EP0011645B1 - Elements photosensibles pour la mise en oeuvre dans une unite de film de transfert par diffusion - Google Patents
Elements photosensibles pour la mise en oeuvre dans une unite de film de transfert par diffusion Download PDFInfo
- Publication number
- EP0011645B1 EP0011645B1 EP19790900514 EP79900514A EP0011645B1 EP 0011645 B1 EP0011645 B1 EP 0011645B1 EP 19790900514 EP19790900514 EP 19790900514 EP 79900514 A EP79900514 A EP 79900514A EP 0011645 B1 EP0011645 B1 EP 0011645B1
- Authority
- EP
- European Patent Office
- Prior art keywords
- silver halide
- layer
- photosensitive
- gelatin
- element according
- 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
Links
- 238000012546 transfer Methods 0.000 title claims abstract description 23
- 238000009792 diffusion process Methods 0.000 title claims abstract description 11
- 239000004332 silver Substances 0.000 claims abstract description 105
- 229910052709 silver Inorganic materials 0.000 claims abstract description 105
- -1 silver halide Chemical class 0.000 claims abstract description 94
- 108010010803 Gelatin Proteins 0.000 claims abstract description 66
- 229920000159 gelatin Polymers 0.000 claims abstract description 66
- 239000008273 gelatin Substances 0.000 claims abstract description 66
- 235000019322 gelatine Nutrition 0.000 claims abstract description 66
- 235000011852 gelatine desserts Nutrition 0.000 claims abstract description 66
- 239000002245 particle Substances 0.000 claims abstract description 50
- 229920000126 latex Polymers 0.000 claims abstract description 24
- 239000004816 latex Substances 0.000 claims abstract description 22
- 238000012545 processing Methods 0.000 claims abstract description 22
- 239000000463 material Substances 0.000 claims abstract description 19
- 239000000203 mixture Substances 0.000 claims abstract description 19
- 230000008961 swelling Effects 0.000 claims abstract description 5
- 239000000975 dye Substances 0.000 claims description 49
- 229920000642 polymer Polymers 0.000 claims description 13
- 229920001577 copolymer Polymers 0.000 claims description 10
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 claims description 8
- 229920003229 poly(methyl methacrylate) Polymers 0.000 claims description 6
- 239000004926 polymethyl methacrylate Substances 0.000 claims description 6
- 238000000149 argon plasma sintering Methods 0.000 claims description 5
- AJDUTMFFZHIJEM-UHFFFAOYSA-N n-(9,10-dioxoanthracen-1-yl)-4-[4-[[4-[4-[(9,10-dioxoanthracen-1-yl)carbamoyl]phenyl]phenyl]diazenyl]phenyl]benzamide Chemical compound O=C1C2=CC=CC=C2C(=O)C2=C1C=CC=C2NC(=O)C(C=C1)=CC=C1C(C=C1)=CC=C1N=NC(C=C1)=CC=C1C(C=C1)=CC=C1C(=O)NC1=CC=CC2=C1C(=O)C1=CC=CC=C1C2=O AJDUTMFFZHIJEM-UHFFFAOYSA-N 0.000 claims description 5
- 239000001043 yellow dye Substances 0.000 claims description 5
- 239000004793 Polystyrene Substances 0.000 claims description 3
- 229920002223 polystyrene Polymers 0.000 claims description 3
- 239000003513 alkali Substances 0.000 abstract description 5
- 230000005855 radiation Effects 0.000 abstract description 2
- 239000010410 layer Substances 0.000 description 117
- 239000000839 emulsion Substances 0.000 description 47
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 12
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 9
- DWYHDSLIWMUSOO-UHFFFAOYSA-N 2-phenyl-1h-benzimidazole Chemical compound C1=CC=CC=C1C1=NC2=CC=CC=C2N1 DWYHDSLIWMUSOO-UHFFFAOYSA-N 0.000 description 6
- 230000008901 benefit Effects 0.000 description 6
- 229920001519 homopolymer Polymers 0.000 description 6
- 239000000178 monomer Substances 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- 238000011161 development Methods 0.000 description 5
- 239000011229 interlayer Substances 0.000 description 5
- 238000000034 method Methods 0.000 description 5
- 239000000047 product Substances 0.000 description 5
- 238000000926 separation method Methods 0.000 description 5
- ZUNKMNLKJXRCDM-UHFFFAOYSA-N silver bromoiodide Chemical compound [Ag].IBr ZUNKMNLKJXRCDM-UHFFFAOYSA-N 0.000 description 5
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 4
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical compound [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 description 4
- 239000002585 base Substances 0.000 description 4
- 239000006185 dispersion Substances 0.000 description 4
- 229920002401 polyacrylamide Polymers 0.000 description 4
- 230000008569 process Effects 0.000 description 4
- 230000002829 reductive effect Effects 0.000 description 4
- 229920006029 tetra-polymer Polymers 0.000 description 4
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 3
- PCSMJKASWLYICJ-UHFFFAOYSA-N Succinic aldehyde Chemical compound O=CCCC=O PCSMJKASWLYICJ-UHFFFAOYSA-N 0.000 description 3
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 description 3
- 239000011248 coating agent Substances 0.000 description 3
- 238000000576 coating method Methods 0.000 description 3
- 230000007423 decrease Effects 0.000 description 3
- 239000003999 initiator Substances 0.000 description 3
- 230000000670 limiting effect Effects 0.000 description 3
