EP0321401B1 - Farbbildende polymerische Kuppler - Google Patents

Farbbildende polymerische Kuppler Download PDF

Info

Publication number
EP0321401B1
EP0321401B1 EP19880810842 EP88810842A EP0321401B1 EP 0321401 B1 EP0321401 B1 EP 0321401B1 EP 19880810842 EP19880810842 EP 19880810842 EP 88810842 A EP88810842 A EP 88810842A EP 0321401 B1 EP0321401 B1 EP 0321401B1
Authority
EP
European Patent Office
Prior art keywords
colour coupler
polymeric
colour
coupler according
hydrogen
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
Application number
EP19880810842
Other languages
English (en)
French (fr)
Other versions
EP0321401A3 (en
EP0321401A2 (de
Inventor
John Leslie Cawse
Philip James Harris
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.)
Ilford Imaging UK Ltd
Original Assignee
Ilford Ltd
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 Ilford Ltd filed Critical Ilford Ltd
Publication of EP0321401A2 publication Critical patent/EP0321401A2/de
Publication of EP0321401A3 publication Critical patent/EP0321401A3/en
Application granted granted Critical
Publication of EP0321401B1 publication Critical patent/EP0321401B1/de
Expired legal-status Critical Current

Links

Images

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
    • G03C7/00—Multicolour photographic processes or agents therefor; Regeneration of such processing agents; Photosensitive materials for multicolour processes
    • G03C7/30—Colour processes using colour-coupling substances; Materials therefor; Preparing or processing such materials
    • G03C7/32—Colour coupling substances
    • G03C7/327—Macromolecular coupling substances
    • G03C7/3275—Polymers obtained by reactions involving only carbon-to-carbon unsaturated bonds, e.g. vinyl polymers

