EP0044813B1 - Process for the formation of negative colour images according to the silver dye-bleaching process, and the silver dye-bleaching material used in this process - Google Patents
Process for the formation of negative colour images according to the silver dye-bleaching process, and the silver dye-bleaching material used in this process Download PDFInfo
- Publication number
- EP0044813B1 EP0044813B1 EP81810291A EP81810291A EP0044813B1 EP 0044813 B1 EP0044813 B1 EP 0044813B1 EP 81810291 A EP81810291 A EP 81810291A EP 81810291 A EP81810291 A EP 81810291A EP 0044813 B1 EP0044813 B1 EP 0044813B1
- Authority
- EP
- European Patent Office
- Prior art keywords
- silver
- layer
- core
- emulsion
- shell
- 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
- 229910052709 silver Inorganic materials 0.000 title claims description 110
- 239000004332 silver Substances 0.000 title claims description 105
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 title claims description 74
- 238000000034 method Methods 0.000 title claims description 43
- 238000004061 bleaching Methods 0.000 title claims description 36
- 230000008569 process Effects 0.000 title claims description 33
- 239000000463 material Substances 0.000 title claims description 30
- 230000015572 biosynthetic process Effects 0.000 title description 2
- 239000000839 emulsion Substances 0.000 claims description 66
- -1 silver halide Chemical class 0.000 claims description 56
- 239000000975 dye Substances 0.000 claims description 38
- ADZWSOLPGZMUMY-UHFFFAOYSA-M silver bromide Chemical compound [Ag]Br ADZWSOLPGZMUMY-UHFFFAOYSA-M 0.000 claims description 18
- 239000011258 core-shell material Substances 0.000 claims description 17
- 229910021607 Silver chloride Inorganic materials 0.000 claims description 15
- HKZLPVFGJNLROG-UHFFFAOYSA-M silver monochloride Chemical compound [Cl-].[Ag+] HKZLPVFGJNLROG-UHFFFAOYSA-M 0.000 claims description 15
- 239000002245 particle Substances 0.000 claims description 12
- 239000000126 substance Substances 0.000 claims description 12
- 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 claims description 9
- 229910021612 Silver iodide Inorganic materials 0.000 claims description 9
- XMBWDFGMSWQBCA-UHFFFAOYSA-N hydrogen iodide Chemical compound I XMBWDFGMSWQBCA-UHFFFAOYSA-N 0.000 claims description 9
- 229940045105 silver iodide Drugs 0.000 claims description 9
- 230000002269 spontaneous effect Effects 0.000 claims description 9
- 239000007844 bleaching agent Substances 0.000 claims description 8
- 238000004519 manufacturing process Methods 0.000 claims description 8
- 239000008139 complexing agent Substances 0.000 claims description 6
- 239000003112 inhibitor Substances 0.000 claims description 5
- 239000011230 binding agent Substances 0.000 claims description 4
- 239000000080 wetting agent Substances 0.000 claims description 4
- SJOOOZPMQAWAOP-UHFFFAOYSA-N [Ag].BrCl Chemical compound [Ag].BrCl SJOOOZPMQAWAOP-UHFFFAOYSA-N 0.000 claims description 2
- 239000006096 absorbing agent Substances 0.000 claims description 2
- 230000009471 action Effects 0.000 claims description 2
- 239000004611 light stabiliser Substances 0.000 claims description 2
- 239000004014 plasticizer Substances 0.000 claims description 2
- 239000002243 precursor Substances 0.000 claims description 2
- 230000000712 assembly Effects 0.000 claims 6
- 238000000429 assembly Methods 0.000 claims 6
- 230000003213 activating effect Effects 0.000 claims 1
- 229910052977 alkali metal sulfide Inorganic materials 0.000 claims 1
- UYJXRRSPUVSSMN-UHFFFAOYSA-P ammonium sulfide Chemical compound [NH4+].[NH4+].[S-2] UYJXRRSPUVSSMN-UHFFFAOYSA-P 0.000 claims 1
- 239000006081 fluorescent whitening agent Substances 0.000 claims 1
- 239000013078 crystal Substances 0.000 description 16
- 238000009792 diffusion process Methods 0.000 description 12
- 229920000159 gelatin Polymers 0.000 description 8
- 235000019322 gelatine Nutrition 0.000 description 8
- 239000000243 solution Substances 0.000 description 8
- 108010010803 Gelatin Proteins 0.000 description 7
- 239000008273 gelatin Substances 0.000 description 7
- 235000011852 gelatine desserts Nutrition 0.000 description 7
- JAAIPIWKKXCNOC-UHFFFAOYSA-N 1h-tetrazol-1-ium-5-thiolate Chemical class SC1=NN=NN1 JAAIPIWKKXCNOC-UHFFFAOYSA-N 0.000 description 6
- 230000035945 sensitivity Effects 0.000 description 6
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 description 5
- 239000000654 additive Substances 0.000 description 5
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 5
- 239000003054 catalyst Substances 0.000 description 4
- 239000000084 colloidal system Substances 0.000 description 4
- 150000001875 compounds Chemical class 0.000 description 4
- 150000004820 halides Chemical class 0.000 description 4
- XMBWDFGMSWQBCA-UHFFFAOYSA-M iodide Chemical compound [I-] XMBWDFGMSWQBCA-UHFFFAOYSA-M 0.000 description 4
- 229940006461 iodide ion Drugs 0.000 description 4
- 238000001556 precipitation Methods 0.000 description 4
- 125000000217 alkyl group Chemical group 0.000 description 3
- 125000003118 aryl group Chemical group 0.000 description 3
- 235000010290 biphenyl Nutrition 0.000 description 3
- 239000004305 biphenyl Substances 0.000 description 3
- 125000006267 biphenyl group Chemical group 0.000 description 3
- 239000006185 dispersion Substances 0.000 description 3
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 125000001624 naphthyl group Chemical group 0.000 description 3
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N phenylbenzene Natural products C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 3
- NLKNQRATVPKPDG-UHFFFAOYSA-M potassium iodide Chemical compound [K+].[I-] NLKNQRATVPKPDG-UHFFFAOYSA-M 0.000 description 3
- FVAUCKIRQBBSSJ-UHFFFAOYSA-M sodium iodide Chemical compound [Na+].[I-] FVAUCKIRQBBSSJ-UHFFFAOYSA-M 0.000 description 3
- YXIWHUQXZSMYRE-UHFFFAOYSA-N 1,3-benzothiazole-2-thiol Chemical compound C1=CC=C2SC(S)=NC2=C1 YXIWHUQXZSMYRE-UHFFFAOYSA-N 0.000 description 2
- GGZHVNZHFYCSEV-UHFFFAOYSA-N 1-Phenyl-5-mercaptotetrazole Chemical compound SC1=NN=NN1C1=CC=CC=C1 GGZHVNZHFYCSEV-UHFFFAOYSA-N 0.000 description 2
- RMSGQZDGSZOJMU-UHFFFAOYSA-N 1-butyl-2-phenylbenzene Chemical group CCCCC1=CC=CC=C1C1=CC=CC=C1 RMSGQZDGSZOJMU-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
- OAKJQQAXSVQMHS-UHFFFAOYSA-N Hydrazine Chemical compound NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
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- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 2
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- 229940006460 bromide ion Drugs 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 125000002704 decyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 2
- 125000005331 diazinyl group Chemical class N1=NC(=CC=C1)* 0.000 description 2
- 125000003438 dodecyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- MTZQAGJQAFMTAQ-UHFFFAOYSA-N ethyl benzoate Chemical compound CCOC(=O)C1=CC=CC=C1 MTZQAGJQAFMTAQ-UHFFFAOYSA-N 0.000 description 2
- 229910052736 halogen Inorganic materials 0.000 description 2
- 150000002367 halogens Chemical class 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 2
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 2
- 125000001421 myristyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 2
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 description 2
- 125000001400 nonyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 230000003287 optical effect Effects 0.000 description 2
- 239000007800 oxidant agent Substances 0.000 description 2
- 125000000913 palmityl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 229920000728 polyester Polymers 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 230000001681 protective effect Effects 0.000 description 2
- ZUNKMNLKJXRCDM-UHFFFAOYSA-N silver bromoiodide Chemical compound [Ag].IBr ZUNKMNLKJXRCDM-UHFFFAOYSA-N 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- GGCZERPQGJTIQP-UHFFFAOYSA-N sodium;9,10-dioxoanthracene-2-sulfonic acid Chemical compound [Na+].C1=CC=C2C(=O)C3=CC(S(=O)(=O)O)=CC=C3C(=O)C2=C1 GGCZERPQGJTIQP-UHFFFAOYSA-N 0.000 description 2
- 125000004079 stearyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 2