- OMNKZBIFPJNNIO-UHFFFAOYSA-N n-(2-methyl-4-oxopentan-2-yl)prop-2-enamide Chemical compound CC(=O)CC(C)(C)NC(=O)C=C OMNKZBIFPJNNIO-UHFFFAOYSA-N 0.000 description 3
- 229920000139 polyethylene terephthalate Polymers 0.000 description 3
- 239000005020 polyethylene terephthalate Substances 0.000 description 3
- 230000009467 reduction Effects 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N Alumina Chemical compound [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 2
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- 239000004215 Carbon black (E152) Substances 0.000 description 2
- 229910019142 PO4 Inorganic materials 0.000 description 2
- 239000004372 Polyvinyl alcohol Substances 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 229920002472 Starch Polymers 0.000 description 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
- 125000005396 acrylic acid ester group Chemical group 0.000 description 2
- 230000002411 adverse Effects 0.000 description 2
- AYJRCSIUFZENHW-UHFFFAOYSA-L barium carbonate Chemical compound [Ba+2].[O-]C([O-])=O AYJRCSIUFZENHW-UHFFFAOYSA-L 0.000 description 2
- OSGAYBCDTDRGGQ-UHFFFAOYSA-L calcium sulfate Chemical compound [Ca+2].[O-]S([O-])(=O)=O OSGAYBCDTDRGGQ-UHFFFAOYSA-L 0.000 description 2
- 239000006229 carbon black Substances 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000003995 emulsifying agent Substances 0.000 description 2
- 238000007720 emulsion polymerization reaction Methods 0.000 description 2
- 239000000693 micelle Substances 0.000 description 2
- 230000007935 neutral effect Effects 0.000 description 2
- 235000021317 phosphate Nutrition 0.000 description 2
- 229920002451 polyvinyl alcohol Polymers 0.000 description 2
- 230000000717 retained effect Effects 0.000 description 2
- 230000035945 sensitivity Effects 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 230000003595 spectral effect Effects 0.000 description 2
- 239000008107 starch Substances 0.000 description 2
- 235000019698 starch Nutrition 0.000 description 2
- 239000004094 surface-active agent Substances 0.000 description 2
- 229920003002 synthetic resin Polymers 0.000 description 2
- 239000000057 synthetic resin Substances 0.000 description 2
- 239000004408 titanium dioxide Substances 0.000 description 2
- 229920002554 vinyl polymer Polymers 0.000 description 2
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 1
- OEPOKWHJYJXUGD-UHFFFAOYSA-N 2-(3-phenylmethoxyphenyl)-1,3-thiazole-4-carbaldehyde Chemical compound O=CC1=CSC(C=2C=C(OCC=3C=CC=CC=3)C=CC=2)=N1 OEPOKWHJYJXUGD-UHFFFAOYSA-N 0.000 description 1
- KFDVPJUYSDEJTH-UHFFFAOYSA-N 4-ethenylpyridine Chemical compound C=CC1=CC=NC=C1 KFDVPJUYSDEJTH-UHFFFAOYSA-N 0.000 description 1
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- 229920008347 Cellulose acetate propionate Polymers 0.000 description 1
- 239000001856 Ethyl cellulose Substances 0.000 description 1
- ZZSNKZQZMQGXPY-UHFFFAOYSA-N Ethyl cellulose Chemical compound CCOCC1OC(OC)C(OCC)C(OCC)C1OC1C(O)C(O)C(OC)C(CO)O1 ZZSNKZQZMQGXPY-UHFFFAOYSA-N 0.000 description 1
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 239000004721 Polyphenylene oxide Substances 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000011149 active material Substances 0.000 description 1
- 239000012670 alkaline solution Substances 0.000 description 1
- 125000005250 alkyl acrylate group Chemical group 0.000 description 1
- 125000002877 alkyl aryl group Chemical group 0.000 description 1
- 125000000129 anionic group Chemical group 0.000 description 1
- 229960005070 ascorbic acid Drugs 0.000 description 1
- 235000010323 ascorbic acid Nutrition 0.000 description 1
- 239000011668 ascorbic acid Substances 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- 229920002678 cellulose Polymers 0.000 description 1
- 229920003086 cellulose ether Polymers 0.000 description 1
- 238000005345 coagulation Methods 0.000 description 1
- 230000015271 coagulation Effects 0.000 description 1
- 239000000084 colloidal system Substances 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- 230000001627 detrimental effect Effects 0.000 description 1
- FDENMIUNZYEPDD-UHFFFAOYSA-L disodium [2-[4-(10-methylundecyl)-2-sulfonatooxyphenoxy]phenyl] sulfate Chemical compound [Na+].[Na+].CC(C)CCCCCCCCCc1ccc(Oc2ccccc2OS([O-])(=O)=O)c(OS([O-])(=O)=O)c1 FDENMIUNZYEPDD-UHFFFAOYSA-L 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- 238000010410 dusting Methods 0.000 description 1
- 229920001249 ethyl cellulose Polymers 0.000 description 1
- 235000019325 ethyl cellulose Nutrition 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 230000009477 glass transition Effects 0.000 description 1
- 239000008131 herbal destillate Substances 0.000 description 1
- 230000002209 hydrophobic effect Effects 0.000 description 1
- 238000010348 incorporation Methods 0.000 description 1
- 229910052809 inorganic oxide Inorganic materials 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 229910000836 magnesium aluminium oxide Inorganic materials 0.000 description 1
