unaffected. The unreacted carboxyl groups are deleterious since they strongly absorb processing solution and increase the time required to remove the absorbed solution. The result is an increase in the time and/or energy required for transiting the photographic processing steps identified above.
  • Peptide couplers such as imidazoliums, described, for example, in JP-A-63 135 935 or EP-A-519 329 are widely accepted as combining a carboxyl group with an amine group to form an amide linkage between binder strands. This is advantageous since the number of free carboxyls is decreased. Unfortunatly, the strength of the peptide-coupled binder is insufficient to transit a processor and total binder destruction is frequently observed.
  • An important consideration in crosslinking a binder is the pH of activity. This is particularly important when comparing amine-amine crosslinking reactions with reactions that form amide linkages.
  • Amine-amine crosslinkers like triazines, are typically stable around a neutral pH ( ⁇ 7) and decomposition, or decreased reactivity, is observed above or below neutrality.
  • Peptide couplers, especially imidazoliums are susceptible to instablility at higher pH and decomposition is accelerated above a pH of approximately 6.2. Therefore, if a pH is employed for optimum amine-amine crosslinking, the decomposition of imidazolium complexes is in competition with crosslinking reactivity.
  • a particular feature of the present invention is the ability to provide a photographic element which has a strong matrix, low fluid absorption and can undergo photographic development without detrimental effects.
  • Photographic elements of the present invention comprise at least one binder layer and at least one emulsion layer is crosslinked with at least one compound defined by Formula I and at least one compound defined by Formula II.
  • Y 1 is an alkyl, or substituted alkyl, of 1 to 24 carbons; aryl, or substituted aryl, of 6 to 24 carbons; aralkyl or substituted aralkyl of 7 to 25 carbons; the atoms chosen from C, N, O, and S necessary to form a substituted or unsubstituted 5- or 6-membered ring; -L 1 CR 8 CH 2 , or a polymer thereof; -C(Y 4 )E; or E is an alkyl, or substituted alkyl, of 1 to 24 carbons; aryl, or substituted aryl, of 6 to 24 carbons; aralkyl or substituted aralkyl of 7 to 25 carbons; -OR 9 ; -CN; the atoms chosen from C
  • L 1 is a linking group preferably chosen from a covalent chemical bond; alkyl, or substituted alkyl, of 1 to 20 carbons; aryl, or substituted aryl, of 6-24 carbons; aralkyl, or substituted aralkyl, of 7 to 25 carbons; carboxyl. Most preferably L 1 represents a chemical linkage; an alkyl, or substituted alkyl, of 1 to 3 carbons.
  • R 1 is hydrogen; alkyl, or substituted alkyl, of 1 to 24 carbons; aryl, or substituted aryl, of 6 to 24 carbons; aralkyl, or substituted aralkyl, of 7 to 25 carbons; halogen; -OR 10 ; halogen; nitro; carboxyl; mercapto; alklyamino or substituted alkylamino of 1 to 24 carbons; the atoms chosen from C, N, O and S necessary to from a 5- or 6-membered ring.
  • R 1 represents hydrogen; alkyl, or substituted alkyl, of 1 to 3 carbons; aryl, or substituted aryl, of 6 to 10 carbons; aralkyl, or substituted aralkyl, of 7 to 11 carbons. Most preferably R 1 represents hydrogen; alkyl, or substituted alkyl, of 1 to 3 carbons.
  • R 2 and R 3 independently represent hydrogen; alkyl, or substituted alkyl, of 1 to 24 carbons; aryl, or substituted aryl, of 6 to 24 carbons; aralkyl, or substituted aralkyl, of 7 to 25 carbons.
  • R 2 and R 3 independently may represent, or be taken together to represent, the atoms C, N, O and S necessary to form a 5- or 6-membered ring.
  • R 2 and R 3 independently represent alkyl, or substituted alkyl, of 1 to 6 carbons; aryl, or substituted aryl, of 6 to 10 carbons; aralkyl, or substituted aralkyl, of 7 to 11 carbons; or taken together R 2 and R 3 represent the atoms C, N and O necessary to form a 5- or 6-membered ring.
  • R 2 and R 3 represent alkyl, or substituted alkyl, of 1 to 3 carbons or R 2 and R 3 are taken together to represent the atoms C, N and O necessary to form a substituted or unsubstituted 5- or 6-membered ring.
  • R 4 and R 5 independently represent hydrogen; alkyl, or substituted alkyl, of 1 to 24 carbons; aryl or substituted aryl of 6 to 24 carbons; aralkyl or substituted aralkyl of 7 to 25 carbons; nitro; carboxyl; mercapto; -OR 11 ; halogen; alkylamino or substituted alkylamino of 1 to 24 carbons; R 4 and R 5 independently may represent the atoms chosen from C, N, O, and S necessary to form a substituted or unsubstituted 5-or 6-member ring or R 4 and R 5 may be taken together to represent the atoms chosen from C, N, O, and S necessary to form a substituted or unsubstituted 5- or 6-membered ring.
  • R 4 and R 5 independently represent hydrogen; alkyl, or unsubstituted alkyl, of 1 to 4 carbon atoms.
  • X- is a counterion preferably chosen from the set consisting of halide, CF 3 SO 3 -, ClO 4 -, BF4- and p-CH 3 C 6 H 4 SO 3 -.
  • Y 2 , Y 3 and Y 4 independently represent O or S.
  • R 6 and R 7 independently represent hydrogen; alkyl, or substituted alkyl, of 1 to 24 carbons; aryl, or substituted aryl, of 6 to 24 carbons; aralkyl, or substituted aralkyl, of 7 to 25 carbons.
  • R 6 and R 7 independently may represent, or be taken together to represent the atoms C, N, O and S necessary to form a substituted or unsubstituted 5- or 6-member ring.