- AOSFMYBATFLTAQ-UHFFFAOYSA-N 1-amino-3-(benzimidazol-1-yl)propan-2-ol Chemical compound C1=CC=C2N(CC(O)CN)C=NC2=C1 AOSFMYBATFLTAQ-UHFFFAOYSA-N 0.000 description 1
- GPMKRLQZBACPED-UHFFFAOYSA-N 1-methyltriazole-4-thiol Chemical compound CN1C=C(S)N=N1 GPMKRLQZBACPED-UHFFFAOYSA-N 0.000 description 1
- NGSULTPMGQCSHK-UHFFFAOYSA-N 2,3-Dihydroxy-acrylaldehyd Natural products OC=C(O)C=O NGSULTPMGQCSHK-UHFFFAOYSA-N 0.000 description 1
- IORISFYTXJVNFE-UHFFFAOYSA-N 2,3-dinitrobenzenesulfonic acid Chemical class OS(=O)(=O)C1=CC=CC([N+]([O-])=O)=C1[N+]([O-])=O IORISFYTXJVNFE-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
- RYYXDZDBXNUPOG-UHFFFAOYSA-N 4,5,6,7-tetrahydro-1,3-benzothiazole-2,6-diamine;dihydrochloride Chemical compound Cl.Cl.C1C(N)CCC2=C1SC(N)=N2 RYYXDZDBXNUPOG-UHFFFAOYSA-N 0.000 description 1
- ONMOULMPIIOVTQ-UHFFFAOYSA-N 98-47-5 Chemical compound OS(=O)(=O)C1=CC=CC([N+]([O-])=O)=C1 ONMOULMPIIOVTQ-UHFFFAOYSA-N 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- 229920002284 Cellulose triacetate Polymers 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- 229940090898 Desensitizer Drugs 0.000 description 1
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 description 1
- 239000001828 Gelatine Substances 0.000 description 1
- NVXLIZQNSVLKPO-UHFFFAOYSA-N Glucosereductone Chemical compound O=CC(O)C=O NVXLIZQNSVLKPO-UHFFFAOYSA-N 0.000 description 1
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- CMEWLCATCRTSGF-UHFFFAOYSA-N N,N-dimethyl-4-nitrosoaniline Chemical compound CN(C)C1=CC=C(N=O)C=C1 CMEWLCATCRTSGF-UHFFFAOYSA-N 0.000 description 1
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- 206010070834 Sensitisation Diseases 0.000 description 1
- DWAQJAXMDSEUJJ-UHFFFAOYSA-M Sodium bisulfite Chemical compound [Na+].OS([O-])=O DWAQJAXMDSEUJJ-UHFFFAOYSA-M 0.000 description 1
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- NNLVGZFZQQXQNW-ADJNRHBOSA-N [(2r,3r,4s,5r,6s)-4,5-diacetyloxy-3-[(2s,3r,4s,5r,6r)-3,4,5-triacetyloxy-6-(acetyloxymethyl)oxan-2-yl]oxy-6-[(2r,3r,4s,5r,6s)-4,5,6-triacetyloxy-2-(acetyloxymethyl)oxan-3-yl]oxyoxan-2-yl]methyl acetate Chemical compound O([C@@H]1O[C@@H]([C@H]([C@H](OC(C)=O)[C@H]1OC(C)=O)O[C@H]1[C@@H]([C@@H](OC(C)=O)[C@H](OC(C)=O)[C@@H](COC(C)=O)O1)OC(C)=O)COC(=O)C)[C@@H]1[C@@H](COC(C)=O)O[C@@H](OC(C)=O)[C@H](OC(C)=O)[C@H]1OC(C)=O NNLVGZFZQQXQNW-ADJNRHBOSA-N 0.000 description 1
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- XYXNTHIYBIDHGM-UHFFFAOYSA-N ammonium thiosulfate Chemical compound [NH4+].[NH4+].[O-]S([O-])(=O)=S XYXNTHIYBIDHGM-UHFFFAOYSA-N 0.000 description 1
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- XWGJFPHUCFXLBL-UHFFFAOYSA-M rongalite Chemical compound [Na+].OCS([O-])=O XWGJFPHUCFXLBL-UHFFFAOYSA-M 0.000 description 1
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- HRZFUMHJMZEROT-UHFFFAOYSA-L sodium disulfite Chemical compound [Na+].[Na+].[O-]S(=O)S([O-])(=O)=O HRZFUMHJMZEROT-UHFFFAOYSA-L 0.000 description 1
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Images
Classifications
-
- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03C—PHOTOSENSITIVE MATERIALS FOR PHOTOGRAPHIC PURPOSES; PHOTOGRAPHIC PROCESSES, e.g. CINE, X-RAY, COLOUR, STEREO-PHOTOGRAPHIC PROCESSES; AUXILIARY PROCESSES IN PHOTOGRAPHY
- G03C7/00—Multicolour photographic processes or agents therefor; Regeneration of such processing agents; Photosensitive materials for multicolour processes
- G03C7/28—Silver dye bleach processes; Materials therefor; Preparing or processing such materials
Definitions
- the present invention relates to a new process for producing negative color photographic images by the silver color bleaching process and the silver color bleaching material used in this process.
- the silver color matching process is based on the fact that certain classes of dyes, especially azo dyes, are reductively bleached in the presence of finely divided silver by strongly acidic baths containing a silver complexing agent. This reaction can be accelerated by catalysts, especially diazine compounds.
- the effect of finely divided silver on dyes can be used to convert photographically produced silver images into color images.
- the primary silver image is negative, i. H. opposed to submission.
- a second image reversal takes place, so that the resulting dye image is positive, i. H. is in sync with the template.
- the silver color bleaching process is therefore primarily used to produce positive color copies based on slides.
- Iodide ion diffusion is one method described in U.S.-A-3,695,881.
- an unveiled interior image emulsion is arranged, which is made difficult to fix by treatment with a heterocyclic nitrogen compound.
- the iodide ions migrating out of the silver iodide emulsion favor the dissolution of the interior image emulsions treated in this way in the fixing step.
- a positive image is thus again obtained in this emulsion, which can be used to produce a color image.
- a disadvantage of the known silver dye bleaching materials is that one is normally forced to store light-absorbing dyes in emulsion layers which are sensitized in the main absorption area of the dye. This causes a great loss of sensitivity.
- the object of the present invention is therefore to provide a method for producing negative photographic color images using iodide ion diffusion, which largely overcomes these disadvantages.
- a core-shell emulsion is used in the layer containing a bleachable dye, the particles of which contain a veiled core which may have been treated with a development retarder.
- the onset of the spontaneous development of the core-shell emulsion can be influenced by the choice of a suitable shell thickness around the veiled core so that the spontaneous development coincides with the diffusion of the development-controlling iodide ions.
- An additional development-retarding effect can be achieved by treating the cores with one of the customary development retarders before the silver halide shell is applied.
- the dye need not be present in the light-sensitive layer.
- This can also be strongly light-absorbing, e.g. B. black dyes are used, the use of which is normally excluded in a silver color bleaching material. This allows the production of a black and white negative material, the silver content of which is completely recoverable.
- the photographic material if it consists of more than one layer package, optionally contains intermediate layers d) between the layer packages, and that the development takes place in a developer solution free of silver complexing agents.
- silver haloiodide emulsion means a silver chloro or silver bromoiodide emulsion.
- Another object of the invention relates to the silver color bleaching material suitable for the method according to the invention.
- iodide ions are formed in the top layer a), which diffuse through the intermediate layer b) to the bottom layer c) and there inhibit the spontaneous development of the veiled core-shell emulsion. This creates a positive silver image in this layer. After bleaching the dye and removing all remaining silver compounds, the desired negative color image is finally obtained in the bottom layer.
- intermediate layers d) may also be arranged between the individual layer packages.
- the highly sensitive silver haloiodide emulsion of layer a) can have its maximum sensitivity both inside and outside the spectral range of the complementary color of the image dye in layer c).
- the trichromatic material described is characterized by particularly high sensitivity.
- Silver halide crystals with a diffusion-inhibiting silver halide shell can be produced in a simple manner using the known core-shell technique.
- Monodisperse emulsions are preferably used, the crystals of which are all within a relatively limited size range.
- Such an emulsion is veiled on the grain surface by customary methods, e.g. B. by exposure or by means known per se, such as u. a. in DE-A-1 597 488, 2 801 127, U.S.-A-3 761 266 and in Research Disclosure 16 345 (1977).
- the veiled crystals can also be treated with a development inhibitor which adheres to their surface by adsorption before being provided with a thin shell covering the development centers by further precipitation of silver halide.