- 239000000395 magnesium oxide Substances 0.000 description 1
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 1
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 238000012856 packing Methods 0.000 description 1
- 230000036961 partial effect Effects 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- 150000003013 phosphoric acid derivatives Chemical class 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 229920000058 polyacrylate Polymers 0.000 description 1
- 229920000515 polycarbonate Polymers 0.000 description 1
- 239000004417 polycarbonate Substances 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 229920000570 polyether Polymers 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 239000013047 polymeric layer Substances 0.000 description 1
- 239000002952 polymeric resin Substances 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- 229920002689 polyvinyl acetate Polymers 0.000 description 1
- 239000011118 polyvinyl acetate Substances 0.000 description 1
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- DCKVNWZUADLDEH-UHFFFAOYSA-N sec-butyl acetate Chemical compound CCC(C)OC(C)=O DCKVNWZUADLDEH-UHFFFAOYSA-N 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- MSFPLIAKTHOCQP-UHFFFAOYSA-M silver iodide Chemical group I[Ag] MSFPLIAKTHOCQP-UHFFFAOYSA-M 0.000 description 1
- 239000002356 single layer Substances 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 229920003169 water-soluble polymer Polymers 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
Classifications
-
- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03C—PHOTOSENSITIVE MATERIALS FOR PHOTOGRAPHIC PURPOSES; PHOTOGRAPHIC PROCESSES, e.g. CINE, X-RAY, COLOUR, STEREO-PHOTOGRAPHIC PROCESSES; AUXILIARY PROCESSES IN PHOTOGRAPHY
- 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
-
- 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
- G03C1/04—Silver halide emulsions; Preparation thereof; Physical treatment thereof; Incorporation of additives therein with macromolecular additives; with layer-forming substances
- G03C1/053—Polymers obtained by reactions involving only carbon-to-carbon unsaturated bonds, e.g. vinyl polymers
-
- 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
- G03C1/76—Photosensitive materials characterised by the base or auxiliary layers
- G03C1/95—Photosensitive materials characterised by the base or auxiliary layers rendered opaque or writable, e.g. with inert particulate additives
-
- 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
- G03C8/00—Diffusion transfer processes or agents therefor; Photosensitive materials for such processes
- G03C8/02—Photosensitive materials characterised by the image-forming section
-
- 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
- G03C8/00—Diffusion transfer processes or agents therefor; Photosensitive materials for such processes
- G03C8/02—Photosensitive materials characterised by the image-forming section
- G03C8/08—Photosensitive materials characterised by the image-forming section the substances transferred by diffusion consisting of organic compounds
Definitions
- diffusion transfer photographic products and processes involve film units having a photosensitive system including at least one silver halide layer, usually integrated with an image-providing material. After photoexposure, the photosensitive system is developed to establish an imagewise distribution of a diffusible image-providing material, at least a portion of which is transferred by diffusion to an image-receiving layer capable of mordanting or otherwise fixing the transferred image-providing material.
- the transfer image is viewed by reflection after separation of the image-receiving element from the photosensitive system. In other products, however, such separation is not required and instead the transfer image-receiving layer is viewed against a reflecting background usually provided by a dispersion of a white reflecting pigment, such as, for example, titanium dioxide.
- the latter type of film unit is generally referred to in the art as integral negative-positive film units and are described, for example, in the above-mentioned U.S. Patents Nos. 3,415,644 and 3,594,165.
- U.S. Patent No. 2,772,166 discloses gelatin silver halide emulsions which also contain a hydrosol resulting from the emulsion polymerization of a mixture of styrene, acrylonitrile or a vinylidene chloride with an alkyl acrylate or alkyl methacrylate and acrylic acid.
- the described hydrosol is used in the range of 1 to 10% of the gelatin.
- U.S. Patent No. 2,835,582 is directed to mixtures of gelatin and polymeric hydrosols in silver halide layers wherein the hydrosol is prepared by polymerizing at least one monoethylenically unsaturated monomer in the presence of an ampholytic surface active agent.
- suitable monomeric materials are mentioned methylmethacrylate and styrene. It is a requirement that the polymeric materials be film formers and the essence of the invention resides in the presence of the ampholytic surface active material to provide its enhanced compatibility with gelatin.
