US3733198A - Direct positive processes utilizing silver halide internal latent image emulsions containing high concentration of heterocyclic thione antifoggants - Google Patents
Direct positive processes utilizing silver halide internal latent image emulsions containing high concentration of heterocyclic thione antifoggants Download PDFInfo
- Publication number
- US3733198A US3733198A US00111706A US3733198DA US3733198A US 3733198 A US3733198 A US 3733198A US 00111706 A US00111706 A US 00111706A US 3733198D A US3733198D A US 3733198DA US 3733198 A US3733198 A US 3733198A
- Authority
- US
- United States
- Prior art keywords
- silver halide
- light
- image
- direct positive
- emulsion
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Lifetime
Links
- 239000000839 emulsion Substances 0.000 title abstract description 112
- 229910052709 silver Inorganic materials 0.000 title abstract description 85
- 239000004332 silver Substances 0.000 title abstract description 85
- -1 silver halide Chemical class 0.000 title abstract description 80
- 238000000034 method Methods 0.000 title abstract description 57
- 241001061127 Thione Species 0.000 title abstract description 15
- 125000000623 heterocyclic group Chemical group 0.000 title description 12
- 230000008569 process Effects 0.000 title description 9
- 239000000463 material Substances 0.000 abstract description 68
- 150000001875 compounds Chemical class 0.000 abstract description 47
- 230000015572 biosynthetic process Effects 0.000 abstract description 7
- 230000002401 inhibitory effect Effects 0.000 description 29
- 239000000243 solution Substances 0.000 description 17
- 238000011161 development Methods 0.000 description 14
- 230000018109 developmental process Effects 0.000 description 14
- 239000007788 liquid Substances 0.000 description 13
- ADZWSOLPGZMUMY-UHFFFAOYSA-M silver bromide Chemical compound [Ag]Br ADZWSOLPGZMUMY-UHFFFAOYSA-M 0.000 description 13
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 12
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 10
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 description 10
- IOLCXVTUBQKXJR-UHFFFAOYSA-M potassium bromide Chemical compound [K+].[Br-] IOLCXVTUBQKXJR-UHFFFAOYSA-M 0.000 description 10
- 230000035945 sensitivity Effects 0.000 description 10
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 9
- 108010010803 Gelatin Proteins 0.000 description 8
- 239000008273 gelatin Substances 0.000 description 8
- 229920000159 gelatin Polymers 0.000 description 8
- 235000019322 gelatine Nutrition 0.000 description 8
- 235000011852 gelatine desserts Nutrition 0.000 description 8
- 238000006243 chemical reaction Methods 0.000 description 7
- 239000003795 chemical substances by application Substances 0.000 description 7
- 239000004615 ingredient Substances 0.000 description 7
- 239000000203 mixture Substances 0.000 description 7
- GEHJYWRUCIMESM-UHFFFAOYSA-L sodium sulfite Chemical compound [Na+].[Na+].[O-]S([O-])=O GEHJYWRUCIMESM-UHFFFAOYSA-L 0.000 description 7
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 6
- 229910021607 Silver chloride Inorganic materials 0.000 description 6
- SJOOOZPMQAWAOP-UHFFFAOYSA-N [Ag].BrCl Chemical compound [Ag].BrCl SJOOOZPMQAWAOP-UHFFFAOYSA-N 0.000 description 6
- 125000003118 aryl group Chemical group 0.000 description 6
- 235000012149 noodles Nutrition 0.000 description 6
- 238000002360 preparation method Methods 0.000 description 6
- HKZLPVFGJNLROG-UHFFFAOYSA-M silver monochloride Chemical compound [Cl-].[Ag+] HKZLPVFGJNLROG-UHFFFAOYSA-M 0.000 description 6
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 description 6
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 5
- 238000004519 manufacturing process Methods 0.000 description 5
- 229920001059 synthetic polymer Polymers 0.000 description 5
- JKFYKCYQEWQPTM-UHFFFAOYSA-N 2-azaniumyl-2-(4-fluorophenyl)acetate Chemical compound OC(=O)C(N)C1=CC=C(F)C=C1 JKFYKCYQEWQPTM-UHFFFAOYSA-N 0.000 description 4
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 description 4
- 229910021612 Silver iodide Inorganic materials 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 230000002349 favourable effect Effects 0.000 description 4
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 4
- 229920000120 polyethyl acrylate Polymers 0.000 description 4
- 229920000036 polyvinylpyrrolidone Polymers 0.000 description 4
- 239000001267 polyvinylpyrrolidone Substances 0.000 description 4
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 description 4
- 229940045105 silver iodide Drugs 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- JCCAUOFIVYLQMS-UHFFFAOYSA-N 1-(2-methoxyphenyl)-2h-tetrazole-5-thione Chemical compound COC1=CC=CC=C1N1C(=S)N=NN1 JCCAUOFIVYLQMS-UHFFFAOYSA-N 0.000 description 3
- 239000012190 activator Substances 0.000 description 3
- 230000002180 anti-stress Effects 0.000 description 3
- QVQLCTNNEUAWMS-UHFFFAOYSA-N barium oxide Chemical compound [Ba]=O QVQLCTNNEUAWMS-UHFFFAOYSA-N 0.000 description 3
- 229910001864 baryta Inorganic materials 0.000 description 3
- 230000008901 benefit Effects 0.000 description 3