  • R 6 and R 7 independently represent alkyl, or substituted alkyl, of 1 to 6 carbons; aryl, or substituted aryl, of 6 to 10 carbons; aralkyl, or substituted aralkyl, of 7 to 11 carbons; taken together R 6 and R 7 may represent the atoms C, N and O necessary to form a substituted or unsubstituted 5- or 6-membered ring.
  • R 6 and R 7 represent alkyl, or substituted alkyl, of 1 to 3 carbons; or R 6 and R 7 are taken together to represent the atoms C, N and O necessary to form a substituted or unsubstituted 5- or 6-membered ring.
  • R 8 represents a hydrogen; an alkyl, or substituted alkyl, of 1 to 24 carbons; -C(O)R 28 ; -CN; aryl or substituted aryl of 6 to 24 carbons.
  • R 9 represents hydrogen; alkyl of substituted alkyl of 1 to 24 carbons; aryl of substituted aryl of 6 to 24 carbons.
  • R 10 and R 11 independently represent hydrogen; an alkyl, or substituted alkyl, of 1 to 5 carbons.
  • R 28 represents hydrogen; alkyl or substituted alkyl of 1 to 24 carbons; alkoxy or substituted alkoxy of 1 to 24 carbons; amine; alkyl amine or substituted alkyl amine of 1 to 24 carbon
  • the compound represented by: represents a vinyl imidazolium.
  • the vinyl group of the vinyl imidazolium can be polymerized as known in the art to form a polymer.
  • the vinyl group of the vinyl imidazolium can be polymerized with other substituted vinyl compounds to form a copolymer.
  • the vinyl imidazole is a copolymer defined by: where R 1 , R 2 , R 3 , R 4 , R 5 , R 8 , L 1 and Y 2 correspond to the definition above for similiarly referenced groups.
  • the subscript "p" represents the mole fraction of vinyl imidazolium monomer in the polymer and is preferably no more than 95% and more preferably no more than 50%.
  • a and B independently represent copolymerized monomers.
  • the monomers A and B are independently chosen from the set consisting of acrylic acid ester, methacrylic acid ester, acrylamide, styrene, styrene sulfonate, maleic anhydride, butadiene and vinyl chloride.
  • R 12 , R 13 and R 14 are independently chosen from the groups represented by halogen, preferably Cl or Br; The most preferred group represented by R 12 , R 13 or R 14 is chlorine or bromine.
  • One of R 12 , R 13 or R 14 may represent hydrogen; alkyl, or substituted alkyl, of 1 to 24 carbons, preferably 1 to 4 carbons; halogen; -OR 21 ; -NR 22 R 23 ; -OM; a linking group to another triazine; sulfonamide; substituted or unsubstituted alkyl ether of 1 to 20 carbons; polyethylene oxide of 2 to 40 carbons; -(OR 24 ) x R 25 where x is an integer from 1 to 24; -L 2 CR 26 CH 2 or a polymer thereof.
  • one substituent chosen from R 12 , R 13 or R 14 is alkyl, of substituted alkyl, of 1 to 4 carbons; a halogen chosen from Cl and Br; -OR 21 ; -NR 22 R 23 ; -OM; a divalent linking group; sulfonamide; substituted or unsubstituted alkyl ether of 1 to 20 carbons; polyethylene oxide of 2 to 40 carbons; -(OR 24 ) x R 25 where x is an integer from 1 to 24; -L 2 CR 26 CH 2 or a polymer thereof.
  • one substituent chosen from R 12 , R 13 or R 14 is -OM.
  • R 15 and R 16 independently represent sodium; potassium; ammonium; alkyl ammonium or substituted alkyl ammonium of 1 to 20 carbons; hydrogen; alkyl or substituted alkyl of 1 to 20 carbons.
  • R 15 and R 16 independently represent sodium; potassium; ammonium; alkylammonium or substituted alkylammonium of 1 to 4 carbons.
  • R 17 and R 18 independently represent sodium; potassium; ammonium; hydrogen; alkyl ammonium or substituted alkyl ammonium of 1 to 20 carbons; alkyl or substituted alkyl or 1 to 20 carbons.
  • R 17 and R 18 independently represent sodium; potassium; ammonium; or alkyl ammonium of 1 to 4 carbons.
  • R 19 and R 20 independently represent sodium; potassium; hydrogen; ammonium; alkyl ammonium or substituted alkyl ammonium of 1 to 20 carbons; alkyl or substituted alkyl or 1 to 20 carbons.
  • R 19 and R 20 independently represent sodium, potassium, ammonium, or alkyl ammonium of 1 to 4 carbons.
  • R 21 represents hydrogen, alkyl or substituted alkyl of 1 to 20 carbons; alkoxyalkyl or substituted alkoxyalkyl of 1 to 40 carbons; aryl or substituted aryl of 6 to 40 carbons; aralkyl or substituted aralkyl of 7 to 41 carbons; alkyl thioether or substituted alkyl thioether of 1 to 40 carbons.
  • R 21 represents hydrogen.
  • R 22 and R 23 independently represent hydrogen; alkyl or substituted alkyl of 1 to 20 carbons; aryl or substituted aryl of 6 to 20 carbons; alkylether or substituted alkylether of 1 to 20 carbons; arylether or substituted arylether of 6 to 20 carbons; alkylthioether or substituted alkylthioether of 1 to 20 carbons; arylthioether or substituted arylthioether of 6 to 20 carbons; sulfonyl; alkylsulfonyl of 1 to 20 carbons.
  • R 22 and R 23 independently represent hydrogen, sulfonyl, alkylsulfonyl of 1 to 4 carbons.
  • R 24 represents an ethylene or substituted ethylene.
  • R 24 represents ethylene or isopropylene.
  • R 25 represents an alkyl or substituted alkyl of 1 to 20 carbons; an ether or substituted ether of 1 to 40 carbons.
  • R 26 represents a hydrogen; alkyl or substituted alkyl of 1 to 24 carbons.
  • R 26 represents a hydrogen or methyl.
  • L 2 is a divalent chemical linkage preferably chosen from a chemical bond; alkylene or substituted alkylene of 1 to 20 carbons; arylene or substituted arylene of 6 to 24 carbons; aralkyl or substituted aralkyl of 7 to 25 carbons; or carbonyl.
  • L 2 represents a chemical bond, alkylene or substituted alkylene of 1 to 10 carbons; arylene or substituted arylene of 6 to 10 carbons; aralkyl or substituted aralkyl of 7 to 12 carbons.