- U.S. Patent No. 3,157,510 is directed to gelatin silver halide emulsions which also include a dispersion of minute particles of a water insoluble soft acrylate polymer resin at a level of about 5 to 40% by weight of gelatin.
- U.S. Patent No. 3,325,286 is directed to gelatin silver halide emulsions which include an aqueous dispersion of a polymeric vinyl compound and at least one anionic dispersing agent specified in the patent.
- the emulsion layer also requires a polyoxyethylene compound as defined in the patent.
- One of the polymeric materials recited is a homopolymer of an a-hydrocarbon substituted acrylic acid ester.
- U.S. Patent No. 3,547,650 is directed to gelatin-silver halide emulsions which include an aqueous dispersion of a polymeric vinyl compound dispersed with a mixture of specified organic phosphates.
- One of the polymerized vinyl compounds recited comprises a homopolymer of an ⁇ -hydrocarbon substituted acrylic acid ester.
- U.S. Patent No. 3,772,032 is directed to a gelatin silver halide emulsion which includes a polymeric latex prepared by emulsion polymerization in the presence of at least 5% by weight of an emulsifying agent to reduce the stress sensitivity of the emulsion.
- This patent states that employing the specified emulsifying agent at a level of at least 5% by weight, no fog is found in emulsions employing large amounts of methylmethacrylate in the latex whereas normally the presence of even 50% of methylmethacrylate in the latex results in intolerable increases in fog.
- U.S. Patent No. 3,773,517 is directed to a gelatin-silver halide emulsion which includes a polymer latex prepared by copolymerization of a monomer yielding a water insoluble homopolymer and a monomer yielding a water soluble polymer.
- the patent requires the polymerization to occur in the presence of a specified alkylaryl polyether phosphate surface active agent.
- One of the monomers which would produce a water insoluble homopolymer is an alkylmethacrylate.
- U.S. Patent No. 3,418,132 is directed to a photographic film unit which, in one embodiment, is particularly suited for rapid access processing by virtue of the incorporation of inert particles into at least one layer of the photographic element.
- the inert particles include starch, barium sulfate, calcium carbonate, synthetic resins etc.
- the inert particles are in the range of 7 to 15 pm.
- U.S. Patent No. 3,505,068 is directed to a photographic element which contains overlying silver halide emulsions wherein the first emulsion is a regular silver haloiodide emulsion and the second contains grains which have an iodide-free shell and a silver iodide core.
- U.S. Patent No. 3,663,228 is directed to a photographic film unit having a plurality of silver halide emulsion layers divided into sets with each set of a different speed while the layers in each set have the same speed but are responsive to different spectral regions. Color filters are disposed between the layers.
- U.S. Patent No. 3,695,882 is directed to a photosensitive element comprising a support carrying two emulsions, each containing a non-diffusing color coupler. Each emulsion has a different speed and different silver halide-coupler molar ratio.
- U.S. Patent No. 3,846,135 is directed to a synergistic increase in the sensitivity of two superposed silver halide layers when the lower layer is less sensitive than the upper layer and has a maximum density of at least 1.5 compared to a maximum density of at least 0.9 for the upper layer.
- the lower layer is about 5 to 15 pm thick.
- U.S. Patents Nos. 3,960,558 and 4,003,744 disclose diffusion transfer film units which employ split silver halide emulsions having dye image-forming material associated therewith and which, in fact, contain dye image-forming material in one of said contiguous layers.
- U.S. Patent No. 3,632,342 is directed to a photographic element comprising a support carrying at least one layer containing a high contrast silver halide emulsion layer containing an acrylic latex material and an additional silver halide layer containing a hydrophilic colloid which is free of latex micelles. It is stated that discrete micelles are preferred but that coalescing may occur. Copolymers of hydrophilic and hydrophobic monomers are disclosed.
- a photosensitive element according to the invention for use in a diffusion transfer film unit comprises a support carrying at least one photosensitive silver halide layer that has a dye image-forming material associated therewith and that comprises silver halide grains having an average diameter of 2.5 ⁇ m or less and gelatin and is characterised in that the said silver halide layer, or at least one of the said silver halide layers, includes inert particles which have an average diameter that is not less than 0.075 jMm but that is less than or equal to the average diameter of the silver halide grains and which are compatible with gelatin, substantially non-swelling in aqueous alkaline processing composition and substantially non-light scattering and which, before and during processing with the aqueous alkaline processing composition, are substantially non-film forming and substantially non-coalescing.
- the provision of the particles results in bulking of the gelatin layer and by choosing particles that are substantially non-swelling in aqueous alkali they provide a non-swelling, sizeable mass to bulk the gelatin layer.
- the particles must be substantially non-film forming and substantially non-coalescing in order that they are sufficiently hard to retain their physical' identity as individual particles in the presence of aqueous alkaline processing composition. If the particles were to coalesce or film form to any significant extent this would inhibit dye transfer and also would reduce the bulking effect of the particles.
- the particles must be substantially non-light scattering in order that the layer containing gelatin and the particles does not cause sufficient light scattering to impair significantly the photographic results obtained with the product. In practice this means that the particles must have a refractive index which is sufficiently close to the refractive index of gelatin to avoid detrimental light scattering.