Definitions

  • This invention relates to new polymeric colour couplers and to their use in photographic materials.
  • camera speed film material which comprises silver halide and colour couplers in a silver halide emulsion layer which yields on colour development a so-called monochromatic dye image.
  • This material has some advantages over the conventional black and white camera speed film material in that the dye images are virtually grainless compared with the silver image obtained using high-speed film material.
  • film material of this type can be processed using conventional colour film processing chemistry.
  • Most processing houses are now set-up to process only colour film and thus it is a great convenience to be able to process the monochromatic camera speed film material in a colour film processing system.
  • a polymeric colour coupler which comprises the residue of three monomeric colour couplers of the formulae :- where R1 is hydrogen, alkyl, chlorine or bromine, R2 is a divalent organic radical and W1, W2 and W3 are each an active colour former moiety capable of forming upon chromogenic development of exposed silver halide material with a primary aromatic amine colour developing agent a dye, W1 forming a yellow dye, W2 forming a magenta dye and W3 forming a cyan dye.
  • the three moieties W1, W2 and W3 are present in the polymer in such a ratio that a black or blackish dye is obtained upon colour development.
  • W1, W2 and W3 can be any coupler moiety known in the art such as those described below.
  • R1 is hydrogen or methyl.
  • R2 the divalent organic radical may be the residue of a urethane, a urea, a carbonate, an ester, an ether, a ketone or an amide. More preferably however it is a simple amido linkage -C(O)-NH-.
  • the polymeric colour coupler of the type described may be formed as a polymer latex which is not isolated but is used as such. Or it may be formed as a water-soluble solid. If it is formed as a polymer latex there is preferably present in the polymer unit at least one other simple, non-colour-coupling photograhically inert comonomer. The presence of other monomers in the polymer is particularly desirable if the polymer is to be incorporated in photographic material as a latex.
  • a latex polymer is produced having optimum physical properties, such as glass transition temperature, compatibility with the gelatin used in preparing coating solutions, suitable refractive index, as well as beneficial rates of copolymerisation between the coupler monomers and the photographically inert comonomers and the ability to confer lowered viscosity and reasonable miscibility with the mixture of coupler monomers.
  • the polymeric colour coupler of the type described is formed as a water-soluble solid there is present in the polymer from 40 - 60% by weight of the residue of a monomer which has the formula IV where R1 has the meaning assigned to it above, L is an alkylene or interrupted alkylene linking group and R1 and R11 are alkyl groups having 1 to 4 carbon atoms and X is an anion.
  • L is preferably an alkylene chain having from 2 to 6 carbon atoms or is an interupted alkylene chain having from 2 to 6 carbon atoms there being an oxygen from or an -NH- group in the chain.
  • a particularly suitable monomer residue of this type has the formula V :-
  • Suitable comonomers which may be present when the polymeric colour coupler is formed as a polymer latex or as a water soluble polymer include methyl acrylate, ethyl acrylate, butyl acrylate, ethyl hexyl acrylate, vinyl acetate; hydroxyethyl methacrylate, hydroxypropylmethacrylate; methacrylic acid, acrylic acid, itaconic acid, 2-carboxyethyl acrylate and the salts thereof, acrylamide, methacrylamide, N-hydroxymethyl acrylamide, styrene, N-vinyl pyrrolidone, 1-vinyl imidazole; 4-vinylpyridine, dimethylaminoethyl methacrylate, tetrahydrofurfuryl methacrylate; sulfphoethyl methacrylate, vinyl sulphonic acid and salts thereof, acrylonitrile and vinylidene chloride, although this list is
  • crosslinking monomers may be present such as divinyl benzene, ethylene dimethacrylate, trivinyl cyclohexane and trimethylol propane triacylate.
  • the surface active agents used in the preparation of the polymer latex may be any of those well known in the art, for example nonionic wetting agents including alcohol ethoxylates, sorbitan esters, aryl phenol alkoxylates, alkyl alkanolamides, anionic wetting agents including alkyl sulphates and sulphonates, sulphosuccinates, aryl sulphonates, polyalkoxy sulphates, alkyl phosphates, aryl phenol phosphates, alkyl taurates, sarcosinates, and copolymerisable surfactants such as allyl sulphosuccinates, again this list is not intended to be exhaustive.
  • nonionic wetting agents including alcohol ethoxylates, sorbitan esters, aryl phenol alkoxylates, alkyl alkanolamides
  • anionic wetting agents including alkyl sulphates and sulphonates, sulpho
  • the initiators and initiator systems used for the preparation of the latices may be persulphates, azo compounds, peroxides or any of the other well known initiators used for emulsion polymerisation, including redox systems. Examples of these initiator systems may be found in the book “Emulsion Polymerisation” by D. Blackely, Applied Science Publishers, 1975 especially pages 155 to 250.
  • latices may make use of techniques such as “seed” polymerisation and core-shell techniques, as well as “power-feed” procedures and other methods well known in the art.