  • M is a counterion. M is preferably chosen from sodium, potassium, lithium, calcium, barium, strontium, ammonium, or alkyl ammonium with 1 to 20 carbons. Most preferably M is chosen from sodium, potassium, ammonium, or alkyl ammonium of 1 to 20 carbons.
  • R 12 , R 13 and R 14 are halogen; one of R 12 , R 13, R 14 is -OR 21 ; NR 22 R 23 ; -OM; a divalent linking group; sulfonamide;
  • a polymer or copolymer formed by the polymerization or copolymerization of the vinyl group is also considered to be within the teachings of the present invention.
  • the process of polymerization, or copolymerization, is well known in the art and includes specifically radical initiated polymerization.
  • atoms chosen from C, N, O, and S necessary to from a 5- or 6-membered ring refers to substituted or unsubstituted rings including but not limited to: the thiazole series; e.g. thiazole, 4-methylthiazole, 4-phenylthiazole, 5-methylthiazole, 5-phenylthiazole, 4,5-dimethylthiazole, 4,5-diphenylthiazole, 4-(2-thienyl)-thiazole;
  • alkyl refers to both unsubstituted and substituted groups unless specified to the contrary.
  • Preferred substituents include halogen, nitro, carboxyl, hydroxyl, alkoxy, amine, thiol, amide, vinyl, sulfate, cyano, thioether, carboxylic acid, sulfonic acid, sulfato, and combination thereof.
  • a preferred embodiment of the present invention is realized when at least one of R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 15 , R 16 , R 17 , R 18 , R 19 , R 20 , R 21 , R 22 , R 23 or one of the set consisting of R 12 , R 13 and R 14 comprises a surfactant moiety incorporated into the chemical structure of the hardener. This allows a single compound to accomplish multiple task, namely, act as a coating aid during the coating process after which they act to crosslink the matrix as detailed above.
  • Surfactant moieties which are known in the art include alkyls chains over 6 carbons, preferably 6 to 24 carbons; polyalkyleneoxide chains such as -(R 27 O) m -, wherein R 27 is ethylene, propylene or combinations thereof and m is an integer of 1 to 30; or combinations of alkylenes, and polyalkyleneoxides.
  • hardeners represented by Formula I are:
  • hardeners represented by Formula II are:
  • the hardeners to be used in the present invention react rapidly with a hydrophilic colloid and therefore addition of the hardener to a solution containing hydrophilic colloid must be done with care. This is particularly important in the present invention since the compounds of Formula I and Formula II are incompatible as detailed previously.
  • the hardeners to be used in the present invention are preferably added by injection into the solution supply line which transports coating solution from the holding tanks to the coater.
  • the injection time is dependent on the coater configuration but the time between injection and coating must be sufficiently long to allow thorough mixing. It is also important that the time is not so long that crosslinking and decomposition begin to occur. An addition time of no more than approximately 5 minutes prior to coating is preferred and no more than 2 minutes is most preferred.
  • Injection is accomplished by passing the coating solution past a "T" and adding a second hardener solution to the flow. After the "T" the two solutions are allowed to mix sufficiently.
  • the photographic element of the present invention can be coated onto a substrate with any method common to the art including but not limited to curtain coating, extrusion coating, slide-bead coating. Slide-bead coating is a preferred method.
  • Slide-bead coating is well known in the art to provide a means for supplying a flowing liquid layer or plurality of liquid layers down a slide surface to an efflux end, or lip, at which a liquid bridge, or bead, is formed in the gap between the lip and the moving substrate.
  • the moving substrate carries away liquid from the liquid inventory in the bead in the same layered structure established on the slide.
  • Exemplary examples include, for example, Russell, et.al., U. S. Patents 2,761,791 and 2,761,419.
  • the amount of hardener solution added depends on the degree of crosslinking desired.
  • the hardener solution is typically added in an amount sufficient to equal approximately 0.01 to 1.0 mmoles of Formula I per gram of hydrophilic colloid and approximately 0.01 to 1.0 mmoles of Formula II per gram of hydrophilic colloid. More preferred is approximately 0.02 to 0.30 mmoles of the hardener represented by Formula I per gram of hydrophilic colloid and approximately 0.02 to 0.30 mmoles of the hardener represented by Formula II per gram of hydrophilic colloid.
  • the amount added may be different for different hydrophilic colloids.
  • the hardeners to be used in the present invention are most suitable for crosslinking a hydrophilic colloid layer.
  • the hardeners to be used in the present invention are used for an emulsion layer containing hydrophilic colloid.
  • a photosensitive layer typically comprises silver halide dispersed in a hydrophilic colloid binder.
  • the silver halide is optionally chemically and optionally spectrally sensitized as known in the art and the layer may contain other adjuvants such as dyes, stabilizers, development agents, color coupling agents, toners, surfactants.
  • An underlayer typically comprises a hydrophilic colloid layer with an optional dye dispersed therein.