- the particles must be compatible with gelatin so as to avoid coagulation within the layer.
- photosensitive silver halide layer as used herein is intended to include a first and second photosensitive silver halide layer sensitive to the same portion of the spectrum and in contiguous relationship, i.e. the so-called “split emulsions”. These are described in more detail below.
- the dye image-forming material is preferably a dye developer which is soluble and diffusable in alkali as a function of the exposure and development of the silver halide emulsion layer and the present invention will be described with respect to dye developers as the dye image-forming materials although it will be understood that other dye image-forming materials may be employed in the present invention.
- Dye developers are well known in the art.
- a dye developer is a compound which contains a silver halide developing moiety and the chromophoric system of a dye.
- a dye developer providing an image dye of appropriate color is associated with each silver halide emulsion layer; for example, a cyan dye developer with a red sensitive silver halide layer; a magenta dye developer with a green sensitive silver halide emulsion layer; and a yellow dye developer with a blue sensitive silver halide emulsion layer.
- Unoxidized dye developer is insoluble in water but soluble and mobile in aqueous alkali. Oxidation of the dye developer as a result of development of exposed silver halide results in its immobilization, while unoxidized dye developer can diffuse to the dyeable image-receiving layer producing a positive image therein.
- the unoxidized dye developer pass through the associated silver halide emulsion layer as rapidly as possible consistent with development thereof. Since gelatin swells to a considerable degree upon contact with the photographic processing composition and thus would be a factor in slowing dye developer transfer, it is desirable to form the silver halide emulsion layer with a minimum of gelatin. The minimum quantity of gelatin employed, however, is controlled to a great degree by the size of the silver halide grains. Thus, it is desirable to employ sufficient gelatin to retain the silver halide grains within the layer, that is, to prevent any projection of the grains or portion of the grains through the gelatin layer at the interface into contact with adjacent layers.
- Inert particles suitable for use in the present invention include starch, barium sulfate, calcium carbonatq, cellulose esters such as cellulose acetate propionate, cellulose ethers such as ethyl cellulose, glass, synthetic resins such as polyvinyl acetate, polycarbonates, homo and copolymers of styrene, inorganic oxides such as zinc oxide, silica, titanium dioxide, magnesium oxide and aluminium oxide, as well as hardened gelatin grains, calcium sulfate, barium carbonate and the like.
- the preferred inert particles for use in the present invention are polymethylmethacrylate and polystyrene and are provided for the film unit by dispersing polymethylmethacrylate latex or polystyrene latex in the emulsion.
- the film forming and hardness characteristics of polymers are properties associated with the glass transition temperature of the polymer.
- the Tg of the polymer should be above the temperature at which the polymer is dried.
- the Tg is above 35°C, more preferably, above 60°C.
- the Tg is above 100°C.
- the polymer latex may be a homopolymer or a copolymer provided that the comonomers do not modify the copolymer to the extent that the required properties are not retained.
- a preferred copolymer is methyl methacrylate/hydroxypropyl methacrylate copolymer.
- the inert particles should be no larger than the silver halide grains with which they are associated.
- the maximum average diameter of the silver halide grains is 2.5 pm or less and preferably less than 2.0 ,am.
- the maximum average diameter of the inert particles is 2.5 pm.
- the lower limit of the particles is determined by the fact that one should avoid packing of the particles such as would impede dye transfer.
- the inert particles must be not less than 0,075 ⁇ m in diameter.
- the inert particles have an average diameter which is 10-15%, of the average diameter of the silver halide grains associated therewith.
- the quantity of polymer latex to be employed may be readily determined for any given silver halide emulsion. For a given silver halide grain size, as the quantity of gelatin decreases, the polymer gelatin ratio goes up to keep the layer dimensions the same. Sufficient gelatin must be present to keep the layer intact and prevent dusting of the polymer particles.
- a ratio (weight basis) of 0.5 to 1 to 10 to 1 polymer latex (solids) to gelatin is employed. Particularly preferred is a 1 to 1 ratio for fine grains (less than about 1 ⁇ m) and 6 to 1 for coarse grains (greater than about 1.3 ⁇ m).
- the average mean diameter of the fine grains is less than about 1 ⁇ m and the large grains, greater than 1.3 ⁇ m.
- At least one of the photosensitive silver halide layers that includes the inert particles may be in the form of a split emulsion.
- it may comprise a first photosensitive silver halide layer distal to the exposure surface of the element and comprising silver halide grains possessing a first mean particle size, and a second photosensitive silver halide layer having a second mean particle size, the second photosensitive layer having a higher intrinsic speed than the first photosensitive silver halide layer, the first and second photosensitive silver halide layers being in contiguous relationship and the inert particles being in at least the second silver halide layer.
- the first and second silver halide layers will generally be free of dye image-forming material but will have associated therewith a dye image-forming material which is diffusible as a function of the point-to-point degree of silver halide exposure to actinic radiation.