- All customary silver halides can be used as silver halide crystals to be coated, that is to say silver chloride, silver bromide and silver iodide or mixed crystals of two or all three components.
- the crystals to be coated are as large as possible. It is therefore primarily used monodisperse emulsions, as known by known methods, for. B. can be made in cubic or octahedral crystal costume. The production of monodisperse emulsions is e.g. B. described in DE-A-1 904 148.
- the shell to be applied can consist of another silver halide or the same silver halide (s) as the core.
- the radius ratio of the core to the shell can also be varied within wide limits, particles which have a shell thickness that is relatively small in relation to the core diameter being primarily suitable for the present invention.
- Another way of influencing the start of development of the core-veiled core-shell emulsions is to choose different concentrations of an ammonium or alkali metal sulfite in the developer solution.
- the kinetics of spontaneous development can be controlled within wide limits by the sulfite concentration (2 to 100 g per liter of developing solution).
- the start and speed of the development process can also be influenced by the use of development-retarding substances.
- development-retarding substances can preferably be adsorbed on the veiled surface of the core before the shell is grown.
- the core-shell technique makes it possible to carry out the usual surface-influencing photographic operations, such as, for example, on the silver halide crystals to be coated.
- Suitable development inhibitors and retarders are e.g. B. benzotriazole, 2-mercaptobenzothiazole, N-methyl mercaptotriazole, phenyl mercaptotetrazole, triazolinedolizine and their derivatives.
- solubility product of the silver salt formed from the development retarder is between that of the silver chloride and that of the silver iodide [cf. A. B. Cohen et al, Potographic Sci. and eng. 9.96, (1965)].
- the veiling of the silver halide crystals, which then form the core of a core-shell particle, is carried out using customary methods, e.g. B. by diffuse exposure or with the usual chemical agents such.
- silver bromide or silver chlorobromide emulsions are preferably used for their production. Smaller proportions of up to about 20 mole percent silver chloride can be used; Emulsions with higher silver chloride contents are generally too quick to develop.
- the proportion of silver iodide should only be small and should not exceed about 1.0 mol percent, since otherwise the influencing of development by immigrant iodide ions, which is important for the process according to the invention, would not be guaranteed.
- the silver halide shell to be applied can consist of a different silver halide (s), of the same silver halides but in different halide proportions or preferably of the same silver halide or the same silver halides in the same halide proportions as the core.
- the surface of the emulsion core is still treated with a development retarder, this is advantageously done after the covering, but before the shell has grown.
- all dyes which are generally used for the silver color bleaching process are suitable as bleachable dyes for the process according to the invention.
- one of the subtractive basic dyes cyan, purple and yellow will be used in a layer package.
- an additional separating layer d) must be arranged between two layer packets in this case.
- the method is also suitable for producing monochromatic negative images, an important application relating to the production of negative black / white images, as can be obtained by using a bleachable black dye.
- the dye of the negative images according to the invention takes on the role of the light-absorbing silver halide of normal photographic materials.
- Bleachable dyes which are suitable for the process according to the invention are described, for example, in US Pat. Nos. 3,454,402, 3,443,933, 3,804,630, 3,716,368, 3,877,949, 3,623,874, 3,931,142 and 4,051,123 described.
- the intermediate layers d) (barrier and separating layers) generally contain only pure binder, e.g. B. gelatin, but no dye and no silver halide. If it is favorable for the overall layer sequence, an already existing emulsion layer or a filter layer can optionally also serve as a separating layer.
- the separating layer can contain further additives, such as substances which inhibit color bleaching, additional binders, such as, for example B. contain water-soluble colloids or water-insoluble dispersion polymers, also the usual additives for the construction of the other photographic layers such as plasticizers, wetting agents, light stabilizers, filter dyes, optical brighteners, UV absorbers or curing agents.
- the highly sensitive silver haloiodide emulsions are normally those which contain silver chloride and / or bromide and silver iodide.
- the iodide content is normally between 0.1 and 10, preferably 1 and 5 mol percent, the rest consists of silver chloride and / or bromide (e.g. 0 to 99.9 mol percent silver bromide).
- Gelatin is usually used as a protective colloid to prepare these emulsions; It Kings - but NEN other water-soluble protective colloids such as polyvinyl alcohol or polyvinyl etc. are used; furthermore, part of the gelatin can be replaced by dispersions of non-water-soluble high-molecular substances. Common is z. B. the use of dispersion polymers of a ,, 8-unsaturated compounds such as acrylic acid esters, vinyl esters and vinyl ethers, vinyl chloride, vinylidene chloride and other mixtures and copolymers.
- the emulsions can be applied to conventional supports for photographic recording material.
- a mixture of several colloids can be used to disperse the silver halides.
- the carrier can consist, for example, of pigmented cellulose triacetate or polyester. If it is made of paper felt, it must be coated on both sides or coated with polyethylene.
- the exposed silver color bleaching materials are processed in the customary manner and include silver development, color bleaching, silver bleaching and fixing and subsequent rinsing and, if appropriate, also between the individual steps (see, for example, DE-A-2448443). Color bleaching and silver bleaching, and possibly also fixation, can be combined in a single treatment step. It is also possible to incorporate developer compounds or developer precursors into the emulsion layers. Suitable buffering ensures that these substances remain inactive in the dry layer during storage. In this case, all that is required to start development is an activator bath with a high pH, which can be free of developer substances.
- Baths of conventional composition can be used for silver development, e.g. B. those that contain hydroquinone as developer or additionally 1-phenyl-3-pyrazolidinone, but do not contain silver complexing agents. It may also be advantageous if the silver developing bath, as described in Swiss Patent 405 929, additionally contains a color bleaching catalyst. Activator baths contain only strong alkalis and possibly other additives such as buffer substances, wetting agents etc. as active substances.
- Combined color and silver color bleaching baths generally contain a water-soluble oxidizing agent in addition to the specified components.
- Suitable color bleaching catalysts are primarily diazine compounds, e.g. B. in DE-B-2 010 280, 2 144 298 and 2 144 297, in FR-A-1 489 460, in US-A-2 270 118 and in DE-A-2 448 443 .
- Strong acids are to be understood here as those which give the color bleach bath or the combined color and silver bleach bath a pH value of at most 2. So it can.
- hydrochloric acid phosphoric acid and especially sulfuric acid or sulfamic acid can be used.
- Alkali iodides such as potassium iodide or sodium iodide can be used as the water-soluble iodide.
- Suitable oxidizing agents are nitroso compounds, such as. B. p-nitrosodimethylaniline, nitro compounds such as. B. aromatic nitro compounds and preferably aromatic mono- or dinitrobenzenesulfonic acids, e.g. B. m-nitrobenzenesulfonic acid.
- Reductones or water-soluble mercapto compounds are used in particular as antioxidants.
- Suitable reductones are especially aci-reductones with a 3-carbonyl-endiol (1,2) grouping such as reductin, triose reductone or preferably ascorbic acid.
- Suitable mercapto compounds are those of the formula HSA (B) m in which A is an aliphatic, cycloalphatic, araliphatic, aromatic or heterocyclic bridge member, B is a water-solubilizing radical and m is an integer of at most 4 (DE-A-2 258 076, 423 819).
- the silver fixing bath can be composed in a known and customary manner.
- Suitable as a fixative is, for. B. sodium thiosulfate or preferably ammonium thiosulfate, if desired with additives such as sodium bisulfite, sodium metabisulfite and / or ammonium bisulfite and optionally complexing agents such as ethylenediaminetetraacetic acid.
- All treatment baths can contain other common additives such as. B. contain hardening agents, wetting agents, optical retainers or UV protection agents.
- a sample of the material coated in this way is exposed to green light under a gradient wedge and processed as follows: After processing has been completed, a negative, ie counter-rotating, black and white image of very high contrast (y ⁇ 5) is obtained.
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Description
Die vorliegende Erfindung betrifft ein neues Verfahren zur Herstellung negativer photgraphischer Farbbilder nach dem Silberfarbbleichverfahren und das in diesem Verfahren verwendete Silberfarbbleichmaterial.The present invention relates to a new process for producing negative color photographic images by the silver color bleaching process and the silver color bleaching material used in this process.
Das Silberfarbleichverfahren beruht bekanntlich darauf, daß gewisse Klassen von Farbstoffen, vor allem Azofarbstoffe, in Gegenwart von feinverteiltem Silber durch stark saure, ein Silberkomplexierungsmittel enthaltende Bäder reduktiv gebleicht werden. Diese Reaktion kann durch Katalysatoren, vor allem Diazinverbindungen, beschleunigt werden.As is known, the silver color matching process is based on the fact that certain classes of dyes, especially azo dyes, are reductively bleached in the presence of finely divided silver by strongly acidic baths containing a silver complexing agent. This reaction can be accelerated by catalysts, especially diazine compounds.