  • Latices may be prepared in bulk, semi-continuously or continuously using any of the known designs of apparatus.
  • photographic material having at least one gelatino silver halide emulsion layer which comprises a polymeric colour coupler of the type described. More preferably, the photographic material comprises a polymeric colour coupler which comprises the residues of monomers A, B and C shown below.
  • the polymeric colour coupler of the type described is present in the silver halide emulsion layer as a polymer latex.
  • the colour coupler of the type described is added to the silver halide emulsion layer as an aqueous solution.
  • any of the monomeric colour couplers described in the prior art may be used in the polymeric colour coupler of the present invention.
  • the colour coupler portion of the monomer may comprise ballasting groups or leaving groups for example so that the colour coupler may act as a two equivalent coupler.
  • yellow dye forming monomeric colour couplers examples include couplers of the general formula VI - wherein each of R3, R4, R5 and R6 are hydrogen, halogen, alkoxy, sulphoxy or sulphonamido, R1 and R2 are as defined above, R7 is hydrogen or a leaving group and L1 and L2 are direct linkages or -NH-.
  • linking groups R2 are -CO-NH- and -O-CH2-CH2-NH SO2 -
  • one of L1 and L2 is a direct linkage.
  • An example of such a monomer is Monomer B which is used in the Examples which follow. This monomer has the formula VII :
  • Another class of yellow dye forming monomeric colour couplers has a pivaloyl end group rather than a benzoyl end group.
  • Such colour couplers have the general formula X :- where R1, R2, R6 and R7 have the meanings assigned to them above.
  • magenta dye forming monomeric colour couplers examples include couplers of the general formula XII :- where R1 and R2 are as defined above, R8 is hydrogen or a leaving group and R10 R11 and R12 are each hydrogen, halogen or alkoxy.
  • the alkoxy group comprises an alkyl moiety having up to six carbon atoms.
  • R1 is hydrogen or -CH3
  • R2 is -CO NH -
  • R2 is -CO NH(CH2) x -O-CO-NH where x is 2 to 6, where in the above two formulae the phenylene group is optionally substituted by chlorine alkyl having 1 to 4 carbon atoms.
  • Particularly useful monomers of formula XII are those wherein at least two of R10, R11 and R12 are chlorine atoms.
  • R7 or R8 examples include the group -S- R9 where R9 is a long chain alkyl group having over 10 carbon atoms or is a substituted phenyl group having at least one alkyl or alkoxy group. Preferably R9 when an alkyl group has from 12 to 20 carbon atoms or the chain.
  • Monomeric magenta colour couplers of formula XII are described in EP 133262.
  • magenta dye forming monomeric colour couplers are those of general formula XVI :- wherein R1, R8 and R10 are as defined above and R19 is alkyl, dialkyl amino, optionally substituted phenyl and optionally substituted acylamino.
  • R1, R8 and R10 are as defined above and R19 is alkyl, dialkyl amino, optionally substituted phenyl and optionally substituted acylamino.
  • Substituents in the phenyl or ecylamino group include alkyl groups having 2 to 6 carbon atom and chloric.
  • couplers may be prepared by reacting magenta colour couplers of the formula with acryloyl or methacryloyl chloride
  • cyan dye forming monomeric colour couplers examples include phenol couplers of the general formula XVIII :- and of general formula XIX : and a naphthol coupler of the general formula XX :- wherein the above three formulae R1 and R12 are as defined above, R14 is hydrogen or a leaving group such as a halogen atom or a substituted alkoxy group, R13 is a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, R15 is an optionally substituted alkyl or acylamino group or is a para - cyano amilino group and R17 is a linking group and y is 0 or 1, and R16 is an alkoxy, amino, amido or sulphonamido group or hydrogen atom.
  • R1 is hydrogen or methyl.
  • linking groups R17 include alkylene chains of 2 to 6 carbon atoms including interrupted alkylene chains and an alkyl group for example
  • interupted alkylene chains have from 2 to 6 carbon atoms and - O - or - NH - group in the chain.
  • Examples of monomers of formula XIX are those of formulae :-
  • Examples of monomers of formula XX are those of formulae :-
  • Monomeric colour couplers of general formula XX are described in GB-A- 2133170.
  • the colour couplers of the type described are of particular use in monochromatic camera speed silver halide film material.
  • the photographic material after imagewise exposure is developed in a colour developing bath by use of a para - phenylene diamine developing agent to yield a developed silver image and black dye image.
  • the material is then subjected to a bleach fix treatment which removes the developed silver image and then unexposed silver halide leaving the black dye negative image which can be used to print all types of black and white paper including variable contrast paper.
  • the colour couplers of the type described can also be used to prepare monochromatic paper. That is to say paper which can be processed using colour processing chemistry to yield a black dye image instead of a silver image. Paper of this type is of particular use from which to prepare proof prints.