- Inert particles may be employed in both layers of the split emulsion.
- the intrinsic speed of the second silver halide emulsion layer is greater than that of the first layer.
- the speed difference between the first and second layers generally ranges from about 2 to about 8 stops, preferably about 5 stops.
- the average mean diameter of the silver halide grains in the first photosensitive silver halide layer is less than about 1 ⁇ m and the average mean diameter of the grains in the second photosensitive layer is greater than about 1.3 ⁇ m.
- the coated layers do not retain their integrity but rather combine, inter-mixing the grain sizes, so that the resulting combined silver halide layer functions as if a single layer of blended grain sizes were coated, thus losing all the benefits achieved in a layered structure and introducing the drawbacks of the single layered, low gelatin system.
- the photosensitive element of the invention preferably comprises a support carrying a red sensitive silver halide unit having associated therewith a cyan dye developer, a green sensitive silver halide unit having associated therewith a magenta dye developer and a blue sensitive silver halide unit having associated therewith a yellow dye developer. At least one of these units will comprise gelatin and inert particles as defined above and in particular it is preferred for the green sensitive silver halide unit to include the polymeric latex or other inert particles.
- the invention includes not only the photosensitive element described above but also diffusion transfer film units comprising a support carrying at least one photosensitive element as defined above and an image receiving element comprising a dyeable receiving layer to receive a dye image diffusing thereto after photoexposure and processing of the photosensitive element.
- the receiving layer which can also be called a polymeric layer, is in superposed relationship with the photosensitive eiement at least after exposure of the element and during processing of the exposed photosensitive silver halide emulsion or emulsions, that is during contact of the emulsion with the aqueous alkali processing composition.
- the image receiving element is affixed to at least one edge of the photosensitive element.
- the film unit may include a rupturable container of processing composition positioned to discharge its contents between a predetermined pair of layers of the film unit.
- the dyeable receiving layer may be capable of being superposed over the silver halide emulsion layer or layers subsequent to photoexposure and may be capable of being separated therefrom after processing.
- the film unit is a permanent laminate wherein the image is viewable in the receiving layer without separation of the receiving layer from the film unit.
- the film unit may be a composite structure comprising the photosensitive element and the image receiving element permanently affixed to each other in superposed relationship, the support layers of each of the elements being outermost.
- the support layer of the image receiving element is preferably transparent.
- polymeric latices preferred for employment in the present invention may be prepared by known techniques.
- the following non-limiting example illustrates the preparation of a latex preferred for use in the present invention.
- a reactor was charge with 102 I of demineralized water and the Dowfax 2A1 and heated under nitrogen to 83°C whereupon 7.65 kg. of methyl methacrylate was added and mixed until the temperature returned to 83°C. After 5 min. at 83°C, 4.93 kg. of initiator solution (0.15 kg. of potassium persulfate and 14.79 kg. water) was added. After the exotherm, the temperature was reduced to 85°C and the remaining methyl methacrylate was added at a rate of about 361 g/min. and the remaining initiator solution at a rate of about 111 g/min. At the end of the monomer and initiator addition, the temperature was maintained at 85°C for 10 min. and then the ascorbic acid was added. The resulting latex had a 30% solids and the latex particles had an average diameter of about a 0.125 IIm.
- a photosensitive element was prepared by coating, in succession, on a gelatin subbed, opaque polyethylene terephthalate film base, the following layers.
- An image-receiving element was prepared by coating the following layers in succession on a 0.01 mm (4 mil) polyethylene terephthalate film base, said layers respectively comprising:
- An aqueous alkaline solution comprising:
- a second film unit was prepared as described above except that layer 2, the green-sensitive silver halide emulsion layer additionally contained 1292 mg/m 2 (120 mg/ft 2 ) (solids) of a polymethylmethacrylate latex having an average particle size of about 0.125 Mm and layer 6 was reduced in coverage by 40%.
- the film units were processed in the following manner:
- the above table illustrates the adverse effect gelatin has on dye transfer.
- the table also shows that a layer with a greater coverage than the gelatin layer but composed of gelatin and latex particles provides transfer rates approaching that obtained with no overcoat at all, especially in the initial time period.
- a photosensitive element was prepared by coating, in succession, on a gelatin subbed, opaque polyethylene terephthalate film base, the following layers:
- a second film unit was prepared as described in Example 4 except that in layer 5 each green-sensitive silver halide emulsion layer additionally contained 4 times the coverage of gelatin of a polymethylmethacrylate latex having an average particle size of about 0.125 pm and layer 6 was reduced in coverage by 40%.
- Example 4 The film units of Examples 4 and 5 were processed in the following manner, using the image-receiving element and processing composition described in Example 1.
- the film unit was exposed to white light and the processing composition was spread between the two elements in a layer approximately 0.07 mm (0.0028") thick in the dark.
- interlayer (layer 6) adjacent the silver halide emulsion layer containing the inert particles were reduced in coverage by 40%. This is an additional and unexpected advantage of the present invention which further enhances dye transfer.