Die Wirkung des feinverteilten Silbers auf Farbstoffe kann dazu benützt werden, photographisch erzeugte Silberbilder in Farbbilder umzuwandeln. Dabei ist im Normalfall das primär entstehende Silberbild negativ, d. h. zur Vorlage gegenläufig. Beim nachfolgenden Farbbleichprozess findet eine zweite Bildumkehr statt, so daß das schließlich entstehende Farbstoffbild positiv, d. h. gleichlaufend mit der Vorlage ist. Das Silberfarbbleichverfahren wird deshalb in erster Linie dazu benützt, um ausgehend von Diapositiven positive Farbkopien herzustellen.The effect of finely divided silver on dyes can be used to convert photographically produced silver images into color images. Normally, the primary silver image is negative, i. H. opposed to submission. In the subsequent color bleaching process, a second image reversal takes place, so that the resulting dye image is positive, i. H. is in sync with the template. The silver color bleaching process is therefore primarily used to produce positive color copies based on slides.
Damit das Silberfarbbleichverfahren auch zur Erzeugung negativer Farbbilder herangezogen werden kann, muß von einem positiven Silberbild ausgegangen werden. Für die Erzeugung von positiven Silberbildern sind mehrere Verfahren bekannt:
- a) Umkehrentwicklung: das primär nach der Belichtung und ersten Entwicklung entstandene negative Silberbild wird oxidativ gebleicht, während das diffus belichtete oder chemisch verschleierte Silberhalogenid durch Zweitentwicklung zu einem Positivbild verarbeitet wird (z. B. DE-B-1 145487).
- b) Direktpositivemulsionen: sie arbeiten entweder nach dem Innenbild- oder Oberflächenschleierprinzip unter Mitwirkung von Desensibilisatoren und liefern direkt ein positives Silberbild.
- c) Silberkomplexdiffusion: man verwendet zur Entwicklung des negativen Silberbildes Entwickler, die Silberkomplexbildner enthalten. Die nichtentwickelten, unbelichteten Silberhalogenidbereiche lösen sich im Entwickler als Silberkomplexe und wandern bildweise in eine Empfangsschicht, die Entwicklungskeime enthält. An diesen Keimen wird durch physikalische Entwicklung aus der silberkomplexhaltigen Entwicklerlösung Silber abgeschieden, wodurch ein Positivbild entsteht (z. B. DE-A-1 572 206 oder GB-A-656 131).
- d) Bromid- oder Jodidionendiffusion: bei der Entwicklung von belichteten Silberbromid- oder Silberchloridemulsionen wird gleichzeitig mit der Entstehung von metallischem Silber das entsprechende Halogenidion freigesetzt, welches nun in der Emulsionsschicht frei diffundieren kann. Solche Ionen besitzen die Eigenschaft, die Entwicklung belichteter Kristalle von leichter löslichen Silberhalogeniden zu stören oder zu verhindern. So hemmen Bromidionen die Entwicklung von Silberchloridemulsionen, Jodidionen die Entwicklung von Silberchlorid- oder Silberbromidemulsionen. Dies gilt sowohl für die übliche chemische als auch für die physikalische Entwicklung von Silberhalogenidemulsionen.
- a) Reverse development: the negative silver image, which primarily arises after exposure and the first development, is bleached oxidatively, while the diffusely exposed or chemically veiled silver halide is processed into a positive image by second development (e.g. DE-B-1 145487).
- b) Direct positive emulsions: they work either on the inside or surface veil principle with the participation of desensitizers and provide a positive silver image directly.
- c) Silver complex diffusion: developers containing silver complexing agents are used to develop the negative silver image. The undeveloped, unexposed silver halide areas dissolve in the developer as silver complexes and migrate imagewise into a receiving layer which contains development nuclei. Silver is deposited on these germs by physical development from the silver complex-containing developer solution, whereby a positive image is created (e.g. DE-A-1 572 206 or GB-A-656 131).
- d) Bromide or iodide ion diffusion: in the development of exposed silver bromide or silver chloride emulsions, the corresponding halide ion is released simultaneously with the formation of metallic silver, which can now diffuse freely in the emulsion layer. Such ions have the property of disrupting or preventing the development of exposed crystals of more soluble silver halides. Bromide ions inhibit the development of silver chloride emulsions, iodide ions inhibit the development of silver chloride or silver bromide emulsions. This applies to both the usual chemical and physical development of silver halide emulsions.
Die Erzeugung von positiven Siberbildern durch Bromidionendiffusion wird in der DE-A-859711 erläutert. In einer Emulsionsschicht des photographischen Materials befinden sich hochempfindliches Silberbromid, wenig empfindliches, verschleiertes Silberchlorid und kolloides Silber, welches die Entwicklungskeime liefert. Bei der Entwicklung des im Silberbromid entstehenden Primärbildes entstehen Bromidionen, welche die spontane Entwicklung benachbarter Silberchloridpartikel unterbinden. Da das damit entstehende positive Bild aus dem Silberchlorid eine viel höhere Deckkraft besitzt als das aus dem Silberbromid gleichzeitig gebildete Negativbild, resultiert als Summe ein Positivbild. In ähnlicher Weise werden positive Silberbilder und die entsprechenden Farbbilder gemäß CH-A-564795 durch Trennung der vorverschleierten silberchloridreichen Schicht, die einen bleichbaren Farbstoff enthält, von der empfindlichen silberbromidreichen Schicht hergestellt.The generation of positive Siberian images by bromide ion diffusion is explained in DE-A-859711. An emulsion layer of the photographic material contains highly sensitive silver bromide, less sensitive, veiled silver chloride and colloidal silver, which supplies the development nuclei. During the development of the primary image formed in the silver bromide, bromide ions are formed which prevent the spontaneous development of neighboring silver chloride particles. Since the resulting positive image from the silver chloride has a much higher opacity than the negative image formed from the silver bromide at the same time, the result is a positive image. Similarly, positive silver images and the corresponding color images according to CH-A-564795 are produced by separating the pre-fogged layer rich in silver chloride, which contains a bleachable dye, from the sensitive layer rich in silver bromide.
Auf Jodidionendiffusion beruht ein Verfahren, das in der U.S.-A-3 695 881 beschrieben ist. Dort wird in der Nachbarschicht zu einer Silberjodid enthaltenden Emulsion eine unverschleierte Innenbildemulsion angeordnet, die durch Behandlung mit einer heterocyclischen Stickstoffverbindung schwer fixierbar gemacht ist. Die aus der Silberjodidemulsion auswandernden Jodidionen begünstigen in der Fixierstufe die Auflösung der so behandelten Innenbildemulsionen. Man erhält somit in dieser Emulsion wiederum ein Positivbild, das zur Herstellung eines Farbbildes herangezogen werden kann.Iodide ion diffusion is one method described in U.S.-A-3,695,881. There, in the adjacent layer to an emulsion containing silver iodide, an unveiled interior image emulsion is arranged, which is made difficult to fix by treatment with a heterocyclic nitrogen compound. The iodide ions migrating out of the silver iodide emulsion favor the dissolution of the interior image emulsions treated in this way in the fixing step. A positive image is thus again obtained in this emulsion, which can be used to produce a color image.
Ein Nachteil der bekannten Silberfarbbleichmaterialien besteht nun darin, daß man normalerweise gezwungen ist, lichtabsorbierende Farbstoffe in Emulsionsschichten einzulagern, die gerade im Hauptabsorptionsgebiet des Farbstoffes sensibilisert sind. Dadurch entsteht ein großer Empfindlichkeitsverlust.A disadvantage of the known silver dye bleaching materials is that one is normally forced to store light-absorbing dyes in emulsion layers which are sensitized in the main absorption area of the dye. This causes a great loss of sensitivity.
Ein weiterer Nachteil wird im Hinblick auf ein besonderes, die Jodidionendiffusion ausnutzendes Silberfarbbleichverfahren sichtbar. Wird z. B. ein photographisches Material, welches auf einem Träger in einer untersten Schicht einen bleichbaren Farbstoff und eine relativ unempfindliche, oberflächenverschleierte Silberhologenidemulsion und in einer darüberliegenden Schicht eine farbstofffreie, hochempfindliche, silberjodidhaltige Silberbromidemulsion enthält, wobei diese beiden Schichten durch eine nur Bindemittel enthaltende dritte Schicht getrennt sind, belichtet und entwickelt und danach dem üblichen Farbbleichprozess unterworfen, so spielen sich folgende Vorgänge ab:
- Die Spontanentwicklung der oberflächenverschleierten Silberhalogenidemulsion setzt ein, bevor die Jodidionen aus der obersten Schicht eindiffundieren können. Damit entsteht kein oder nur ein sehr kontrastarmes, positives Silberbild.