- 239000011230 binding agent Substances 0.000 description 3
- 239000011248 coating agent Substances 0.000 description 3
- 238000000576 coating method Methods 0.000 description 3
- 239000006185 dispersion Substances 0.000 description 3
- 239000000499 gel Substances 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 239000004816 latex Substances 0.000 description 3
- 229920000126 latex Polymers 0.000 description 3
- 229920001515 polyalkylene glycol Polymers 0.000 description 3
- NLKNQRATVPKPDG-UHFFFAOYSA-M potassium iodide Chemical compound [K+].[I-] NLKNQRATVPKPDG-UHFFFAOYSA-M 0.000 description 3
- 229910001961 silver nitrate Inorganic materials 0.000 description 3
- 235000010265 sodium sulphite Nutrition 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- SHRKLWFRBJXQDI-UHFFFAOYSA-N 1-(2-phenylphenyl)-2h-tetrazole-5-thione Chemical compound SC1=NN=NN1C1=CC=CC=C1C1=CC=CC=C1 SHRKLWFRBJXQDI-UHFFFAOYSA-N 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- 239000004133 Sodium thiosulphate Substances 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 238000004061 bleaching Methods 0.000 description 2
- PAFZNILMFXTMIY-UHFFFAOYSA-N cyclohexylamine Chemical compound NC1CCCCC1 PAFZNILMFXTMIY-UHFFFAOYSA-N 0.000 description 2
- 238000009792 diffusion process Methods 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 230000003287 optical effect Effects 0.000 description 2
- 229920001223 polyethylene glycol Polymers 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 229910000029 sodium carbonate Inorganic materials 0.000 description 2
- AKHNMLFCWUSKQB-UHFFFAOYSA-L sodium thiosulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=S AKHNMLFCWUSKQB-UHFFFAOYSA-L 0.000 description 2
- 235000019345 sodium thiosulphate Nutrition 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- CYXJEHCKVOQFOV-UHFFFAOYSA-N (4-amino-2-methylphenyl) hydrogen sulfate Chemical compound CC1=CC(N)=CC=C1OS(O)(=O)=O CYXJEHCKVOQFOV-UHFFFAOYSA-N 0.000 description 1
- POZVYOVYIZCFLB-UHFFFAOYSA-N 1-(2h-benzotriazol-5-yl)-3-phenylurea Chemical compound C1=CC2=NNN=C2C=C1NC(=O)NC1=CC=CC=C1 POZVYOVYIZCFLB-UHFFFAOYSA-N 0.000 description 1
- JPMTVROFUSMNMU-UHFFFAOYSA-N 1-anthracen-9-yl-2H-tetrazole-5-thione Chemical compound C1=CC=CC2=CC3=CC=CC=C3C(=C12)N1N=NNC1=S JPMTVROFUSMNMU-UHFFFAOYSA-N 0.000 description 1
- XOHZHMUQBFJTNH-UHFFFAOYSA-N 1-methyl-2h-tetrazole-5-thione Chemical compound CN1N=NN=C1S XOHZHMUQBFJTNH-UHFFFAOYSA-N 0.000 description 1
- GXBDORPZPAFTBG-UHFFFAOYSA-N 1-phenylimidazolidine-2-thione Chemical compound S=C1NCCN1C1=CC=CC=C1 GXBDORPZPAFTBG-UHFFFAOYSA-N 0.000 description 1
- XNWFRZJHXBZDAG-UHFFFAOYSA-N 2-METHOXYETHANOL Chemical compound COCCO XNWFRZJHXBZDAG-UHFFFAOYSA-N 0.000 description 1
- QZKRHPLGUJDVAR-UHFFFAOYSA-K EDTA trisodium salt Chemical compound [Na+].[Na+].[Na+].OC(=O)CN(CC([O-])=O)CCN(CC([O-])=O)CC([O-])=O QZKRHPLGUJDVAR-UHFFFAOYSA-K 0.000 description 1
- PDQAZBWRQCGBEV-UHFFFAOYSA-N Ethylenethiourea Chemical compound S=C1NCCN1 PDQAZBWRQCGBEV-UHFFFAOYSA-N 0.000 description 1
- WRUZLCLJULHLEY-UHFFFAOYSA-N N-(p-hydroxyphenyl)glycine Chemical compound OC(=O)CNC1=CC=C(O)C=C1 WRUZLCLJULHLEY-UHFFFAOYSA-N 0.000 description 1
- 239000000020 Nitrocellulose Substances 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- FJWGYAHXMCUOOM-QHOUIDNNSA-N [(2s,3r,4s,5r,6r)-2-[(2r,3r,4s,5r,6s)-4,5-dinitrooxy-2-(nitrooxymethyl)-6-[(2r,3r,4s,5r,6s)-4,5,6-trinitrooxy-2-(nitrooxymethyl)oxan-3-yl]oxyoxan-3-yl]oxy-3,5-dinitrooxy-6-(nitrooxymethyl)oxan-4-yl] nitrate Chemical compound O([C@@H]1O[C@@H]([C@H]([C@H](O[N+]([O-])=O)[C@H]1O[N+]([O-])=O)O[C@H]1[C@@H]([C@@H](O[N+]([O-])=O)[C@H](O[N+]([O-])=O)[C@@H](CO[N+]([O-])=O)O1)O[N+]([O-])=O)CO[N+](=O)[O-])[C@@H]1[C@@H](CO[N+]([O-])=O)O[C@@H](O[N+]([O-])=O)[C@H](O[N+]([O-])=O)[C@H]1O[N+]([O-])=O FJWGYAHXMCUOOM-QHOUIDNNSA-N 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 239000000084 colloidal system Substances 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 230000001808 coupling effect Effects 0.000 description 1
- 230000001419 dependent effect Effects 0.000 description 1
- 235000014113 dietary fatty acids Nutrition 0.000 description 1
- 239000000194 fatty acid Substances 0.000 description 1
- 229930195729 fatty acid Natural products 0.000 description 1
- 150000004665 fatty acids Chemical class 0.000 description 1
- 239000011888 foil Substances 0.000 description 1
- XMBWDFGMSWQBCA-UHFFFAOYSA-N hydrogen iodide Chemical compound I XMBWDFGMSWQBCA-UHFFFAOYSA-N 0.000 description 1
- 230000002209 hydrophobic effect Effects 0.000 description 1
- 238000010348 incorporation Methods 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 229920001220 nitrocellulos Polymers 0.000 description 1
- SYXUBXTYGFJFEH-UHFFFAOYSA-N oat triterpenoid saponin Chemical class CNC1=CC=CC=C1C(=O)OC1C(C=O)(C)CC2C3(C(O3)CC3C4(CCC5C(C)(CO)C(OC6C(C(O)C(OC7C(C(O)C(O)C(CO)O7)O)CO6)OC6C(C(O)C(O)C(CO)O6)O)CCC53C)C)C4(C)CC(O)C2(C)C1 SYXUBXTYGFJFEH-UHFFFAOYSA-N 0.000 description 1
- CMCWWLVWPDLCRM-UHFFFAOYSA-N phenidone Chemical compound N1C(=O)CCN1C1=CC=CC=C1 CMCWWLVWPDLCRM-UHFFFAOYSA-N 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 108090000623 proteins and genes Proteins 0.000 description 1