  • the overcoat is typically coated supra to the photosensitive layer as protection from, e.g., abrasion and may comprise dyes, surfactants, or other adjuvants as known in the art.
  • hydrophilic colloid or its homologues "gelatin” and “proteinaceous material” are used herein to refer to the protein substances which are derived from collagen.
  • hydrophilic colloid also refers to substantially equivalent substances such as synthetic analogues of gelatin.
  • gelatin is classified as alkaline gelatin, acidic gelatin or enzymatic gelatin.
  • Alkaline gelatin is obtained from the treatment of collagen with a base such as calcium hydroxide, for example.
  • Acidic gelatin is that which is obtained from the treatment of collagen in acid such as, for example, hydrochloric acid and enzymatic gelatin is generated with a hydrolase treatment of collagen.
  • the teachings of the present invention are not restricted to gelatin type or the molecular weight of the gelatin.
  • the film support for the emulsion layers used in the novel process may be any suitable transparent plastic.
  • the cellulosic supports e.g. cellulose acetate, cellulose triacetate, cellulose mixed esters may be used.
  • Polymerized vinyl compounds e.g., copolymerized vinyl acetate and vinyl chloride, polystyrene, and polymerized acrylates may also be mentioned.
  • Preferred films include those formed from the polyesterification product of a dicarboxylic acid and a dihydric alcohol made according to the teachings of Alles, U.S. Patent 2,779,684 and the patents referred to in the specification thereof.
  • Suitable supports are the polyethylene terephthalate/isophthalates of British Patent 766,290 and Canadian Patent 562,672 and those obtainable by condensing terephthalic acid and dimethyl terephthalate with propylene glycol, diethylene glycol, tetramethylene glycol or cyclohexane 1,4-dimethanol (hexahydro-p-xylene alcohol).
  • the films of Bauer et al., U.S. Patent 3,052,543 may also be used.
  • the above polyester films are particularly suitable because of their dimensional stability.
  • Meltpoint was measured by observing the melting temperature in 0.1 M NaOH for a hardened gelatin coating. Melt time was measured by observing the time, in minutes, required for the hardened layer to dissolve in a 1.5% NaOH solution at 50 o C.
  • Water absorption was determined by weighing a dry 10cmx10cm film sample, submerging the sample for 30 minutes in an aqueous solution buffered to a pH of approximately 10.0 by a borate buffer, allowing the excess water on the surface to drain off of the film, and weighing the swollen film.
  • Wet gouge is a measure of the strength of the binder under processing conditions and is measured by dragging a stylus which increases force with distance over a film submerged in a mock developer solution comprising all ingredients except hydroquinone and phenidone. The wet gouge is then determined as the distance traversed by the stylus prior to destruction of the film surface. A larger distance indicates a stronger matrix.
  • 7.5 g. (0.05 mole) morpholino-4-carbonyl chloride are added to a solution of 3.4 g. (0.05 mole) imidazole and 5.5 g. triethylamine in 60 ml dry tetrahydrofuran. The mixture is stirred 30 minutes at 50 o C. The precipitated triethyl-ammonium chloride is filtered off. An additional 7.5 g morpholino-4-carbonyl chloride are added to the filtrate. After standing 2 days at room temperature, crystals of 1,3-bis-(morpholinocarbonyl)-imidazolium chloride separate, are filtered off, washed with ether and vacuum dried.
  • Standard organic reaction synthetic procedures can be employed as known in the art. While other synthetic procedures may be employed, the hardeners of Formula I were prepared in a consistent manner according to the following procedure.
  • the appropriate N-substituted imidazol (0.2 mol) and the appropriate carbonyl chloride, or thiocarbaomyl chloride (0.2 mol) were dissolved in 100 ml. of acetone and refuxed for approximately 2 hrs.
  • the reaction mixture was cooled to precipate the product which was then recovered by filtration.
  • the filtrate was rinsed with acetone and dried in a dessicator at ambient conditions.
  • the upper layer contained largely unreacted bromodecane and the lower yielded 12 g (0.043 mole for a 21.4% theorical yield) of the imidazolium salt as a waxy solid upon cooling to 5 o C.
  • the purity and identity of this product was confirmed by proton and carbon NMR in deuterium oxide solution.
  • a photographic emulsion was prepared as known in the art.
  • the emulsion comprised tabular silver halide grains and 70 grams of gelatin per mole of silver halide.
  • the emulsion was coated on a subbed polyethylene terephthalate support to a silver coating weight of approximately 4.8 g/M 2 .
  • the combinations of hardeners listed in Table 1 were added either as a 2% solution (hardener I) or as a 10% solution (hardener II). The samples were held for approximately 1 week and analyzed yielding the results provided in Table 1.
  • Example 2 An emulsion substantially similar to that used in Example 1 was prepared. Various hardener levels were added to individual aliquots as recorded in Table 2. The melt time (MT) and water absorption (WA mg/cm 2 ) were measured after approximately 1 month and recorded in Table 2.
  • Example 2 An emulsion substantially similar to that described in Example 1 was prepared.
  • %WP represents the amount of water absorbed as a percentage of the total weight of the film; MT is the melt time in minutes; WG is wet gouge in grams.