- The surface veiled silver halide emulsion begins to develop spontaneously before the iodide ions can diffuse from the top layer. This creates no or only a very low-contrast, positive silver image.
Aufgabe der vorliegenden Erfindung ist es deshalb, ein Verfahren zur Herstellung negativer photographischer Farbbilder unter Ausnutzung der Jodidionendiffusion bereitzustellen, welches diese Nachteile weitgehend überwindet.The object of the present invention is therefore to provide a method for producing negative photographic color images using iodide ion diffusion, which largely overcomes these disadvantages.
Es wurde nun gefunden, daß man eine Kontrasterhöhung des positiven Silberbildes erzielen kann, wenn in der einen bleichbaren Farbstoff enthaltenden Schicht eine Core-shell-Emulsion verwendet wird, deren Partikel einen verschleierten, gegebenenfalls mit einem Entwicklungsverzögerer behandelten Kern enthalten. Das Einsetzen der Spontanentwicklung der Core-shell-Emulsion läßt sich durch die Wahl einer geeigneten Schalendicke um den verschleierten Kern so beeinflussen, daß die Spontanentwicklung mit dem Eindiffundieren der entwicklungssteuernden Jodidionen zeitlich übereinstimmt.It has now been found that an increase in the contrast of the positive silver image can be achieved if a core-shell emulsion is used in the layer containing a bleachable dye, the particles of which contain a veiled core which may have been treated with a development retarder. The onset of the spontaneous development of the core-shell emulsion can be influenced by the choice of a suitable shell thickness around the veiled core so that the spontaneous development coincides with the diffusion of the development-controlling iodide ions.
Eine zusätzliche entwicklungsverzögernde Wirkung kann dadurch erzielt werden, daß die Kerne vor dem Aufbringen der Silberhalogenidschale noch mit einem der gebräuchlichen Entwicklungsverzögerer behandelt werden.An additional development-retarding effect can be achieved by treating the cores with one of the customary development retarders before the silver halide shell is applied.
Ferner wird eine Empfindlichkeitsverbesserung erreicht, da der Farbstoff nicht in der lichtempfindlichen Schicht vorhanden sein muß. Damit können auch stark lichtabsorbierende, z. B. schwarze Farbstoffe verwendet werden, deren Anwendung in einem Silberfarbbleichmaterial normalerweise ausgeschlossen ist. Dies erlaubt die Herstellung eines Schwarz/Weiß-Negativmaterials, dessen Silbergehalt vollständig zurückgewinnbar ist.Furthermore, an improvement in sensitivity is achieved since the dye need not be present in the light-sensitive layer. This can also be strongly light-absorbing, e.g. B. black dyes are used, the use of which is normally excluded in a silver color bleaching material. This allows the production of a black and white negative material, the silver content of which is completely recoverable.
Gegenstand der Erfindung ist somit ein Verfahren zur Herstellung negativer Farbbilder nach dem Silberfarbbleichverfahren, durch Belichtung eines photographischen Materials, Silberentwicklung, Farbbleichung, Silberbleichung und Fixierung, wobei die Silberbleichung gegebenenfalls mit der Farbbleichung und/oder Fixierung in einem einzigen Behandlungsbad kombiniert werden kann, wobei das photographische Material aus einem Träger mit mindestens einem Schichtpaket von je drei Schichten besteht, dadurch gekennzeichnet, daß jedes Schichtpaket, von der Seite des Lichteinfalls betrachtet,
- a) eine erste Schicht, die eine hochempfindliche, gegebenenfalls spektral sensibilisierte Silberhalojodidemulsion enthält,
- b) eine weder Silberhalogenid noch Bildfarbstoff enthaltende Zwischenschicht und
- c) eine dritte Schicht enthält, die einen bleichbaren Biidfarbstoff und eine jodidfreie oder jodidarme Core-shell-Emulsion enthält, deren Partikel aus einem oberflächenverschleierten und gegebenenfalls mit einem Entwicklungsverzögerer behandelten Silberhalogenidkern und einer diesen umhüllenden Silberhalogenidschale bestehen, wobei sich diese Emulsion durch Einwirkung eines Entwicklers spontan bis zur Maximaldichte entwickeln läßt,
- a) a first layer which contains a highly sensitive, optionally spectrally sensitized, silver haloiodide emulsion,
- b) an intermediate layer containing neither silver halide nor image dye and
- c) contains a third layer which contains a bleachable biidye and a iodide-free or low-iodide core-shell emulsion, the particles of which consist of a surface-fogged silver halide core, optionally treated with a development retarder, and a silver halide shell enveloping it, this emulsion being formed by the action of a developer spontaneously develop up to the maximum density,
daß das photographische Material, falls es aus mehr als einem Schichtpaket besteht, gegebenenfalls zwischen den Schichtpaketen Zwischenschichten d) enthält, und daß die Entwicklung in einer von Silberkomplexbildner freien Entwicklerlösung erfolgt.that the photographic material, if it consists of more than one layer package, optionally contains intermediate layers d) between the layer packages, and that the development takes place in a developer solution free of silver complexing agents.
In Schicht a) bedeutet Silberhalojodidemulsion eine Silberchloro- oder Silberbromojodidemulsion.In layer a), silver haloiodide emulsion means a silver chloro or silver bromoiodide emulsion.
Ein weiterer Gegenstand der Erfindung betrifft das für das erfindungsgemäße Verfahren geeignete Silberfarbbleichmaterial.Another object of the invention relates to the silver color bleaching material suitable for the method according to the invention.
Wird das oben beschriebene, erfindungsgemäße photographische Material belichtet und entwikkelt und danach dem üblichen Farbbleichprozeß unterworfen, so spielen sich die folgenden in Fig. 1 dargestellten Vorgänge ab:
- Die in oberster Position befindliche hochempfindliche, jodidhaltige Silberbromidemulsionsschicht a) wird bildmäßig belichtet. Da diese Schicht keinen Farbstoff enthält, erreicht man eine sehr hohe photographische Empfindlichkeit. Die verschleierte Core-shell-Emulsion in der untersten Schicht c) wird wegen ihrer geringen Empfindlichkeit höchstens schwach anbelichtet, doch spielt dies wegen ihrer spontanen Entwickelbarkeit keine Rolle.
- The highly sensitive, iodide-containing silver bromide emulsion layer a) located in the top position is exposed imagewise. Since this layer contains no dye, very high photographic sensitivity is achieved. The veiled core-shell emulsion in the bottom layer c) is at most weakly exposed due to its low sensitivity, but this does not matter because of its spontaneous developability.
Bei der nachfolgenden Entwicklung entstehen in der obersten Schicht a) bildmäßig Jodidionen, die durch die Zwischenschicht b) bis zur untersten Schicht c) diffundieren und dort bildmäßig die Spontanentwicklung der verschleierten Core-shell-Emulsion hemmen. In dieser Schicht entsteht damit ein positives Silberbild. Nach Bleichung des Farbstoffs und Entfernung aller restlichen Silberverbindungen erhält man schließlich in der untersten Schicht das gewünschte negative Farbbild.In the subsequent development, iodide ions are formed in the top layer a), which diffuse through the intermediate layer b) to the bottom layer c) and there inhibit the spontaneous development of the veiled core-shell emulsion. This creates a positive silver image in this layer. After bleaching the dye and removing all remaining silver compounds, the desired negative color image is finally obtained in the bottom layer.
Werden drei der oben beschriebenen Schichtpakete, welche je einen blaugrünen, einen purpurfarbenen und einem gelben Bildfarbstoff in den Schichten c) enthalten, zu einem trichromatischen Silberfarbbleichmaterial kombiniert, so sind zwischen den einzelnen Schichtpaketen gegebenenfalls noch Zwischenschichten d) angeordnet.If three of the layer packages described above, each containing a blue-green, a purple and a yellow image dye in layers c), are combined to form a trichromatic silver color bleaching material, intermediate layers d) may also be arranged between the individual layer packages.
Die hochempfindliche Silberhalojodidemulsion der Schicht a) kann ihre maximale Empfindlichkeit sowohl innerhalb als auch außerhalb des Spektralbereiches der Komplementärfarbe des Bildfarbstoffes in der Schicht c) aufweisen.The highly sensitive silver haloiodide emulsion of layer a) can have its maximum sensitivity both inside and outside the spectral range of the complementary color of the image dye in layer c).