  • the colour coupler of the type described can also be used to reinforce silver halide images at such time that, as occurred some years ago, the price of silver becomes too prohibitive to use in photography when a very dense silver image is required.
  • the photographic material of the present invention preferably comprises gelatin as the binder in the silver halide emulsion layer.
  • the halide used can be any of the silver halides normally used in photography e.g. silver bromide, silver iodobromide, silver chloride, silver chlorobromide and silver iodochlorobromide.
  • the silver halide grains may be both optically and chemically sensitised.
  • the silver halide emulsion may contain stabiliser, bacteriocides and any of the other additives commonly found in photographic silver halide emulsions.
  • the gelatin may have been hardened and may contain coating aids as usual when preparing coated silver halide emulsions.
  • the base can be any of the usual transparent bases used in photography for example subbed polyester, polycarbonate or polystyrene base, or may be a cellulose triacetate or cellulose acetate - butyrate base. If the material is to be used for proof prints the base may be any opaque base in common use for photographic print material for example baryta coated paper base or polyethylene laminated paper base.
  • a monomer solution was made by dissolving in 2.00 g hydroxy propyl methacrylate and 3.00 g butyl acrylate 0.34 g Monomer A, (magenta monomer), 0.34g Monomer B (yellow monomer) and 0.34 g Monomer C (cyan monomer).
  • the vessel containing this solution was maintained at about 30 to 40°C.
  • a surfactant solution was prepared by dissolving in 5.80 g water sodium oleylmethyl taurate 0.16 g and potassium persulphate 40 mg.
  • the surfactant and monomer solutions were then fed slowly into the 100 ml vessel which comprised the initiator solution first set forth. These additions were made over 2 hours.
  • the resultant latex formed in the 100 ml vessel was maintained at 80°C for 1 1 ⁇ 2 hours. The contents were then cooled and filtered.
  • the latex as just prepared was used to prepare colour photographic material.
  • To 2.2 ml of an undyed twinned crystal iodobromide gelatino emulsion there was added 0.4 ml of the latex and 7 ml of water.
  • To this emulsion there was added 0.4 ml. of water.
  • To this emulsion there was added 0.4 ml of a 3% solution of a triazine hardener.
  • the emulsion was then coated on clear cellulose triacetate base to provide a silver coating weight of 12 mg/dm2.
  • the coating was dried and inspected in green light to show a clear, glossy coating.
  • This photographic material was then exposed to a white light source for 10 seconds and processed in a colour developing solution for 3.25 minutes at 38°C.
  • the photographic material was then passed to a bleach bath for 6.5 minutes at 35°C.
  • the formula of the bleach bath used is as follows :-
  • the material was then washed for 3 minutes in water at 30°C and then dried. A neutral grey image was present on the photographic material. This image has the visible absorption spectrum shown in the accompanying Figure 1. This shows that the material has good absorption in the blue, green and red regions of the visible spectrum.
  • One of the negatives obtained thereby was placed in a photographic enlarger and was used to print normal non-optically sensitised black and white paper. After processing the exposed paper a bright image having clear highlights and dark shadows was obtained.
  • the other of the negatives obtained was placed in a photographic enlarger provided with a filter to enable variable contrast photographic paper to be printed. An inspection of the image on the enlarger baseboard indicated that a No. 2 contrast filter should be used. This was placed in position with a sheet of variable contrast material below it and was printed using the negative. After processing the print was examined. As before a bright print having clear highlights and dark shadows was obtained.
  • p-Toluene sulphonic acid (4g) was dissolved in industrial alcohol (30 ml). Sufficient of the monomer dimethyl-aminoethyl methacrylate was added with stirring to raise the pH to 7. This required 5.2 g.
  • This solution was placed in a 50 ml flask to which were added 1 g of Monomer A (the magenta monomer), 0.5 g of Monomer B (the yellow monomer) and 0.5 g of Monomer C (the cyan monomer).
  • the flask was equipped with a condenser, nitrogen inlet, oil bath and magnetic stirrer. Nitrogen was bubbled through for 10 minutes at room temperature. The flask was then heated to 70°C and maintained at that temperature.
  • a free radical initiator solution was prepared which comprised 0.5 g azobis(isobutyronitrile) in 50 ml of industrial alcohol. 4.8 ml of this solution was added to the flask. After 2 hours a further 1.2 ml of the initiator solution was added and this was repeated after a further 2 hours. After 7 hours reaction time the contents of the flask were added to ether (500 ml) and a tacky brown solid precipitated. This solid was dissolved in industrial alcohol and reprecipitated in ether to give a free flowing white powder. Yield 7.13 g (67.3 %). This powder was found to be completely water soluble.
  • Example 1 0.1g of this solid was then added to an emulsion as prepared in Example 1. A clear glossy coating was used in Example 1. A clear glossy coating was found on inspection in green light. As in Example 1 the coating was exposed to white light for 10 seconds and then was processed as set forth in Example 1.