- 102000004169 proteins and genes Human genes 0.000 description 1
- 230000005070 ripening Effects 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- ZUNKMNLKJXRCDM-UHFFFAOYSA-N silver bromoiodide Chemical compound [Ag].IBr ZUNKMNLKJXRCDM-UHFFFAOYSA-N 0.000 description 1
- 238000002791 soaking Methods 0.000 description 1
- 230000003595 spectral effect Effects 0.000 description 1
- 230000007480 spreading Effects 0.000 description 1
- 238000003892 spreading Methods 0.000 description 1
- 229910021653 sulphate ion Inorganic materials 0.000 description 1
- 150000003567 thiocyanates Chemical class 0.000 description 1
- DHCDFWKWKRSZHF-UHFFFAOYSA-L thiosulfate(2-) Chemical compound [O-]S([S-])(=O)=O DHCDFWKWKRSZHF-UHFFFAOYSA-L 0.000 description 1
- 150000004764 thiosulfuric acid derivatives Chemical class 0.000 description 1
- 238000009736 wetting Methods 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
- 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
- G03C7/3022—Materials with specific emulsion characteristics, e.g. thickness of the layers, silver content, shape of AgX grains
-
- 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
- G03C1/485—Direct positive emulsions
- G03C1/48538—Direct positive emulsions non-prefogged, i.e. fogged after imagewise exposure
-
- 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
- G03C1/485—Direct positive emulsions
- G03C1/48592—Positive image obtained by various effects other than photohole bleaching or internal image desensitisation, e.g. Sabatier, Clayden effect
Definitions
- a so-called internal image emulsion treating the exposed material with a surface developer and overall exposing the material during this treatment to actinic light of low intensity, an image having minimum density and contrast is obtained by incorporating within the emulsion layer a fog-inhibiting compound of the class of the heterocyclic thione compounds in an amount of at least about 0.1 mole per 100 mole of silver halide and which is substantially larger than normal fog-inhibiting amounts.
- the concept can be applied to the formation of black and white images as well as to colored images.
- the present invention relates to a novel method of producing photographic direct positive images and more particularly to a simple method according to which direct positive images of good quality are produced rapidly.
- German patent specification 749,864 a method is described of producing a photographic direct positive image that comprises the steps of exposing a silver halide emulsion layer to an object or image, predeveloping the thus exposed layer for a considerably long time, subjecting it to an overall exposure with actinic light of low intensity and finally developing the said emulsion layer to cause a direct positive image to be formed.
- the said predeveloping occurs preferably in a fine grain developer or flat-working developer and the said developing in an energetic developer.
- the silver halide emulsion layer for use in the process of said German patent specification must be such that its negative image sensitometric curve shows a maximum density that does not exceed the value 0.5.
- a method is described of producing a photographic direct positive image that comprises the steps of exposing to an object or image a light-sensitive silver halide emulsion layer, treating said emulsion layer to render it capable of forming a surface latent image and then subjecting it to a uniform exposure of sutficient intensity and time to cause a direct positive image to develop by treating it in a developer that will develop the surface latent image but will not or only slightly develop the first formed internal latent image.
- the silver halide emulsion layer used must be of the type in which the latent image isform'ed mostly or entirely inside the grains.
- Image-Wise exposing a light-sensitive material which comprises a layer of a silver halide emulsion of the type that forms a latent image predominantly in the inner part of the silver halide grains,
- a fog-inhibiting compound that inhibits fogging during the development stage and that belongs to the class of the heterocyclic thione compounds has been incorporated within said emulsion layer in an amount of at least about 0.1 mole per moles of said silver halide and which is substantially larger than normal fog-inhibiting amounts.
- the material is generally fixed, e.g. in a usual fixing solution such as a thiosulphate solution, and washed, whereupon the material may be dried or glazed.
- the present invention provides a method of producing direct positive images of good quality in a rapid and simple way. This method is particularly suitable for producing continuous tone direct positive images but it is also appropriate for reproducing line originals.
- the light-sensitive material of use according to the present invention generally comprises a support, for in stance a paper support or a hydrophobic film support that is either transparent or not, to which the light-sensitive silver halide emulsion layer is applied, if need be by means of an appropriate subbing layer.