- Example 5 A film unit similar to Example 5 was prepared except that the polymer latex employed was a 90/10 methylmethacrylate/hydroxypropyl acrylate copolymer. Upon exposure and processing similar advantageous results were obtained.
Landscapes
- Physics & Mathematics (AREA)
- Chemical & Material Sciences (AREA)
- General Physics & Mathematics (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Spectroscopy & Molecular Physics (AREA)
- Silver Salt Photography Or Processing Solution Therefor (AREA)
- Photosensitive Polymer And Photoresist Processing (AREA)
Abstract
Claims (11)
Applications Claiming Priority (4)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US90199578A | 1978-05-02 | 1978-05-02 | |
| US901995 | 1978-05-02 | ||
| US93925778A | 1978-09-05 | 1978-09-05 | |
| US939257 | 1978-09-05 |
Publications (3)
| Publication Number | Publication Date |
|---|---|
| EP0011645A1 EP0011645A1 (fr) | 1980-06-11 |
| EP0011645A4 EP0011645A4 (fr) | 1980-09-29 |
| EP0011645B1 true EP0011645B1 (fr) | 1983-05-25 |
Family
ID=27129310
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| EP19790900514 Expired EP0011645B1 (fr) | 1978-05-02 | 1979-12-04 | Elements photosensibles pour la mise en oeuvre dans une unite de film de transfert par diffusion |
Country Status (4)
| Country | Link |
|---|---|
| EP (1) | EP0011645B1 (fr) |
| JP (1) | JPS5936253B2 (fr) |
| DE (1) | DE2965489D1 (fr) |
| WO (1) | WO1979001020A1 (fr) |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB8918723D0 (en) * | 1989-08-16 | 1989-09-27 | Kodak Ltd | Method of photographic processing |
| US5705311A (en) * | 1996-02-26 | 1998-01-06 | Polaroid Corporation | Heat-developable image-recording element |
| US6255044B1 (en) | 1998-01-21 | 2001-07-03 | Eastman Kodak Company | Silver halide elements that produce sharp images without fixing and processes for their use |
Family Cites Families (24)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2772166A (en) * | 1953-02-11 | 1956-11-27 | Eastman Kodak Co | Hydrophilic compositions and their preparation |
| US2835582A (en) * | 1954-02-03 | 1958-05-20 | Eastman Kodak Co | Gelatin-polymeric hydrosol mixtures and photographic articles prepared therefrom |
| US3142568A (en) * | 1961-03-13 | 1964-07-28 | Du Pont | Photographic emulsions, elements, and processes |
| US3325286A (en) * | 1961-08-28 | 1967-06-13 | Du Pont | Photographic emulsions and elements |
| US3450536A (en) * | 1961-03-24 | 1969-06-17 | Eg & G Inc | Silver halide photographic film having increased exposure-response characteristics |
| US3157510A (en) * | 1962-04-02 | 1964-11-17 | Eastman Kodak Co | Silver-resin print paper |
| US3287289A (en) * | 1962-06-11 | 1966-11-22 | Eastman Kodak Co | Plasticizers for radiation sensitive systems |
| US3411907A (en) * | 1965-03-04 | 1968-11-19 | Eastman Kodak Co | Photographic compositions containing combination of soft and hard matting agents |
| US3411911A (en) * | 1965-05-10 | 1968-11-19 | Eastman Kodak Co | Novel photographic materials containing water insoluble interpolymers |
| US3418132A (en) * | 1965-06-01 | 1968-12-24 | Eastman Kodak Co | Aldehyde gelatin hardening composition with carbocyclic diones |
| US3428455A (en) * | 1965-05-28 | 1969-02-18 | Eastman Kodak Co | Optically sensitized photographic element containing a developing agent |
| US3846135A (en) * | 1966-05-12 | 1974-11-05 | Agfa Gevaert Ag | Light-sensitive photographic material with increased sensitivity to light |
| US3505068A (en) * | 1967-06-23 | 1970-04-07 | Eastman Kodak Co | Photographic element |
| US3620747A (en) * | 1968-05-20 | 1971-11-16 | Eastman Kodak Co | Photographic element including superimposed silver halide layers of different speeds |
| US3632342A (en) * | 1969-03-03 | 1972-01-04 | Eastman Kodak Co | Photographic element containing acrylic latex polymers |
| JPS5223565B1 (fr) * | 1969-08-01 | 1977-06-25 | ||
| GB1337984A (en) * | 1970-06-17 | 1973-11-21 | Minnesota Mining & Mfg | Photographic silver halide emulsions |
| GB1333663A (en) * | 1971-04-16 | 1973-10-10 | Ilford Ltd | Photographic silver halide material |
| US3773517A (en) * | 1971-04-16 | 1973-11-20 | Ilford Ltd | Production of photographic silver halide emulsions |
| BE792598A (fr) * | 1971-12-10 | 1973-06-12 | Eastman Kodak Co | Produit photographique contenant des composes oxychromiques et procede pour obtenir une image a partir de ce produit |
| US4003744A (en) * | 1972-12-07 | 1977-01-18 | Polaroid Corporation | Photographic products with photosensitive layers of same spectral sensitivity and different speed |
| US3960558A (en) * | 1974-04-29 | 1976-06-01 | Polaroid Corporation | Dye free, spectrally sensitive silver halide layers in diffusion transfer films |