Das beschriebene trichromatische Material zeichnet sich durch besonders hohe Empfindlichkeit aus.The trichromatic material described is characterized by particularly high sensitivity.
Silberhalogenidkristalle mit einer diffusionshemmenden Silberhalogenidhülle lassen sich in einfacher Weise nach der bekannten Core-shell-Technik herstellen. Man verwendet dazu vorzugsweise monodisperse Emulsionen, deren Kristalle alle innerhalb eines relativ beschränkten Größenbereichs liegen. Man verschleiert eine solche Emulsion auf der Kornoberfläche nach üblichen Methoden, z. B. durch Belichtung oder mittels an sich bekannter Mittel, wie u. a. in den DE-A-1 597 488, 2 801 127, der U.S.-A-3 761 266 sowie in Research Disclosure 16 345 (1977) beschrieben.Silver halide crystals with a diffusion-inhibiting silver halide shell can be produced in a simple manner using the known core-shell technique. Monodisperse emulsions are preferably used, the crystals of which are all within a relatively limited size range. Such an emulsion is veiled on the grain surface by customary methods, e.g. B. by exposure or by means known per se, such as u. a. in DE-A-1 597 488, 2 801 127, U.S.-A-3 761 266 and in Research Disclosure 16 345 (1977).
Falls gewünscht, können die verschleierten Kristalle noch mit einem Entwicklungsinhibitor behandelt werden, der sich an deren Oberfläche durch Adsorption festsetzt, bevor sie durch weitere Ausfällung von Silberhalogenid mit einer dünnen, die Entwicklungszentren bedeckenden Hülle versehen werden.If desired, the veiled crystals can also be treated with a development inhibitor which adheres to their surface by adsorption before being provided with a thin shell covering the development centers by further precipitation of silver halide.
Als zu umhüllende Silberhalogenidkristalle können alle gebräuchlichen Silberhalogenide verwendet werden, also Silberchlorid, Silberbromid und Silberjodid oder Mischkristalle aus zwei oder allen drei Komponenten. Um ein gleichmäßiges Aufwachsen der Schale zu gewährleisten, ist es vorteilhaft, wenn die zu umhüllenden Kristalle möglichst gleich groß sind. Man verwendet deshalb in erster Linie monodisperse Emulsionen, wie sie nach bekannten Methoden, z. B. in kubischer oder oktaendrischer Kristalltracht hergestellt werden können. Die Herstellung monodisperser Emulsionen ist z. B. in der DE-A-1 904 148 beschrieben.All customary silver halides can be used as silver halide crystals to be coated, that is to say silver chloride, silver bromide and silver iodide or mixed crystals of two or all three components. In order to ensure a uniform growth of the shell, it is advantageous if the crystals to be coated are as large as possible. It is therefore primarily used monodisperse emulsions, as known by known methods, for. B. can be made in cubic or octahedral crystal costume. The production of monodisperse emulsions is e.g. B. described in DE-A-1 904 148.
Die aufzubringende Schale kann aus (einem) anderen oder dem (den) selben Silberhalogenid(en) bestehen wie der Kern. Auch das Radienverhältnis von Kern zu Schale kann in weiten Grenzen variiert werden, wobei für die vorliegende Erfindung in erster Linie Partikel in Frage kommen, deren Schalendicke im Verhältnis zum Kerndurchmesser verhältnismäßig klein ist.The shell to be applied can consist of another silver halide or the same silver halide (s) as the core. The radius ratio of the core to the shell can also be varied within wide limits, particles which have a shell thickness that is relatively small in relation to the core diameter being primarily suitable for the present invention.
Zum Aufbringen der Schale auf den Kern sind vor allem drei Methoden gebräuchlich:
- a) das Auffällen von weiterem Silberhalogenid durch gleichzeitige Zugabe von löslichem Silbersalz und löslichem Halogenid, wobei die Fällungsbedingungen (Konzentration, Zulaufgeschwindigkeit) so gewählt werden, daß keine neuen Kristallisationskeime entstehen (z. B. DE-A-2 015 070).
- b) Zugabe einer feindispersen Silberhalogendemulsion, deren Kristalle wesentlich kleiner sind als die zu umhüllenden Kristalle. Die feindispersen Kristalle verschwinden, indem sich wie bei der Ostwaldreifung um die größeren Kristalle eine Schale aus dem Material der zugefügten feindispersen Emulsion bildet (z. B. U.S.-A-3 206 313).
- c) Durch Fällung während periodischem Wechsel des pAg-Wertes zwischen Silber- bzw. Halogenid- überschuss. Auf diese Art können Partikel mit mehrschichtigem Aufbau erzeugt werden (z. B. U.S.-A-3 917 485).
- a) the precipitation of further silver halide by simultaneous addition of soluble silver salt and soluble halide, the precipitation conditions (concentration, feed rate) being chosen so that no new crystallization nuclei are formed (e.g. DE-A-2 015 070).
- b) adding a finely dispersed silver halide emulsion, the crystals of which are significantly smaller than the crystals to be coated. The finely dispersed crystals disappear by forming a shell from the material of the finely dispersed emulsion added (for example BUS-A-3 206 313) as in the Ostwald ripening around the larger crystals.
- c) By precipitation during periodic change of the pAg value between excess silver or halide. In this way, particles with a multilayer structure can be produced (for example BUS-A-3 917 485).
Es wurde gefunden, daß die Wahl einer geeigneten Schalendicke um den verschleierten Kern eines Core-shell-Partikels ein ausgezeichnetes Mittel darstellt, um das Einsetzen der Spontanentwicklung so zu verzögern, daß die Spontanentwicklung mit dem Eindiffundieren der entwicklungssteuernden Jodidionen zeitlich übereinstimmt. Schalendicken zwischen 5 und 100 mm, entsprechend etwa 7 bis 140 Silberhalogenidgitterebenen, vorzugsweise 10 bis 25 mm, bilden einen geeigneten Bereich für das erfindungsgemäße Verfahren.It has been found that the choice of a suitable shell thickness around the veiled core of a core-shell particle is an excellent means of delaying the onset of spontaneous development so that the spontaneous development coincides with the diffusion of the development-controlling iodide ions. Shell thicknesses between 5 and 100 mm, corresponding to approximately 7 to 140 silver halide lattice planes, preferably 10 to 25 mm, form a suitable range for the process according to the invention.
Eine weitere Möglichkeit, den Entwicklungsbeginn der kernverschleierten Core-shell-Emulsionen zu beeinflussen, besteht in der Wahl verschiedener Konzentrationen eines Ammonium- oder Alkalimetallsulfits in der Entwicklerlösung. Durch die Sulfitkonzentration (2 bis 100 g je Liter Entwicklungslösung) kann die Kinetik der Spontanentwicklung in weiten Grenzen gesteuert werden.Another way of influencing the start of development of the core-veiled core-shell emulsions is to choose different concentrations of an ammonium or alkali metal sulfite in the developer solution. The kinetics of spontaneous development can be controlled within wide limits by the sulfite concentration (2 to 100 g per liter of developing solution).
Der Beginn und die Geschwindigkeit des Entwicklungsvorgangs kann zusätzlich durch die Verwendung von entwicklungsverzögernden Substanzen beeinflußt werden. Solche Substanzen können vorzugsweise vor dem Aufwachsen der Schale auf der verschleierten Oberfläche des Kerns adsorbiert werden.The start and speed of the development process can also be influenced by the use of development-retarding substances. Such substances can preferably be adsorbed on the veiled surface of the core before the shell is grown.
Die Core-shell-Technik ermöglicht es, an den zu umhüllenden Silberhalogenidkristallen die üblichen oberflächenbeeinflussenden photographischen Operationen, wie z. B. Reifung, Verschleierung, Sensibilisierung oder die Anlagerung weiterer Substanzen wie Stabilisatoren, Entwicklungsbeschleuniger und -verzögerer vorzunehmen, und die so behandelte Oberfläche nachher durch das zusätzliche Aufwachsen der Schale ins Innere des Kristalls zu verlegen [z. B. DE-A-2 260 117 und E. Moisar, S. Wagner, Ber. Bunsengesellschaft 67,356 (1963)].The core-shell technique makes it possible to carry out the usual surface-influencing photographic operations, such as, for example, on the silver halide crystals to be coated. B. ripening, obscuring, sensitization or the addition of other substances such as stabilizers, development accelerators and retarders to carry out, and then to move the surface thus treated by the additional growth of the shell inside the crystal [z. B. DE-A-2 260 117 and E. Moisar, S. Wagner, Ber. Bunsen Society 67, 356 (1963)].