Landscapes

  • Physics & Mathematics (AREA)
  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Spectroscopy & Molecular Physics (AREA)
  • General Physics & Mathematics (AREA)
  • Silver Salt Photography Or Processing Solution Therefor (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)

Claims (15)

1. Polymerer Farbkuppler, bestehend aus dem Rest dreier monomerer Farbkuppler der Formeln:
Figure imgb0041
Figure imgb0042
Figure imgb0043
 worin R₁ Wasserstoff, Alkyl, Chlor oder Brom, R₂ einen zweiwertigen organischen Rest und W₁, W₂ und W₃ jeweils einen aktiven Farbbildnerrest bedeuten, der dazu in der Lage ist, bei chromogener Entwicklung von belichtetem Silberhalogenidmaterial mit einem Farbentwicklungsmittel aus primärem aromatischem Amin einen Farbstoff zu bilden, wobei W₁ einen gelben Farbstoff, W₂ einen Magentafarbstoff und W₃ einen Cyanfarbstoff bildet.
2. Polymerer Farbkuppler nach Anspruch 1, worin R₁ Wasserstoff oder Methyl bedeutet.
3. Polymerer Farbkuppler nach Anspruch 1, worin R₂ den Rest eines Urethans, Harnstoffs, Carbonats, Esters, Ketons oder Amids darstellt.
4. Polymerer Farbkuppler nach Anspruch 3, worin R₂ -C(O)-NH- bedeutet.
5. Polymerer Farbkuppler nach Anspruch 1, worin das Polymer als Latex entsteht, der nicht isoliert, sondern als solcher verwendet wird.
6. Polymerer Farbkuppler nach Anspruch 5, worin das Polymer aus Einheiten besteht, die von mindestens einem nichtfarbkuppelnden, fotografisch inerten Comonomeren abgeleitet sind.
7. Polymerer Farbkuppler nach Anspruch 6, worin es sich bei dem fotografisch inerten Comonomeren um Methylacrylat, Ethylacrylat, Butylacrylat, Ethylhexylacrylat, Vinylacetat; Hydroxyethylmethacrylat, Hydroxypropylmethacrylat; Methacrylsäure, Acrylsäure, Itaconsäure, 2-Carboxyethylacrylat sowie deren Salze, Acrylamid, Methacrylamid, N-Hydroxymethylacrylamid, Styrol, N-Vinylpyrrolidon, 1-Vinylimidazol; 4-Vinylpyridin, Dimethylaminoethylmethacrylat, Vinylsulfonsäure sowie deren Salze, Acrylnitril und Vinylidenchlorid handelt.
8. Polymerer Farbkuppler nach Anspruch 1, worin das Polymer als wasserlöslicher Feststoff entsteht.
9. Polymerer Farbkuppler nach Anspruch 8, worin in dem Polymer 40-60 Gew.% des Restes eines Monomeren der Formel
Figure imgb0044
 worin R₁ die in Anspruch 1 angegebene Bedeutung aufweist, L eine Alkylen- oder unterbrochene Alkylenverknüpfungsgruppe darstellt und R₁ sowie R¹¹ Alkylgruppen mit 1 bis 4 Kohlenstoffatomen und X⁻ ein Anion bedeuten, vorliegen.
10. Polymerer Farbkuppler nach Anspruch 1, bestehend aus dem Rest eines gelbfarbstoffbildenden monomeren Farbkupplers der allgemeinen Formel:
Figure imgb0045
 worin R₃, R₄, R₅ und R₆ jeweils Wasserstoff, Halogen, Alkoxy, Sulfoxy oder Sulfonamido bedeuten, R₁ und R₂ die in Anspruch 1 angegebene Bedeutung aufweisen, R₇ Wasserstoff oder eine Abgangsgruppe und L₁ und L₂ Direktverknüpfungen oder -NH- bedeuten.
11. Polymerer Farbkuppler nach Anspruch 1, bestehend aus dem Rest eines gelbfarbstoffbildenden monomeren Farbkupplers der allgemeinen Formel:
Figure imgb0046
 worin R₁ und R₂ die in Anspruch 1 angegebene Bedeutung und R₆ und R₇ die in Anspruch 10 angegebene Bedeutung aufweisen.
12. Polymerer Farbkuppler nach Anspruch 1, bestehend aus dem Rest eines magentafarbstoffbildenden monomeren Farbkupplers der allgemeinen Formel:
Figure imgb0047
 worin R₁ und R₂ die in Anspruch 1 angegebene Bedeutung aufweisen, R₈ Wasserstoff oder eine Abgangsgruppe bedeutet und R₁₀, R₁₁ und R₁₂ jeweils Wasserstoff, Halogen oder Alkoxy darstellen.
13. Polymerer Farbkuppler nach Anspruch 1, bestehend aus dem Rest eines magentafarbstoffbildenden monomeren Farbkupplers der allgemeinen Formel:
Figure imgb0048
 worin R₁ die in Anspruch 1 und R₈ und R₁₀ die in Anspruch 12 angegebene Bedeutung aufweisen und R₉ Alkyl, Dialkylamino, gegebenenfalls substituiertes Aryl und gegebenenfalls substituiertes Acylamino bedeutet.
14. Polymerer Farbkuppler nach Anspruch 1, bestehend aus dem Rest eines cyanfarbstoffbildenden monomeren Farbkupplers, bei dem es sich um einen Phenolkuppler der allgemeinen Formel:
Figure imgb0049
 oder um einen Phenolkuppler der allgemeinen Formel:
Figure imgb0050
 oder um einen Naphtholkuppler der allgemeinen Formel:
Figure imgb0051
 worin in den obigen drei Formeln R₁ und R₁₂ die in Anspruch 13 angegebene Bedeutung aufweisen, R₁₄ Wasserstoff oder eine Abgangsgruppe wie ein Halogenatom oder eine substituierte Alkoxygruppe, R₁₃ ein Wasserstoffatom oder eine Alklgruppe mit 1 bis 5 Kohlenstoffatomen, R₁₅ eine gegebenenfalls substituierte- Alkyl- oder Acylaminogruppe oder eine para- Cyananilingruppe und R₁₇ eine Verknüpfungsgruppe und y 0 oder 1 und R₁₆ eine Alkoxy-, Amino-, Amido- oder Sulfonamidgruppe oder ein Wasserstoffatom bedeuten, handelt.
15. Fotografisches Material mit mindestens einer Gelatine-Silberhalogenidemulsionsschicht, die einen polymeren Farbkuppler nach Anspruch 1 enthält.
EP19880810842 1987-12-15 1988-12-07 Farbbildende polymerische Kuppler Expired EP0321401B1 (de)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
GB8729196 1987-12-15
GB878729196A GB8729196D0 (en) 1987-12-15 1987-12-15 Polymeric colour couplers