- the silver halide emulsion used in carrying out the method of this invention is of the type in which the latent image is formed predominantly in the inner part of the silver halide grains. This means an emulsion only few or none of which exposed grains are developable to silver by a developing solution which cannot act as a developer for latent image inside the grains, i.e. a so called surface developer, such as the following developing solution:
- a developing solution which acts as a developer for latent image inside the grains, i.e. a so-called internal developer such as the following developing solution:
- any reference in the description and in the claims to a silver halide emulsion of the type that forms a latent image predominantly in the inner part of the silver halide grains is limited to a silver halide emulsion, a test layer of which, upon exposure to a light intensity scale for a fixed time between A and 1 second and development for 3 minutes at 20 C. in the above internal developer, exhibits a maximum density at least 3 times and preferably at least times, the maximum density obtained when an identical test layer of the said silver halide emulsion is equally ex posed and then developed for 4 minutes at 20 C. in the above surface developer.
- Said preference for a maximum density of at least 5 times as large particularly applies to the case the method of the invention is applied to the production of black and white direct positive images.
- the method of the invention is applied to the production of color images, wherein the formed silver image is eliminated as will be explained detailedly further in the description, 3 times said maximum density will suffice in order to obtain good results.
- the silver halide emulsions used according to the invention are generally not or only slightly chemically ripened silver halide emulsions, since the ability of forming the surface latent image increases with the degree of chemical ripening.
- Silver chlorobromide emulsions comprising at least 20 mole percent of silver bromide and pure silver bromide emulsions have proved to be specially suitable for the purpose of the invention. These emulsions may contain up to 5 mole percent of silver iodide relative to the total amount of silver halide. Washed as well as unwashed silver halide emulsions may be used.
- the silver halide emulsions for use in the present process are generally gelatino silver halide emulsions.
- the gelatin may at least partly be replaced, e.g., by another protein, a hydrophilic not proteinaceous colloid, e.g. a polyvinylpyrrolidone or a synthetic polymer applied from an aqueous dispersion, i.e., a latex, e.g. a polyethyl acrylate latex.
- a latex e.g. a polyethyl acrylate latex
- the presence of such other binders often has also a favourable photographic effect on the formation of the direct positive image. For instance, the addition of polyvinylpyrrolidone and of said polyethyl acrylate latex in most cases increases the maximum density of the direct positive image.
- the light-sensitive silver halide emulsions used according to the invention may be prepared according to any technique known in the art.
- a method according to which emulsions are prepared, which have proved to be particularly suitable for the purpose of the invention is the so-called conversion method.
- a more soluble silver halide is converted into a less soluble silver halide e.g. a silver chloride emulsion is converted in the presence of water-soluble bromide and occasionally iodide, the amounts of which are adapted in view of the final composition aimed at, into a silver chlorobromide or a silver bromide emulsion which may occasionally comprise small amounts of silver iodide.
- This conversion is carried out preferably very slowly by several consecutive steps.
- a fog-inhibiting compound is incorporated that inhibits fogging during the development stage and that belongs to the class of the heterocyclic thione compounds.
- This compound is incorporated within said emulsion layer in an amount of at least about 0.1 mole per moles of silver halide and which is substantially larger than normal fog-inhibiting amounts.
- the presence of this large amount of fog-inhibiting compound causes the favorable elfect of the invention, 'viz. the production of a direct positive image showing a low minimum density and an improved contrast.
- the fog-inhibiting compound is incorporated Within the silver halide emulsion layer by adding it to the liquid silver halide emulsion, generally just before coating.
- the fog-inhibiting compound may also be incorporated within the emulsion layer by diffusion from or through another layer, which is in water-permeable relationship with the emulsion layer. This diffusion occurs automatically and immediately when the silver halide emulsion is applied to a water-permeable layer containing the fog-inhibiting compound or when an aqueous coating liquid containing said compound is applied to the silver halide emulsion layer or to a waterpermeable layer present on top of the emulsion layer.
- the fog-inhibiting compound has to be present in the silver halide emulsion layer before the aqueous energetic surface developer is applied to the image-wise exposed light-sensitive material.
- the foginhibiting compound is applied in an amount which is substantially larger than normal fog-inhibiting amounts, i.e. in an amount, which is normally not incorporated within a silver halide emulsion layer because it would too strongly desensitize the light-sensitive material.
- normal fog-inhibiting amounts i.e. in an amount, which is normally not incorporated within a silver halide emulsion layer because it would too strongly desensitize the light-sensitive material.
- Suitable fog-inhibiting compounds belonging to the class of the heterocyclic thione compounds are:
- any reference in the description and in the claims to fog-inhibiting compounds of the class of the heterocyclic thione compounds is intended to refer also to the tautomeric structures of said com:- pounds and to salts of said-compounds or occasionally of said tautomeric structures. Mixtures of two or more foginhibiting compounds may also be employed.
- a first step for the preparation of the direct-positive image the light-sensitive material is image-wise exposed to the original to be reproduced.
- This exposure can be either a high-intensity exposure such as flash exposure or a normal-intensity exposure such as day-light exposure as well as low-intensity exposure such as an exposure by means of a printer or an exposure of still lower intensity, the exposure-time being dependent on the sensitivity of the light-sensitive material for the direct positive image formation which sensitivity according to the present invention may be a camera speed as well as a lower sensitivity.
- the image-wise exposed light-sensitive material is treated with an aqueous energetic surface developing liquid.
- This treatment may be carried out according to any technique known in the art, e.g. by soaking or by wetting only one side of the light-sensitive material, e.g. by means of a lick roller, by spreading a paste, e.g. contained in a pod or by spraymg.