Als Entwicklungsinhibitoren und -verzögerer eignen sich z. B. Benzotriazol, 2-Mercaptobenzthiazol, N-Methylmercaptotriazol, Phenylmercaptotetrazol, Triazolindolizin und deren Derivate.Suitable development inhibitors and retarders are e.g. B. benzotriazole, 2-mercaptobenzothiazole, N-methyl mercaptotriazole, phenyl mercaptotetrazole, triazolinedolizine and their derivatives.
Eine wichtige Bedingung ist dabei, daß das Löslichkeitsprodukt des aus dem Entwicklungsverzögerer gebildeten Silbersalzes zwischen demjenigen des Silberchlorids und demjenigen des Silberjodids liegt [vgl. A. B. Cohen et al, Potographic Sci. and Eng. 9,96, (1965)].An important condition is that the solubility product of the silver salt formed from the development retarder is between that of the silver chloride and that of the silver iodide [cf. A. B. Cohen et al, Potographic Sci. and eng. 9.96, (1965)].
Geeignet sind grundsätzlich alle bekannten Entwicklungsverzögerer, welche diese Bedingung erfüllen. Vorzugsweise eignen sich jedoch solche Verbindungen, die in den photographischen Schichten diffusionsfest eingelagert werden können. Dies sind in erster Linie in Wasser schwer- oder unlösliche Verbindungen, die Ballastgruppen enthalten. Als solche eignen sich z. B. 5-Mercaptotetrazole, die in 1-Stellung mit Acrylgruppen, vorzugsweise mehrkernigen Aryl, wie Naphthyl oder Diphenyl, gegebenenfalls auch mit vorzugsweise längeren Alkyl-(C13-C18) substituierte Arylgruppen, insbesondere Phenyl, ferner mit Aralkyl oder mit Alkyl mit vorzugsweise mindestens 3, insbesondere 3 bis 18 Kohlenstoffatomen substituiert sind.In principle, all known development retarders that meet this condition are suitable. However, preference is given to those compounds which can be embedded in the photographic layers in a diffusion-resistant manner. These are primarily compounds which are difficult or insoluble in water and contain ballast groups. As such, z. B. 5-mercaptotetrazoles, which in 1-position with acrylic groups, preferably polynuclear aryl, such as naphthyl or diphenyl, optionally also with preferably longer alkyl (C 13 -C 18 ) substituted aryl groups, in particular phenyl, furthermore with aralkyl or with alkyl with preferably at least 3, in particular 3 to 18 Carbon atoms are substituted.
Als Entwicklungsverzögerer sind z. B. insbesondere geeignet: 5-Mercaptotetrazole, die in 1-Stellung mit einer der folgenden Gruppen substituiert sind:
- n-Propyl, i-Propyl, n-Butyl, i-Butyl, t-Butyl, i-Amyl, i-Octyl, t-Octyl, Nonyl, Decyl, Lauryl, Myristyl, Palmityl, Stearyl, Ditert.butyl-phenyl, Octylphenyl, Dodecylphenyl, Naphthyl, a- oderd-Naphthyl oder Diphenyl. Nicht diffusionsfeste Mercaptotetrazole ohne eigentliche Ballastgruppen können ebenfalls verwendet werden. Es muß aber in diesem Fall dafür gesorgt werden, daß der Entwicklungsverzögerer nicht in unerwünschter Richtung in eine Nachbarschicht diffundiert und z. B. die Entwicklung der Jodidionen liefernden Emulsionen verzögert. Dies kann z. B. durch Einschaltung einer Zwischenschicht geschehen. Unter dieser Bedingung können auch z. B. mit folgenden Gruppen in 1-Stellung substituierte 5-Mercaptotetrazole verwendet werden: Phenyl, mit Hydroxyl, Halogen (Chlor, Brom) oder Niederalkyl (C2-C3) substituiertes Phenyl, Benzoesäure-methyl- oder -äthylester, Methyl oder Aethyl. Im allgemeinen ist jedoch die Verwendung diffusionsfester Entwicklungsverzögerer vorzuziehen, weil dadurch der Schichtaufbau, insbesondere von solchen Materialien mit einer Vielzahl von Farb- und Emulsionsschichten wesentlich vereinfacht werden kann. Die Entwicklungsverzögerer werden in Mengen von 1 bis 80 mMol, vorzugsweise von 3 bis 40 mMol pro Mol Silber in der vorverschleierten Emulsion eingesetzt.
- n-propyl, i-propyl, n-butyl, i-butyl, t-butyl, i-amyl, i-octyl, t-octyl, nonyl, decyl, lauryl, myristyl, palmityl, stearyl, ditert.butyl-phenyl, Octylphenyl, dodecylphenyl, naphthyl, a- or d-naphthyl or diphenyl. Non-diffusion resistant mercaptotetrazoles without actual ballast groups can also be used. In this case, however, it must be ensured that the development retardant does not diffuse in an undesirable direction into a neighboring layer and z. B. delayed the development of the emulsions providing iodide ions. This can e.g. B. done by switching on an intermediate layer. Under this condition, z. B. with the following groups in the 1-position substituted 5-mercaptotetrazoles: phenyl, with hydroxyl, halogen (chlorine, bromine) or lower alkyl (C 2 -C 3 ) substituted phenyl, methyl or ethyl benzoate, methyl or ethyl . In general, however, the use of diffusion-resistant development retarders is preferred because the layer structure, in particular of such materials with a large number of color and emulsion layers, can be significantly simplified. The development retarders are used in amounts of 1 to 80 mmol, preferably 3 to 40 mmol, per mol of silver in the pre-fogged emulsion.
Die Verschleierung der Silberhalogenidkristalle, welche dann den Kern eines Core-shell-Partikels bilden, erfolgt nach üblichen Methoden, z. B. durch diffuse Anbelichtung oder mit den gebräuchlichen chemischen Mitteln wie z. B. Thioharnstoffdioxid, Zinn(2)-Chlorid, Hydrazin, Boranen, Formaldehydsulfoxylaten oder Goldsalzen (Komplexen). Da die verschleierten Kerne nicht zu schnell entwickeln sollen, verwendet man zu ihrer Herstellung vorzugsweise Silberbromid- oder Silberchlorobromidemulsionen. Geringere Anteile bis zu etwa 20 Mol-Prozent Silberchlorid können eingesetzt werden; Emulsionen mit höheren Silberchloridgehalten sind im allgemeinen zu schnell entwickelbar. Der Anteil an Silberjodid sollte nur gering sein und etwa 1,0 Mol-Prozent nicht übersteigen, da sonst die für das erfindungsgemäße Verfahren wichtige Beeinflußung der Entwicklung durch einwandernde Jodidionen nicht gewährleistet wäre.The veiling of the silver halide crystals, which then form the core of a core-shell particle, is carried out using customary methods, e.g. B. by diffuse exposure or with the usual chemical agents such. B. thiourea dioxide, tin (2) chloride, hydrazine, boranes, formaldehyde sulfoxylates or gold salts (complexes). Since the veiled cores should not develop too quickly, silver bromide or silver chlorobromide emulsions are preferably used for their production. Smaller proportions of up to about 20 mole percent silver chloride can be used; Emulsions with higher silver chloride contents are generally too quick to develop. The proportion of silver iodide should only be small and should not exceed about 1.0 mol percent, since otherwise the influencing of development by immigrant iodide ions, which is important for the process according to the invention, would not be guaranteed.
Die aufzubringende Silberhalogenidschale kann aus (einem) anderen Silberhalogenid(en), aus denselben Silberhalogeniden, jedoch in unterschiedlichen Halogenidanteilen oder vorzugsweise aus demselben Silberhalogenid oder denselben Silberhalogendien in denselben Halogenidanteilen wie der Kern bestehen.The silver halide shell to be applied can consist of a different silver halide (s), of the same silver halides but in different halide proportions or preferably of the same silver halide or the same silver halides in the same halide proportions as the core.
Falls die Oberfläche des Emulsionskerns noch mit einem Entwicklungsverzögerer behandelt wird, so erfolgt dies vorteilhaft nach der Verschleierung, jedoch noch vor dem Aufwachsen der Schale.If the surface of the emulsion core is still treated with a development retarder, this is advantageously done after the covering, but before the shell has grown.