Publications (3)

Publication Number Publication Date
EP0321401A2 EP0321401A2 (de) 1989-06-21
EP0321401A3 EP0321401A3 (en) 1989-09-13
EP0321401B1 true EP0321401B1 (de) 1992-06-24

Family

ID=10628499

Family Applications (1)

Application Number Title Priority Date Filing Date
EP19880810842 Expired EP0321401B1 (de) 1987-12-15 1988-12-07 Farbbildende polymerische Kuppler

Country Status (4)

Country Link
EP (1) EP0321401B1 (de)
JP (1) JPH02953A (de)
DE (1) DE3872365T2 (de)
GB (1) GB8729196D0 (de)

Families Citing this family (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5141844A (en) * 1990-05-07 1992-08-25 Eastman Kodak Company Polymeric dye-forming couplers
US5362616A (en) * 1991-12-19 1994-11-08 Eastman Kodak Company Chromogenic black-and-white photographic imaging systems
US5364747A (en) * 1992-11-25 1994-11-15 Eastman Kodak Company Color correcting layers consisting essentially of at least one dye-forming coupler and gelatin in chromogenic black-and-white photographic imaging systems
US5972586A (en) * 1995-11-22 1999-10-26 Fuji Photo Film Co., Ltd. Silver halide color photosensitive material
DE69813757T2 (de) * 1998-01-19 2004-03-18 Société des Produits Nestlé S.A. Gekühltes wässriges Gelee und Verfahren zu dessen Herstellung

Family Cites Families (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3497350A (en) * 1965-06-28 1970-02-24 Eastman Kodak Co Multicolor elements for color photography
JPS6011342B2 (ja) * 1975-11-07 1985-03-25 小西六写真工業株式会社 ハロゲン化銀写真感光材料の画像形成方法
JPS6026221B2 (ja) * 1977-06-24 1985-06-22 キヤノン株式会社 スクリ−ン状感光体の張設方法
JPS5810737B2 (ja) * 1978-10-25 1983-02-26 コニカ株式会社 ハロゲン化銀多層カラ−写真感光材料
JPS58215645A (ja) * 1982-06-10 1983-12-15 Mitsubishi Paper Mills Ltd 画像形成方法
US4520093A (en) * 1984-01-30 1985-05-28 E. I. Du Pont De Nemours And Company Photosensitive composition and method for forming a neutral black image