- the developer of use in the process of the invention must be a surface developer i.e. a developer that contains no or at least no effective amount of solvents for silver halide.
- solvents for silver halide there are meant particularly strong solvents for silver halide such as water-soluble thiocyanates, thiosulphates, ammonia, etc.
- compounds that may be considered to be but very weak solvents for silver halide, such as sodium sulphite in case the silver halide is sliver bromide, silver chlorobromide, or silver bromoiodide may be present in the developer.
- the developer has to be an energetic developer.
- the high energy required can be realized by taking, e.g. one or more of the following measures:
- developing activators such as cyclohexylamine, polyethylene glycols and derivatives in the developer.
- suitable developing substances are among others the combination of l-phenyl-S-pyrazolidinone with hydroquinone and the combination of monomethyl-paminophenol sulphate with hydroquinone. In general there may be said that the more energetic the developer is the better the result obtained will be.
- the developing agents may also be incorporated partially or even completely into the light-sensitive material. This incorporation may be accomplished during the preparation stage of the material or later on by means of a processing liquid, with which the light-sensitive material is wetted prior to the development of the direct positive image. In doing so the energetic surface developer can be reduced to a mere alkaline liquid substantially free from developing agents.
- a processing liquid with which the light-sensitive material is wetted prior to the development of the direct positive image.
- the energetic surface developer can be reduced to a mere alkaline liquid substantially free from developing agents.
- Such an alkaline aqueous liquid often called activator, offers the advantage of having a longer activity, i.e. of being less rapidly exhausted.
- the developer (occasionally activator) may be sup plied in an amount which suflices for the treatment of exactly one foil of light-sensitive material.
- a bath of this type offers the advantage that ageing and contamination of the bath composition are avoided.
- the image-wise exposed light-sensitive layer is present in the developer or is moistened therewith in some other way the said light-sensitive material is overall and generally uniformly exposed to actinic light of low intensity, i.e. of an intensity, which is lower than a normal daylight intensity.
- This exposure may begin simultaneously with the treatment of the light-sensitive material with developer but occurs favourably a little later for instance from 5 to 30 seconds later.
- the duration of the secondary or overall exposure is not very critical and may amount from 10 seconds to many minutes according to the nature of the light-sensitive material, the composition and the temperature of the developer, the intensity of the light-source employed, etc. In many cases the overall exposure lasts till the direct positive image is completely developed.
- the density of the direct positive image can be made more intense or reduced locally during the second or overall exposure by the well known technique of burning in and dodging. In general the total development of the direct positive image does not take much time and in most cases may be carried out in from 1 to 5 minutes.
- the uniformity of the said overall exposure to actinic light of low intensity is mostly achieved by interposing between the light-source and the light-sensitive material to be exposed a light-diffusing member that transmits at least part of the light rays of the spectral region for which the light-sensitive material is sensitive.
- the required low intensity of the light rays, which reach the light-sensitive material can be obtained by adapting the light-source and/ or the light-diffusing member.
- the direct positive images obtained according to the present invention are of good quality in the high-light areas as well as in the dark areas.
- the maxi mum or minimum density of the direct positive image can still be improved and the characteristics of the lightsensitive material can be altered by using all kinds of ingredients which are geneally known in the art of emulsion preparation and some of which will be set out specifically hereinafter.
- ingredients are preferably incorporated into the light-sensitive material itself, in effective contact with the silver halide emulsion layer and favourably in the latter layer itself.
- Many of these ingredients may be incorporated into the energetic surface developer with the same favourable result. Combinations of two or more of said ingredients, of course, may also be used.
- binders for at least partially replacing gelatin as a binder for the silver halide grains may be mentioned some binders for at least partially replacing gelatin as a binder for the silver halide grains and referred to already above in the description, futher optical sensitizers which increase the maximum density of the direct positive image, and moistening agents such as polyalkylene glycols, e.g. polyethylene glycols, sulphonated fatty acids, saponine and the like. Still further ingredients are mentioned later on in the description.
- the process according to the present invention is not restricted to black and white photography; it may also be applied for the preparation of direct positive colour images by carrying out the development in an energic colour developer in the presence of a colour coupler and by bleaching away the silver developed.
- the light-sensitive material may be a multilayer colour material each layer of which absorbs a particular part of the spectrum and for which layers appropriate colour couplers are provided. Besides their developing or coupling action may colour developing compounds and colour couplers exert an advantageous effect on the mechanism of the production itself of the direct positive image in that they contribute to a higher maximum and/or a lower minimum density.
- a negative image is formed in the silver halide emulsion layer in addition to the direct positive image, just as is the case with the Sabattier effect.
- the positive and negative image overlap with each other, whereas according to our invention there is a clear separation between the direct positive image and the negative image that forms in a lower sensitivity range.
- This separation is clearest when the image-wise exposure is a high-intensity exposure, e.g. a flash exposure, and is less clear according as the intensity of the image-wise exposure is lower. Nevertheless, excellent results still can be obtained with a normal day-light exposure and even with an exposure of still lower intensity, e.g. an exposure by means of a printer.
- a negative image in the low sensitivity range can also be obtained by developing this material after image-wise exposure in a surface developer without subjecting it to a second or overall exposure.
- EXAMPLE 1 A gelatino silver bromide emulsion that mainly forms internal latent image and little external latent image is prepared through conversion of a silver chloride emulsion by very slowly adding to said emulsion whilst stirring a 35% aqueous potassium bromide solution in an amount that is 70% higher than the amount, which is theoretically needed for converting all the silver chloride. Then the emulsion is kept for 1 hour at 60 C. After the emulsion has been cooled and allowed to gel for 6 hours the emulsion is noodled. The noodles are washed for 1 hour with water (10 litres of water per minute). By heating the washed noodles a liquid silver bromide emulsion is obtained containing 50 g. of gelatin and 0.4 mole of silver bromide per kg.