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)
  • Nitrogen Condensed Heterocyclic Rings (AREA)
  • Plural Heterocyclic Compounds (AREA)
  • Silver Salt Photography Or Processing Solution Therefor (AREA)

Claims (8)

  1. Procédé pour former un élément photographique, comprenant les étapes consistant à:
    former au moins une émulsion photographique liquide dans au moins un récipient de stockage, dans lequel ladite émulsion photographique liquide comprend un halogénure d'argent, un colloïde hydrophile et un solvant;
    transporter ladite émulsion photographique liquide à une région d'interface;
    ajouter au moins un composé I tel que défini ci-dessous et au moins un composé II tel que défini ci-dessous;
    mélanger ladite émulsion photographique liquide avec ledit composé I et avec ledit composé II pour ainsi former une solution de couchage;
    transporter ladite solution de couchage à une coucheuse;
    couler ladite solution de couchage sur un substrat pour ainsi former une couche liquide;
    éliminer ledit solvant de ladite couche liquide pour former une couche sèche à l'état coulé,
    dans lequel le laps de temps qui s'écoule entre l'addition des durcisseurs et le couchage n'est pas à ce point long qu'une réticulation et qu'une décomposition commencent à se manifester;
    le composé I est un composé répondant à la formule I:
    Figure 00400001
    dans laquelle:
    Y1
    représente un groupe alkyle ou un groupe alkyle substitué contenant de 1 à 24 atomes de carbone; un groupe aryle ou un groupe aryle substitué contenant de 6 à 24 atomes de carbone; un groupe aralkyle ou un groupe aralkyle substitué contenant de 7 à 25 atomes de carbone; les atomes choisis parmi le groupe comprenant un atome de carbone, un atome d'azote, un atome d'oxygène et un atome de soufre, nécessaires pour former un noyau penta- ou hexagonal substitué ou non substitué; un groupe -L1CR8CH2 ou un polymère de ce dernier'; un groupe -C(Y4)E; ou encore un groupe répondant à la formule
    Figure 00410001
    E
    représente un groupe alkyle ou un groupe alkyle substitué contenant de 1 à 24 atomes de carbone; un groupe aryle ou un groupe aryle substitué contenant de 6 à 24 atomes de carbone; un groupe aralkyle ou un groupe aralkyle substitué contenant de 7 à 25 atomes de carbone; un groupe -OR9; un groupe -CN; les atomes choisis parmi le groupe comprenant un atome de carbone, un atome d'azote, un atome d'oxygène et un atome de soufre, nécessaires pour former un noyau penta- ou hexagonal substitué ou non substitué;
    L1
    représente un groupe de liaison;
    R1
    représente un atome d'hydrogène; un groupe alkyle ou un groupe alkyle substitué contenant de 1 à 24 atomes de carbone; un groupe aryle ou un groupe aryle substitué contenant de 6 à 24 atomes de carbone; un groupe aralkyle ou un groupe aralkyle substitué contenant de 7 à 25 atomes de carbone; un groupe -OR10; un atome d'halogène; un groupe nitro; un groupe carboxyle; un groupe mercapto; un groupe alkylamino ou un groupe alkylamino substitué contenant de 1 à 24 atomes de carbone; les atomes choisis parmi le groupe comprenant un atome de carbone, un atome d'azote, un atome d'oxygène et un atome de soufre, nécessaires pour former un noyau penta- ou hexagonal substitué ou non substitué;
    R2 et R3
    représentent, indépendamment l'un de l'autre, un atome d'hydrogène; un groupe alkyle ou un groupe alkyle substitué contenant de 1 à 24 atomes de carbone; un groupe aryle ou un groupe aryle substitué contenant de 6 à 24 atomes de carbone; un groupe aralkyle ou un groupe aralkyle substitué contenant de 7 à 25 atomes de carbone; R2 et R3 peuvent représenter indépendamment l'un de l'autre ou peuvent être pris ensemble pour représenter les atomes choisis parmi le groupe comprenant un atome de carbone, un atome d'azote, un atome d'oxygène et un atome de soufre, nécessaires pour former un noyau penta- ou hexagonal;
    R4 et R5
    représentent, indépendamment l'un de l'autre, un atome d'hydrogène; un groupe alkyle ou un groupe alkyle substitué contenant de 1 à 24 atomes de carbone; un groupe aryle ou un groupe aryle substitué contenant de 6 à 24 atomes de carbone; un groupe aralkyle ou un groupe aralkyle substitué contenant de 7 à 25 atomes de carbone; un groupe nitro; un groupe carboxyle; un groupe mercapto; un groupe -OR11; un atome d'halogène; un groupe alkylamino ou un groupe alkylamino substitué contenant de 1 à 24 atomes de carbone; les atomes choisis parmi le groupe comprenant un atome de carbone, un atome d'azote, un atome d'oxygène et un atome de soufre, nécessaires pour former un noyau penta- ou hexagonal substitué ou non substitué;
    R4 et R5
    peuvent être pris ensemble pour représenter les atomes choisis parmi le groupe comprenant un atome de carbone, un atome d'azote, un atome d'oxygène et un atome de soufre, nécessaires pour former un noyau penta- ou hexagonal substitué ou non substitué;
    X-
    représente un ion complémentaire;
    Y2, Y3 et Y4
    représentent, indépendamment l'un de l'autre, un atome d'oxygène ou un atome de soufre;
    R6 et R7
    représentent, indépendamment l'un de l'autre, un atome d'hydrogène; un groupe alkyle ou un groupe alkyle substitué contenant de 1 à 24 atomes de carbone; un groupe aryle ou un groupe aryle substitué contenant de 6 à 24 atomes de carbone; un groupe aralkyle ou un groupe aralkyle substitué contenant de 7 à 25 atomes de carbone; les atomes choisis parmi le groupe comprenant un atome de carbone, un atome d'azote, un atome d'oxygène et un atome de soufre, nécessaires pour former un noyau penta- ou hexagonal substitué ou non substitué;
    R6 et R7