Also Published As

Publication number Publication date
JPH02953A (ja) 1990-01-05
DE3872365T2 (de) 1993-02-11
EP0321401A3 (en) 1989-09-13
GB8729196D0 (en) 1988-01-27
EP0321401A2 (de) 1989-06-21
DE3872365D1 (de) 1992-07-30

Similar Documents

Publication Publication Date Title
US4435503A (en) Silver halide color photographic light-sensitive material
JPH0682962A (ja) 高分子紫外線吸収剤を組み込んだ写真要素
US4409320A (en) Silver halide color photographic light-sensitive material
US4612278A (en) Photographic materials and process comprising polymeric couplers with alkoxyalkylacrylate comonomers
US4388404A (en) Silver halide color photographic light-sensitive material
US3370952A (en) Color formers
US4201589A (en) Silver halide photo-sensitive material prepared with solvent and solvent soluble polymer
US4128427A (en) Silver halide emulsions containing polymeric color couplers
US3767412A (en) Polymeric colour couplers and their use in colour photography
GB2133170A (en) Silver halide color photographic material containing polymeric cyan-forming coupler
US4474870A (en) Silver halide color photographic light-sensitive material
GB2125571A (en) Polymeric cyan-forming coupler
EP0321401B1 (de) Farbbildende polymerische Kuppler
EP0321399A2 (de) Herstellung von Latizes von Farbkuppler-Polymeren
JPS5943733B2 (ja) 写真現像抑制剤スキャベンジャ−
US4106941A (en) Photographic silver halide elements containing optical brightening water-soluble interpolymers
JPS5965844A (ja) ハロゲン化銀カラ−写真感光材料
US5547819A (en) Silver halide photographic material
US4557998A (en) Colorless ligand-releasing monomers and polymers and their use to provide dyes with metal ions
US4496650A (en) Silver halide color photographic light-sensitive material
CA1046189A (en) Polymers having active methylene group
US4555478A (en) Photographic element and process for providing metal complex color images
DE3341352A1 (de) Photographisches lichtempfindliches silberhalogenidmaterial
DE3223316A1 (de) Lichtempfindliches photographisches silberhalogenidmaterial
US3986877A (en) Development promoting compounds for silver halide photography

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: 19881209

AK Designated contracting states

Kind code of ref document: A2

Designated state(s): BE CH DE FR GB IT LI NL

PUAL Search report despatched

Free format text: ORIGINAL CODE: 0009013

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

Owner name: ILFORD LIMITED

AK Designated contracting states

Kind code of ref document: A3

Designated state(s): BE CH DE FR GB IT LI NL

17Q First examination report despatched

Effective date: 19910619

GRAA (expected) grant

Free format text: ORIGINAL CODE: 0009210

AK Designated contracting states

Kind code of ref document: B1

Designated state(s): BE CH DE FR GB IT LI NL

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: NL

Effective date: 19920624

Ref country code: LI

Effective date: 19920624

Ref country code: CH

Effective date: 19920624

REF Corresponds to:

Ref document number: 3872365

Country of ref document: DE

Date of ref document: 19920730

ET Fr: translation filed
ITF It: translation for a ep patent filed
REG Reference to a national code

Ref country code: CH

Ref legal event code: PL

NLV1 Nl: lapsed or annulled due to failure to fulfill the requirements of art. 29p and 29m of the patents act
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: FR

Payment date: 19941108

Year of fee payment: 7

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

Ref country code: GB

Payment date: 19941116

Year of fee payment: 7

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

Ref country code: DE

Payment date: 19941122

Year of fee payment: 7

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

Ref country code: BE

Payment date: 19941125

Year of fee payment: 7

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: GB

Effective date: 19951207

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: BE

Effective date: 19951231

BERE Be: lapsed

Owner name: ILFORD LTD

Effective date: 19951231

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

Effective date: 19951207

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: FR

Effective date: 19960830

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: DE

Effective date: 19960903

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: 20051207