| JPS523653A (en) * | 1975-06-27 | 1977-01-12 | Fuji Photo Film Co Ltd | Process for producing fine polymer particles |
| US4133687A (en) * | 1977-07-08 | 1979-01-09 | Eastman Kodak Company | Photographic elements having hydrophilic colloid layers containing compounds having activator precursors and hydrophobic developing agents uniformly loaded in latex polymer particles |
-
1979
- 1979-05-01 DE DE7979900514T patent/DE2965489D1/de not_active Expired
- 1979-05-01 JP JP54500794A patent/JPS5936253B2/ja not_active Expired
- 1979-05-01 WO PCT/US1979/000294 patent/WO1979001020A1/fr not_active Ceased
- 1979-12-04 EP EP19790900514 patent/EP0011645B1/fr not_active Expired
Also Published As
| Publication number | Publication date |
|---|---|
| DE2965489D1 (en) | 1983-07-07 |
| EP0011645A4 (fr) | 1980-09-29 |
| WO1979001020A1 (fr) | 1979-11-29 |
| EP0011645A1 (fr) | 1980-06-11 |
| JPS55500266A (fr) | 1980-05-01 |
| JPS5936253B2 (ja) | 1984-09-03 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CA1225796A (fr) | Mordants polymeres | |
| US5176972A (en) | Imaging medium with low refractive index layer | |
| EP0742800B1 (fr) | Compositions aqueuses acides a deux phases pour produits de diffusion-transfert | |
| EP0115054B1 (fr) | Polymères capables de subir l'élimination bêta comme couches de contrôle de diffusion dans des produits photographiques | |
| JPS5931696B2 (ja) | カラ−拡散転写法用写真材料 | |
| US3785815A (en) | Spacer or timing layer in color diffusion transfer film | |
| US4131469A (en) | Photographic element with polymeric ammonium mordant | |
| EP0683430B1 (fr) | Compositions de traitement photographiques incluant un agent éprassissant hydrophobiquement modifié | |
| EP0011645B1 (fr) | Elements photosensibles pour la mise en oeuvre dans une unite de film de transfert par diffusion | |
| US3833369A (en) | Color diffusion transfer films and processes with polymer encapsulated reflecting agents | |
| US4347301A (en) | Novel diffusion transfer film units | |
| EP0317920B1 (fr) | Produits photographiques contenant des mordants copolymèriques | |
| EP0672268B1 (fr) | ELEMENT RECEPTEUR D'IMAGES POUR PRODUITS DE FILMS PHOTOGRAPHIQUES à DIFFUSION-TRANSFERT | |
| US4190447A (en) | Cover sheets for integral imaging receiver elements | |
| CA1148008A (fr) | Elements photosensibles a couche d'halogenure d'argent renfermant des particules inertes et une matiere colorante captrice d'images | |
| US4374919A (en) | Diffusion transfer color photographic element with U.V. absorbing agent adjacent protective layer | |
| EP0139963B1 (fr) | Unité integrale du film negativ- positif pour la transmission par diffusion avec un élément récepteur d'images comprenant une couche unitaire de réception d'image et de décolorisation | |
| US3756816A (en) | Orming polymer dispersion photographic film units including a layer comprising an aqueous filmf | |
| US3856522A (en) | Spacer layer for dye diffusion transfer film | |
| JPS5931687B2 (ja) | 写真記録材料 | |
| EP0066341B1 (fr) | Elément photosensible et procédé photographique | |
| CA1115109A (fr) | Feuille de surface contenant une couche hydrophile permeable aux alcalis entre une couche a effet temporisateur et un element recepteur d'images | |
| JPS6149658B2 (fr) | ||
| US5607812A (en) | Color diffusion transfer film unit | |
| EP0127787A2 (fr) | Produits photographiques comprenant des couches de contrôle de la diffusion hydrolysables |
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 |
Designated state(s): DE FR GB |
|
| 17P | Request for examination filed | ||
| GRAA | (expected) grant |
Free format text: ORIGINAL CODE: 0009210 |
|
| AK | Designated contracting states |
Designated state(s): DE FR GB |
|
| ET | Fr: translation filed | ||
| REF | Corresponds to: |
Ref document number: 2965489 Country of ref document: DE Date of ref document: 19830707 |
|
| 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: 19910410 Year of fee payment: 13 |
|
| PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: GB Payment date: 19910412 Year of fee payment: 13 |
|
| PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: DE Payment date: 19910426 Year of fee payment: 13 |
|
| PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: GB Effective date: 19920501 |
|
| GBPC | Gb: european patent ceased through non-payment of renewal fee |
Effective date: 19920501 |
|
| PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: FR Effective date: 19930129 |
|
| PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: DE Effective date: 19930202 |
|
| REG | Reference to a national code |
Ref country code: FR Ref legal event code: ST |