- the light-sensitive emulsion is coated practically immediately after the addition of the said solution in ethanol on a baryta coated paper support of 130 g./sq. m in such a way that an amount of silver halide equivalent to 4 g. of silver nitrate is present per sq. m of light-sensitive material.
- the emulsion layer is overcoated with a conventional hardened gelatin antistress layer.
- the light-sensitive silver halide material obtained is image-wise exposed for sec. through a step-wedge by means of a flash exposure of 130 lux sec.
- a first strip of the exposed light-sensitive material is developed for 4 min. at 20 C. in a surface developer of the following composition:
- the strip is then fixed, rinsed and dried in the conventional way. A very faint negative image of the original to be reproduced is obtained.
- a second strip of the above exposed light-sensitive material is treated in the same way as the first strip with the difference, however, that 30 sec. after the development has started the light-sensitive material is overall exposed for the remaining time of the development through a gray filter having a density of 1.5 by means of a 15 watt lamp placed at a distance of 75 cm. from the light-sensitive material.
- a direct positive image of the original is obtained having a good maximum density and a very low minimum density and forming in a higher sensitivity range than that wherein the negative image of the first strip is formed.
- the direct positive image obtained according to the method of the invention as described in this example shows a much lower minimum density and a maximum density that has not lowered to the same extent as the said minimum density but to a much smaller degree.
- Example 1 is repeated with the difference, however, that in the preparation of the silver halide emulsion the amount of 1-(o-methoxyphenyl)-2-tetrazoline-S-thione is replaced by 20 ccs of a 2.5% solution in methyl glycol of 5- 3-phenylureido 1 H-benzotriazole.
- EXAMPLE 3 A gelatino silver bromide emulsion that mainly forms internal latent image and little external latent image is prepared through conversion of a silver chloro-bromide emulsion (10 mole percent of bromide) by very slowly adding to said emulsion whilst stirring a 35% aqueous potassium bromide solution in an amount that is higher than the amount which is theoretically needed for converting all the silver chloride. The emulsion is then kept for 1 h. at 60 C.
- the emulsion After the emulsion has been chilled and allowed to gel for 6 hours the emulsion is noodled. The noodles are washed for 1 hour with water (10 litres of water per minute). By heating the washed noodles a liquid silver bromide emulsion is obtained containing 50 g. of gelatin and 0.4 mole of silver bromide per kg.
- an appropriate colour coupler for yellow is added in the common concentration whereupon l-(o-methoxyphenyl)-2-tetrazoline-5-thione is added from a 5% solution in ethanolzto a first part of the emulsion 5 ccs./kg, to a second part 10 ccs./kg. and to a third part 20 ccs./kg.
- each of these lightsensitive emulsions is coated on a baryta coated paper support of g./sq. m in such a way that an amount of silver halide equivalent to 4 g. of silver nitrate is present per sq. m of light-sensitive material.
- the emulsion layer of each of the materials is overcoated with a conventional hardened gelatin antistress layer.
- the three silver halide materials obtained are further treated in a completely identical way. Each material is image-wise exposed for sec. through a step-wedge by means of a flash exposure of 130 lux sec. Then, each material is developed for 3 min. at 26 C. in a developer of the following composition:
- Each light-sensitive material is first developed for 30 sec. in the dark and then for the remaining time while being overall exposed through a grey filter with a density of 2.1 by means of a 15 watt lamp placed at a distance of 70 cm. from the light-sensitive material.
- each material is treated in a stop bath, bleached, fixed and rinsed With water as is the case with conventional photographic colour material.
- a yellow positive image of the step-wedge is obtained in each of the three materials.
- the three images all have a high maximum density and a very low minimum density, which is the lower the more fog-inhibiting compound is present.
- the direct positive images obtained according to the method of the invention as described in this example show a much lower minimum density and a maximum density that has not lowered to the same extent as the said minimum density but to a much smaller degree.
- EXAMPLE 4 A gelatino silver bromide emulsion that forms a latent image predominantly in the inner part of the silver halide grains was prepared through conversion of a silver chloride emulsion by very slowly adding to said emulsion Whilst stirring a 35% aqueous potassium bromide solution in an amount that was 70% higher than the amount theoretically necessary for converting all the silver chloride. The emulsion was then kept for 1 hour at 60 C. .After the emulsion had been chilled and allowed to gel for 6 hours it was noodled. The noodles were washed for 1 hour with Water (10 litres of water per minute). By heating the Washed noodles a liquid silver bromide emulsion was obtained containing 50 g. of gelatin and 0.4 mole of silver bromide per kg.
- the silver halide emulsion was applied to a baryta-coated paper support provided with a thin layer of cellulose nitrate. It was applied in such a way that an amount of silver halide equivalent to 5.5 g. of silver nitrate was present per sq. m. of the lightsensitive material.
- the emulsion layer was provided with a conventional hardened gelatin antistress layer.
- the light-sensitive material was image-wise exposed for 1 second through a step-wedge having a wedge constant of 0.1 by means of a low intensity lamp. It was then 10 developed for 65 seconds at 30 C. in a developer having the following composition:
- a second direct positive image was prepared in an analogous manner with the difference, however, that 1- (o-methoxyphenyl)-2-tetrazoline-5-thione was omitted from the light-sensitive material and instead thereof was incorporated into the developer by adding 25 cos. of a 5% solution in ethanol per liter of developer. The amount of fog-inhibiting compound in the developer had been chosen in such a Way that the most favorable result was obtained.