    peuvent être pris ensemble pour représenter les atomes choisis parmi le groupe comprenant un atome de carbone, un atome d'azote, un atome d'oxygène et un atome de soufre, nécessaires pour former un noyau penta- ou hexagonal substitué ou non substitué;
    R8
    représente un atome d'hydrogène; un groupe alkyle ou un groupe alkyle substitué contenant de 1 à 24 atomes de carbone; un groupe -C(O)R28; un groupe -CN; un groupe aryle ou un groupe aryle substitué contenant de 6 à 24 atomes de carbone;
    R9
    représente un atome d'hydrogène; un groupe alkyle ou un groupe alkyle substitué contenant de 1 à 24 atomes de carbone; un groupe aryle ou un groupe aryle substitué contenant de 6 à 24 atomes de carbone;
    R10 et R11
    représentent, indépendamment l'un de l'autre, un atome d'hydrogène, un groupe alkyle ou un groupe alkyle substitué contenant de 1 à 5 atomes de carbone;
    R28
    représente un atome d'hydrogène; un groupe alkyle ou un groupe alkyle substitué contenant de 1 à 24 atomes de carbone; un groupe alcoxy ou un groupe alcoxy substitué contenant de 1 à 24 atomes de carbone; un groupe amine; un groupe alkylamine ou un groupe alkylamine substitué contenant de 1 à 24 atomes de carbone;
    et le composé II est un composé répondant à la formule II:
    Figure 00430001
    dans laquelle:
    au moins deux des radicaux R12, R13 et R14 sont choisis, indépendamment l'un de l'autre, parmi le groupe comprenant des atomes d'halogène, de préférence un atome de chlore ou un atome de brome; les groupes
    Figure 00430002
    un des radicaux R12, R13 ou R14
    peut représenter un atome d'hydrogène; un groupe alkyle ou un groupe alkyle substitué contenant de 1 à 24 atomes de carbone; un atome d'halogène; un groupe -OR21; un groupe -NR22R23; un groupe -OM; un groupe de liaison divalent à une autre triazine; un groupe sulfonamide; un éther alkylique substitué ou non substitué contenant de 1 à 20 atomes de carbone; un oxyde de polyéthylène contenant de 2 à 40 atomes de carbone; un groupe -(OR24)xR25; un groupe -L2CR26CH2 ou un de ses polymères;
    R15 et R16
    représentent, indépendamment l'un de l'autre, le sodium; le potassium; l'ammonium; un groupe alkylammonium ou un groupe alkylammonium substitué contenant de 1 à 20 atomes de carbone; un atome d'hydrogène; un groupe alkyle ou un groupe alkyle substitué contenant de 1 à 20 atomes de carbone;
    R17 et R18
    représentent, indépendamment l'un de l'autre, le sodium; le potassium; l'ammonium; un atome d'hydrogène; un groupe alkylammonium ou un groupe alkylammonium substitué contenant de 1 à 20 atomes de carbone; un groupe alkyle ou un groupe alkyle substitué contenant de 1 à 20 atomes de carbone;
    R19 et R20
    représentent, indépendamment l'un de l'autre, le sodium; le potassium; un atome d'hydrogène; l'ammonium; un groupe alkylammonium ou un groupe alkylammonium substitué contenant de 1 à 20 atomes de carbone; un groupe alkyle ou un groupe alkyle substitué contenant de 1 à 20 atomes de carbone;
    R21
    représente un atome d'hydrogène; un groupe alkyle ou un groupe alkyle substitué contenant de 1 à 20 atomes de carbone; un groupe alcoxyalkyle ou un groupe alcoxyalkyle substitué contenant de 1 à 40 atomes de carbone; un groupe aryle ou un groupe aryle substitué contenant de 6 à 40 atomes de carbone; un groupe aralkyle ou un groupe aralkyle substitué contenant de 7 à 41 atomes de carbone; un groupe thioéther alkylique ou un groupe thioéther alkylique substitué contenant de 1 à 40 atomes de carbone;
    R22 et R23
    représentent, indépendamment l'un de l'autre, un atome d'hydrogène; un groupe alkyle ou un groupe alkyle substitué contenant de 1 à 20 atomes de carbone; un groupe aryle ou un groupe aryle substitué contenant de 6 à 20 atomes de carbone; un groupe éther alkylique ou un groupe éther alkylique substitué contenant de 1 à 20 atomes de carbone; un groupe éther arylique ou un groupe éther arylique substitué contenant de 6 à 20 atomes de carbone; un groupe thioéther alkylique ou un groupe thioéther alkylique substitué contenant de 1 à 20 atomes de carbone; un groupe thioéther arylique ou un groupe thioéther arylique substitué contenant de 6 à 20 atomes de carbone; un groupe sulfonyle; un groupe alkylsulfonyle contenant de 1 à 20 atomes de carbone;
    R24
    représente un groupe éthylène ou un groupe éthylène substitué;
    R25
    représente un groupe alkyle ou un groupe alkyle substitué contenant de 1 à 20 atomes de carbone; un groupe éther ou un groupe éther substitué contenant de 1 à 40 atomes de carbone;
    R26
    représente un atome d'hydrogène; un groupe alkyle ou un groupe alkyle substitué contenant de 1 à 24 atomes de carbone;
    L2
    représente une liaison chimique;
    M
    représente un ion complémentaire;
    X
    représente un entier de 1 à 24.
  2. Procédé selon la revendication 1, dans lequel, dans le composé de formule I:
    Y2
    représente un atome d'oxygène;
    R1
    représente un atome d'hydrogène; un groupe alkyle ou un groupe alkyle substitué contenant de 1 à 24 atomes de carbone; un groupe aryle ou un groupe aryle substitué contenant de 6 à 24 atomes de carbone; un groupe aralkyle ou un groupe aralkyle substitué contenant de 7 à 25 atomes de carbone; un atome d'halogène;
    R2 et R3
    représentent, indépendamment l'un de l'autre, un atome d'hydrogène; un groupe alkyle ou un groupe alkyle substitué contenant de 1 à 24 atomes de carbone; un groupe aryle ou un groupe aryle substitué contenant de 6 à 24 atomes de carbone; un groupe aralkyle ou un groupe aralkyle substitué contenant de 7 à 25 atomes de carbone; R2 et R3 peuvent représenter indépendamment l'un de l'autre ou peuvent être pris ensemble pour représenter les atomes choisis parmi le groupe comprenant un atome de carbone, un atome d'azote, un atome d'oxygène et un atome de soufre, nécessaires pour former un noyau penta- ou hexagonal;