- the direct positive image thus obtained shows a somewhat lower minimum density (0.24) indeed, but also shows a considerably lower maximum density (1.25) and a lower gradation.
- EXAMPLE 5 A series of direct positive images was prepared in an analogous manner as the first direct positive image described in Example 4. However, instead of adding 20 cos. of a 5% solution of 1-(o-methoxyphenyl)-2-tetrazoline-5-thione in ethanol per kg. of the liquid silver bromide emulsion, the fog-inhibiting compounds listed in the table hereinafter were added to the liquid emulsion in the given amounts. The following results were obtained:
- a method of producing a photographic direct positive image that comprises the steps of image-wise exposing a light-sensitive material, which comprises a layer of a silver halide emulsion of the type that forms a latent image predominantly in the inner part of the silver halide grains, treating the light-sensitive material thus exposed with an aqueous energetic surface developing liquid, and overall exposing the light-sensitive material during the treatment stage to actinic light having an intensity, which is lower than a normal daylight intensity, whereby a direct positive image is developed in said emulsion layer,
- the improvement which comprises incorporating within said emulsion layer a fog-inhibiting compound inhibiting fogging during the development of said direct positive image, wherein the fog-inhibiting compound belongs to the class of the heterocyclic thione compounds and is present in said emulsion layer in an amount of at least about 0.1 mole per 100 moles of said silver halide and which is substantially larger than normal fog-inhibiting amounts.
- the foginhibiting compound is a five-membered heterocyclic thione compound carrying an aryl substituent or a fusedon aromatic group.
- a method according to claim 1, wherein the foginhibiting compound is l-(o-methoxy-phenyl)-2-tetrazoline-S-thione.
- the silver halide emulsion is a silver bromide emulsion or a silver chlorobromide emulsion comprising at least 20 mole percent of silver bromide and containing at most 5 mole percent of silver iodide relative to the total amount of silver halide.
- said moistening agent is a polyalkylene glycol.
- the silver halide emulsion layer includes polyvinylpyrrolidone.
- the silver halide emulsion layer includes an aqueous dispersion of a synthetic polymer.
- a light-sensitive material which comprises a layer of a silver halide emulsion of the type that forms a latent image predominantly in the inner part of the silver halide grains, treating the light-sensitive material thus exposed with an aqueous energetic color surface developing liquid in the presence of a color coupler,
- the improvement which comprises incorporating within said emulsion layer a fog-inhibiting compound inhibiting fogging during the development of said direct positive image, wherein the fog-inhibiting compound belongs to the class of the heterocyclic thione compounds and is present in said emulsion layer in an amount of at least about 0.1 mole per moles of said silver halide and which is substantially larger than normal fog-inhibiting amounts.
- a method according to claim 11, wherein the foginhibiting compound is a five-membered heterocyclic thione compound carrying an aryl substituent or a fusedon aromatic group.
- a method according to claim 11, wherein the foginhibiting compound is 1-(o-methoxy-phenyl)-2-tetrazoline-S-thione.
- the silver halide emulsion is a silver bromide emulsion or a silver chlorobromide emulsion comprising at least 20 mole percent of silver bromide and containing at most 5 mole percent of silver iodide relative to the total amount of silver halide.
- said moistening agent is a polyalkylene glycol.
- the silver halide emulsion layer includes polyvinylpyrrolidone.
- the silver halide emulsion layer includes an aqueous dispersion of a synthetic polymer.
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- Chemical & Material Sciences (AREA)
- Physics & Mathematics (AREA)
- General Physics & Mathematics (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Silver Salt Photography Or Processing Solution Therefor (AREA)
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
GB18335/65A GB1150553A (en) | 1965-04-30 | 1965-04-30 | A Method of Producing Photographic Images |
Publications (1)
Publication Number | Publication Date |
---|---|
US3733198A true US3733198A (en) | 1973-05-15 |
Family
ID=10110704
Family Applications (2)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
US00111706A Expired - Lifetime US3733198A (en) | 1965-04-30 | 1971-02-01 | Direct positive processes utilizing silver halide internal latent image emulsions containing high concentration of heterocyclic thione antifoggants |
US00111705A Expired - Lifetime US3708298A (en) | 1965-04-30 | 1971-02-01 | Method of producing direct positive images with photographic silver halide material containing compound releasing iodide ions |
Family Applications After (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
US00111705A Expired - Lifetime US3708298A (en) | 1965-04-30 | 1971-02-01 | Method of producing direct positive images with photographic silver halide material containing compound releasing iodide ions |
Country Status (8)
Country | Link |
---|---|
US (2) | US3733198A (enrdf_load_stackoverflow) |
AT (2) | AT283908B (enrdf_load_stackoverflow) |
BE (2) | BE680391A (enrdf_load_stackoverflow) |
CH (2) | CH477710A (enrdf_load_stackoverflow) |
DE (2) | DE1522374C2 (enrdf_load_stackoverflow) |
GB (1) | GB1150553A (enrdf_load_stackoverflow) |
NL (2) | NL6605890A (enrdf_load_stackoverflow) |
SE (1) | SE347362B (enrdf_load_stackoverflow) |
Cited By (8)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3993490A (en) * | 1974-02-12 | 1976-11-23 | E. I. Du Pont De Nemours And Company | Direct positive photographic elements containing developers |
US4081281A (en) * | 1972-02-18 | 1978-03-28 | Agfa-Gevaert N.V. | Developing low fogged, direct-positive silver halide emulsion with an energetic developer free from halide ions |
US4105450A (en) * | 1973-07-27 | 1978-08-08 | Fuji Photo Film Co., Ltd. | Spectrally sensitized positive light-sensitive o-quinone diazide containing composition |
US4262086A (en) * | 1978-06-22 | 1981-04-14 | F. F. D., Inc. | Photograph developing solution |
US4263396A (en) * | 1974-04-06 | 1981-04-21 | Agfa-Gevaert Ag | Direct-positive photographic material |
US4440851A (en) * | 1981-10-22 | 1984-04-03 | Konishiroku Photo Industry Co., Ltd. | Method for the formation of a direct positive image |
US4840879A (en) * | 1982-01-12 | 1989-06-20 | Konishiroku Photo Industry Co., Ltd. | Direct positive image-forming process |
US4954427A (en) * | 1986-06-12 | 1990-09-04 | Fuji Photo Film Co., Ltd. | Process for the formation of direct positive images |
Families Citing this family (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3622318A (en) * | 1970-03-20 | 1971-11-23 | Eastman Kodak Co | Photographic materials and processes |
US3761276A (en) * | 1971-03-10 | 1973-09-25 | Eastman Kodak Co | Photographic element containing monodispersed unfogged silver halide grains chemically sensitized internally and externally |
US4165986A (en) * | 1973-07-27 | 1979-08-28 | Polaroid Corporation | Substituted-halide silver halide emulsions and products containing same |
JPS63239439A (ja) * | 1986-11-25 | 1988-10-05 | Konica Corp | 直接ポジハロゲン化銀写真感光材料 |
JPH0690436B2 (ja) * | 1987-12-02 | 1994-11-14 | 富士写真フイルム株式会社 | 直接ポジ写真感光材料 |
JPH0690437B2 (ja) | 1987-12-02 | 1994-11-14 | 富士写真フイルム株式会社 | 直接ポジ写真感光材料 |
Family Cites Families (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DD4420A (enrdf_load_stackoverflow) * | ||||
BE388620A (enrdf_load_stackoverflow) * | 1926-05-21 | |||
BE489282A (enrdf_load_stackoverflow) * | 1948-05-27 |
-
1965
- 1965-04-30 GB GB18335/65A patent/GB1150553A/en not_active Expired
-
1966
- 1966-04-29 SE SE05905/66A patent/SE347362B/xx unknown
- 1966-04-30 DE DE1522374A patent/DE1522374C2/de not_active Expired
- 1966-04-30 DE DE1522373A patent/DE1522373C3/de not_active Expired
- 1966-05-02 CH CH631866A patent/CH477710A/de not_active IP Right Cessation
- 1966-05-02 CH CH631966A patent/CH475579A/de not_active IP Right Cessation
- 1966-05-02 AT AT412266A patent/AT283908B/de not_active IP Right Cessation
- 1966-05-02 NL NL6605890A patent/NL6605890A/xx unknown
- 1966-05-02 NL NL6605891A patent/NL6605891A/xx unknown
- 1966-05-02 AT AT412366A patent/AT283909B/de not_active IP Right Cessation
- 1966-05-03 BE BE680391D patent/BE680391A/xx unknown
- 1966-05-03 BE BE680392D patent/BE680392A/xx unknown
-
1971
- 1971-02-01 US US00111706A patent/US3733198A/en not_active Expired - Lifetime
- 1971-02-01 US US00111705A patent/US3708298A/en not_active Expired - Lifetime
Cited By (8)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4081281A (en) * | 1972-02-18 | 1978-03-28 | Agfa-Gevaert N.V. | Developing low fogged, direct-positive silver halide emulsion with an energetic developer free from halide ions |
US4105450A (en) * | 1973-07-27 | 1978-08-08 | Fuji Photo Film Co., Ltd. | Spectrally sensitized positive light-sensitive o-quinone diazide containing composition |
US3993490A (en) * | 1974-02-12 | 1976-11-23 | E. I. Du Pont De Nemours And Company | Direct positive photographic elements containing developers |
US4263396A (en) * | 1974-04-06 | 1981-04-21 | Agfa-Gevaert Ag | Direct-positive photographic material |
US4262086A (en) * | 1978-06-22 | 1981-04-14 | F. F. D., Inc. | Photograph developing solution |
US4440851A (en) * | 1981-10-22 | 1984-04-03 | Konishiroku Photo Industry Co., Ltd. | Method for the formation of a direct positive image |
US4840879A (en) * | 1982-01-12 | 1989-06-20 | Konishiroku Photo Industry Co., Ltd. | Direct positive image-forming process |
US4954427A (en) * | 1986-06-12 | 1990-09-04 | Fuji Photo Film Co., Ltd. | Process for the formation of direct positive images |
Also Published As
Publication number | Publication date |
---|---|
NL6605890A (enrdf_load_stackoverflow) | 1966-10-25 |
AT283908B (de) | 1970-08-25 |
DE1522373C3 (de) | 1981-07-23 |
SE347362B (enrdf_load_stackoverflow) | 1972-07-31 |
DE1522374C2 (de) | 1982-04-01 |
GB1150553A (en) | 1969-04-30 |
DE1522373B2 (de) | 1980-12-11 |
DE1522374A1 (de) | 1969-08-14 |
NL6605891A (enrdf_load_stackoverflow) | 1966-10-25 |
BE680392A (enrdf_load_stackoverflow) | 1966-11-03 |
DE1522373A1 (de) | 1969-07-17 |
CH475579A (de) | 1969-07-15 |
CH477710A (de) | 1969-08-31 |
AT283909B (de) | 1970-08-25 |
US3708298A (en) | 1973-01-02 |
BE680391A (enrdf_load_stackoverflow) | 1966-11-03 |
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