    R2 et R3
    peuvent être pris ensemble pour représenter les atomes choisis parmi le groupe comprenant un atome de carbone, un atome d'azote, un atome d'oxygène et un atome de soufre, nécessaires pour former un noyau penta- ou hexagonal substitué ou non substitué;
    Y1
    représente un groupe
    Figure 00450001
    dans laquelle Y3 représente un atome d'oxygène;
    R6 et R7
    représentent, indépendamment l'un de l'autre, un atome d'hydrogène; un groupe alkyle ou un groupe alkyle substitué contenant de 1 à 24 atomes de carbone; un groupe aryle ou un groupe aryle substitué contenant de 6 à 24 atomes de carbone; un groupe aralkyle ou un groupe aralkyle substitué contenant de 7 à 25 atomes de carbone; ou encore représentent les atomes choisis parmi le groupe comprenant un atome de carbone, un atome d'azote, un atome d'oxygène et un atome de soufre, nécessaires pour former un noyau penta- ou hexagonal substitué ou non substitué;
    R6 et R7
    peuvent être pris ensemble pour représenter les atomes choisis parmi le groupe comprenant un atome de carbone, un atome d'azote, un atome d'oxygène et un atome de soufre, nécessaires pour former un noyau penta- ou hexagonal substitué ou non substitué.
  3. Procédé selon la revendication 2, dans lequel le composé de formule I est choisi parmi le groupe comprenant:
    Figure 00460001
    Figure 00460002
    Figure 00460003
    Figure 00460004
    Figure 00460005
       et
    Figure 00470001
  4. Procédé selon la revendication 1, dans lequel, dans le composé de formule I:
    Y1
    représente un groupe alkyle ou un groupe alkyle substitué contenant de 1 à 24 atomes de carbone; un groupe aryle ou un groupe aryle substitué contenant de 6 à 24 atomes de carbone; les atomes choisis parmi le groupe comprenant un atome de carbone, un atome d'azote, un atome d'oxygène et un atome de soufre, nécessaires pour former un noyau penta- ou hexagonal substitué ou non substitué; un groupe -L1CR8CH2 ou un polymère de ce dernier;
    L1
    représente un groupe de liaison;
    R8
    représente un atome d'hydrogène; un groupe alkyle ou un groupe alkyle substitué contenant de 1 à 3 atomes de carbone.
  5. Procédé selon la revendication 4, dans lequel le composé de formule I est choisi parmi le groupe comprenant:
    Figure 00470002
    Figure 00470003
    Figure 00470004
    Figure 00470005
    Figure 00480001
    Figure 00480002
    Figure 00480003
    Figure 00480004
    Figure 00480005
    Figure 00480006
    Figure 00480007
       et
    Figure 00480008
  6. Procédé selon la revendication 1, dans lequel, dans le composé de formule II, au moins deux des radicaux R12, R13 et R14 représentent un atome d'halogène; un des radicaux R12, R13, R14 représente un groupe -OR21; un groupe -NR22R23; un groupe -OM; un groupe de liaison divalent; un groupe sulfonamide;
    R21
    représente un atome d'hydrogène; un groupe alkyle ou un groupe alkyle substitué contenant de 1 à 20 atomes de carbone; un groupe alcoxyalkyle ou un groupe alcoxyalkyle substitué contenant de 1 à 40 atomes de carbone; un groupe aryle ou un groupe aryle substitué contenant de 6 à 10 atomes de carbone; un groupe aralkyle ou un groupe aralkyle substitué contenant de 7 à 41 atomes de carbone; un groupe thioéther alkylique ou un groupe thioéther alkylique substitué contenant de 1 à 40 atomes de carbone;
    R22 et R23
    représentent, indépendamment l'un de l'autre, un atome d'hydrogène; un groupe alkyle ou un groupe alkyle substitué contenant de 1 à 20 atomes de carbone; un groupe aryle ou un groupe aryle substitué contenant de 6 à 20 atomes de carbone; un groupe éther alkylique ou un groupe éther alkylique substitué contenant de 1 à 20 atomes de carbone; un groupe éther arylique ou un groupe éther arylique substitué contenant de 6 à 20 atomes de carbone; un groupe thioéther alkylique ou un groupe thioéther alkylique substitué contenant de 1 à 20 atomes de carbone; un groupe thioéther arylique ou un groupe thioéther arylique substitué contenant de 6 à 20 atomes de carbone; un groupe sulfonyle; un groupe alkylsulfonyle contenant de 1 à 20 atomes de carbone;
    R24
    représente un groupe éthyle ou un groupe éthyle substitué;
    R25
    représente un groupe alkyle contenant de 1 à 20 atomes de carbone; un groupe éther contenant de 1 à 20 atomes de carbone;
    R26
    représente un atome d'hydrogène; un groupe alkyle ou un groupe alkyle substitué contenant de 1 à 24 atomes de carbone;
    L2
    représente une liaison chimique;
    M
    représente un ion complémentaire choisi parmi le sodium, le potassium, le lithium, le calcium, le baryum, le strontium, l'ammonium ou un alkylammonium contenant de 1 à 20 atomes de carbone;
    X
    représente un entier de 1 à 24.
  7. Procédé selon la revendication 6, dans lequel le composé répondant à la formule II est choisi parmi le groupe comprenant:
    Figure 00500001
    Figure 00510001
    Figure 00510002
    Figure 00510003
    Figure 00510004
    Figure 00510005
    Figure 00520001
    Figure 00520002
    Figure 00520003
  8. Elément photographique que l'on obtient par le procédé selon les revendications 1 à 7.
EP19950103145 1994-03-11 1995-03-06 Durcissement amélioré de colloids hydrophyliques à l'aide de combinaisons imidazolium/triazine Expired - Lifetime EP0671655B1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US20877894A 1994-03-11 1994-03-11
US208778 1994-03-11

Publications (3)

Publication Number Publication Date
EP0671655A2 EP0671655A2 (fr) 1995-09-13
EP0671655A3 EP0671655A3 (fr) 1996-02-28
EP0671655B1 true EP0671655B1 (fr) 2000-06-21

Family

ID=22776029

Family Applications (1)

Application Number Title Priority Date Filing Date
EP19950103145 Expired - Lifetime EP0671655B1 (fr) 1994-03-11 1995-03-06 Durcissement amélioré de colloids hydrophyliques à l'aide de combinaisons imidazolium/triazine

Country Status (3)

Country Link
EP (1) EP0671655B1 (fr)
JP (1) JPH07325363A (fr)
DE (1) DE69517541T2 (fr)

Family Cites Families (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3288775A (en) * 1961-04-07 1966-11-29 Ciba Ltd Method of hardening gelatin by reacting with conjugated heterocyclic compounds containing halogen atoms and water-solubilizing acid groups
US3325287A (en) * 1963-11-26 1967-06-13 Fuji Photo Film Co Ltd Photographic gelatin hardening composition
JPH0627926B2 (ja) * 1986-11-27 1994-04-13 コニカ株式会社 ハロゲン化銀写真感光材料
DE4119982C2 (de) * 1991-06-18 1993-09-30 Du Pont Deutschland 1,3-Bis-carbamoylimidazoliumverbindungen und Verfahren zum Härten von Gelatine enthaltenden Schichten
US5378842A (en) * 1993-12-21 1995-01-03 E. I. Du Pont De Nemours And Company Imidazolium hardeners for proteinaceous materials

Also Published As

Publication number Publication date
JPH07325363A (ja) 1995-12-12
DE69517541T2 (de) 2001-02-08
DE69517541D1 (de) 2000-07-27
EP0671655A2 (fr) 1995-09-13
EP0671655A3 (fr) 1996-02-28

Similar Documents

Publication Publication Date Title
EP0267598B1 (fr) Matériau photographique à l'halogénure d'argent de type négatif à contraste élevé
US5330884A (en) Photographic element with near-infrared antihalation layer
JPS63296032A (ja) ハロゲン化銀写真感光材料
CA1332030C (fr) Materiaux photographiques a halogenure d'argent
US5459029A (en) Photographic element hardened with imidazolium hardeners
US3444138A (en) Mordants for bleachable filter layers
EP0456163B1 (fr) Matériaux photographiques à l'halogénure d'argent
EP0314104B1 (fr) Matériau photographique à l'halogénure d'argent
EP0671655B1 (fr) Durcissement amélioré de colloids hydrophyliques à l'aide de combinaisons imidazolium/triazine
EP0398355B1 (fr) Matériau photographique à l'halogénure d'argent
EP0690337B1 (fr) Tannants d'imidazolium améliorés
US5601971A (en) Hardening of hydrophilic colloids with imidazolium and triazine combinations
EP0652470A1 (fr) Composé hydrazine et matériau photographique à l'halogénure d'argent le contenant
EP0866365B1 (fr) Durcissement amelioré des colloides hydrophiles
JPH0816777B2 (ja) 画像形成方法
US4826758A (en) Silver halide emulsion and process for preparing it, and light-sensitive halide photographic material employing said silver halide emulsion
EP0626427B1 (fr) Colorants absorbant dans l'infra-rouge proche et élément photographique contenant de tels colorants
US4894323A (en) Silver halide photographic material comprising a polyoxyethylenic compound and a sensitizing dye
US4917995A (en) Silver halide photographic material
EP0552010B1 (fr) Matériaux à l'halogénure d'argent pour l'enregistrement d'images
JPS6259944A (ja) ハロゲン化銀写真感光材料
JP3248026B2 (ja) ハロゲン化銀写真感光材料
JPH0348840A (ja) ハロゲン化銀写真感光材料
JPH10175946A (ja) 新規ヒドラジン化合物とハロゲン化銀写真感光材料及びその処理方法
JPH11167177A (ja) ハロゲン化銀写真感光材料

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: A2

Designated state(s): BE DE FR GB IT

PUAL Search report despatched

Free format text: ORIGINAL CODE: 0009013

AK Designated contracting states

Kind code of ref document: A3

Designated state(s): BE DE FR GB IT

17P Request for examination filed

Effective date: 19960813

17Q First examination report despatched

Effective date: 19961007

RAP1 Party data changed (applicant data changed or rights of an application transferred)

Owner name: STERLING DIAGNOSTIC IMAGING, INC.

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

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

RAP1 Party data changed (applicant data changed or rights of an application transferred)

Owner name: AGFA-GEVAERT N.V.

AK Designated contracting states

Kind code of ref document: B1

Designated state(s): BE DE FR GB IT

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 FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRE;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.SCRIBED TIME-LIMIT

Effective date: 20000621

Ref country code: BE

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20000621

REF Corresponds to:

Ref document number: 69517541

Country of ref document: DE

Date of ref document: 20000727

ET Fr: translation filed
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: 20010306

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

Effective date: 20010306

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: 20011130

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: DE

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20020101