Als bleichbare Farbstoffe für das erfindungsgemäße Verfahren eignen sich grundsätzlich alle Farbstoffe, die für das Silberfarbbleichverfahren allgemein Verwendung finden. Falls trichromatische Negativbilder hergestellt werden sollen, wird man in je einem Schichtpaket je einen der subtraktiven Grundfarbstoffe Blaugrün, Purpur und Gelb verwenden. Zur Vermeidung von Bleichkopplungen muß in diesem Fall zwischen je zwei Schichtpaketen eine zusätzliche Trennschicht d) angeordnet werden. Das Verfahren eignet sich aber auch zur Herstellung von monochromatischen Negativbildern, wobei eine wichtige Anwendung die Herstellung von negativen Schwarz/Weiß-Bildern betrifft, wie sie durch Verwendung eines bleichbaren schwarzen Farbstoffs erhalten werden können.In principle, all dyes which are generally used for the silver color bleaching process are suitable as bleachable dyes for the process according to the invention. If trichromatic negative images are to be produced, one of the subtractive basic dyes cyan, purple and yellow will be used in a layer package. To avoid bleach coupling, an additional separating layer d) must be arranged between two layer packets in this case. However, the method is also suitable for producing monochromatic negative images, an important application relating to the production of negative black / white images, as can be obtained by using a bleachable black dye.
Eine weiter Verwendung von monochromatischen Negativbildern besteht in der Herstellng von positiven Schwarzweißbildern. Der Farbstoff der erfindungsgemäßen Negativbilder übernimmt hierbei die Rolle des lichtabsorbierenden Silberhalogenids normaler photographischer Materialien. Bleichbare Farbstoffe, die für das erfindungsgemäße Verfahren geeignet sind, werden beispielsweise in den US-A-3 454 402, 3 443 933, 3 804 630, 3 716 368, 3 877 949, 3 623 874, 3 931 142 und 4 051 123 beschrieben.Another use of monochromatic negative images is in the production of positive black and white images. The dye of the negative images according to the invention takes on the role of the light-absorbing silver halide of normal photographic materials. Bleachable dyes which are suitable for the process according to the invention are described, for example, in US Pat. Nos. 3,454,402, 3,443,933, 3,804,630, 3,716,368, 3,877,949, 3,623,874, 3,931,142 and 4,051,123 described.
Die Zwischenschichten d) (Sperr- und Trennschichten) enthalten im allgemeinen nur reines Bindemittel, z. B. Gelatine, jedoch keinen Farbstoff und kein Silberhalogenid. Falls es für die Gesamtschichtenfolge günstig ist, kann aber gegebenenfalls auch eine bereits vorhandene Emulsionsschicht oder eine Filterschicht als Trennschicht dienen. Die Trennschicht kann außer Gelatine noch weitere Zusätze, wie die Farbbleichung hemmende Stoffe, zusätzliche Bindemittel, wie z. B. wasserlösliche Kolloide oder auch wasserunlösliche Dispersionspolymerisate enthalten, ferner auch die für den Aufbau der anderen photographischen Schichten üblichen Zusätze wie Weichmacher, Netzmittel, Lichtschutzmittel, Filterfarbstoffe, optische Aufheller, UV-Absorber oder Härtungsmittel.The intermediate layers d) (barrier and separating layers) generally contain only pure binder, e.g. B. gelatin, but no dye and no silver halide. If it is favorable for the overall layer sequence, an already existing emulsion layer or a filter layer can optionally also serve as a separating layer. In addition to gelatin, the separating layer can contain further additives, such as substances which inhibit color bleaching, additional binders, such as, for example B. contain water-soluble colloids or water-insoluble dispersion polymers, also the usual additives for the construction of the other photographic layers such as plasticizers, wetting agents, light stabilizers, filter dyes, optical brighteners, UV absorbers or curing agents.
Als hochempfindliche Silberhalojodidemulsionen (erste Schicht eines Schichtpakets von der Seite des Lichteinfalls betrachtet) werden normalerweise solche verwendet, welche Silberchlorid und/oder -bromid und Silberjodid enthalten. Der Jodidgehalt liegt normalerweise zwischen 0,1 und 10, vorzugsweise 1 und 5 Molprozent, der Rest besteht aus Silberchlorid und/oder -bromid (z. B. 0 bis 99,9 Molprozent Silberbromid).The highly sensitive silver haloiodide emulsions (first layer of a layer package viewed from the side of the light) are normally those which contain silver chloride and / or bromide and silver iodide. The iodide content is normally between 0.1 and 10, preferably 1 and 5 mol percent, the rest consists of silver chloride and / or bromide (e.g. 0 to 99.9 mol percent silver bromide).
Zur Herstellung dieser Emulsionen wird gewöhnlich Gelatine als Schutzkolloid verwendet; es kön- nen aber auch andere wasserlösliche Schutzkolloide wie Polyvinylalkohol oder Polyvinylpyrrolidon usw. verwendet werden; ferner kann ein Teil der Gelatine durch Dispersionen nichtwasserlöslicher hochmolekularer Stoffe ersetzt werden. Gebräuchlich ist z. B. die Verwendung von Dispersionspolymerisaten aus a,,8-ungesättigten Verbindungen wie Acrylsäurestern, Vinylestern und -äthern, Vinylchlorid, Vinylidenchlorid sowie aus anderen Gemischen und Copolymerisaten.Gelatin is usually used as a protective colloid to prepare these emulsions; It Kings - but NEN other water-soluble protective colloids such as polyvinyl alcohol or polyvinyl etc. are used; furthermore, part of the gelatin can be replaced by dispersions of non-water-soluble high-molecular substances. Common is z. B. the use of dispersion polymers of a ,, 8-unsaturated compounds such as acrylic acid esters, vinyl esters and vinyl ethers, vinyl chloride, vinylidene chloride and other mixtures and copolymers.
Die Emulsionen können auf übliche Schichtträger für photographisches Aufzeichnungsmaterial aufgebracht werden. Gegebenenfalls kann ein Gemisch aus mehreren Kolloiden zum Dispergieren der Silberhalogenide verwendet werden.The emulsions can be applied to conventional supports for photographic recording material. Optionally, a mixture of several colloids can be used to disperse the silver halides.
Der Träger kann beispielsweise aus gegebenenfalls pigmentiertem Cellulosetriacetat oder Polyester bestehen. Wenn er aus Papierfilz besteht, muß dieser beidseitig lackiert oder mit Polyäthylen beschichtet sein.The carrier can consist, for example, of pigmented cellulose triacetate or polyester. If it is made of paper felt, it must be coated on both sides or coated with polyethylene.
Die Verarbeitung der belichteten Silberfarbbleichmaterialien erfolgt in üblicher Weise und umfaßt die Silberentwicklung, die Farbbleichung, die Silberbleichung und die Fixierung und anschließende sowie gegebenenfalls auch zwischen den einzelnen Stufen liegende Wässerungen (vgl. z. B. DE-A-2448443). Die Farbbleichung und die Silberbleichung, gegebenenfalls auch die Fixierung, können in einer einzigen Behandlungsstufe zusammengefaßt werden. Es ist auch möglich, Entwicklerverbindungen oder Entwicklervorläufer in die Emulsionsschichten einzubauen. Man sorgt dabei durch geeignete Pufferung dafür, daß diese Substanzen in der trockenen Schicht während der Lagerung inaktiv bleiben. Man benötigt in diesem Fall zur Ingangsetzung der Entwicklung lediglich ein Aktivatorbad mit hohem pH-Wert, das frei von Entwicklersubstanzen sein kann.The exposed silver color bleaching materials are processed in the customary manner and include silver development, color bleaching, silver bleaching and fixing and subsequent rinsing and, if appropriate, also between the individual steps (see, for example, DE-A-2448443). Color bleaching and silver bleaching, and possibly also fixation, can be combined in a single treatment step. It is also possible to incorporate developer compounds or developer precursors into the emulsion layers. Suitable buffering ensures that these substances remain inactive in the dry layer during storage. In this case, all that is required to start development is an activator bath with a high pH, which can be free of developer substances.
Zur Silberentwicklung können Bäder üblicher Zusammensetzung verwendet werden, z. B. solche, die als Entwicklersubstanz Hydrochinon oder zusätzlich noch 1-Phenyl-3-pyrazolidinon, jedoch keine Silberkomplexbildner enthalten. Außerdem kann es günstig sein, wenn das Silberentwicklungsbad, wie in der schweizerischen Patentschrift 405 929 beschrieben, noch zusätzlich einen Farbbleichkatalysator enthält. Aktivatorbäder enthalten als wirksame Substanzen lediglich starke Alkalien und gegebenenfalls weitere Zusätze wie Puffersubstanzen, Netzmittel usw.Baths of conventional composition can be used for silver development, e.g. B. those that contain hydroquinone as developer or additionally 1-phenyl-3-pyrazolidinone, but do not contain silver complexing agents. It may also be advantageous if the silver developing bath, as described in Swiss Patent 405 929, additionally contains a color bleaching catalyst. Activator baths contain only strong alkalis and possibly other additives such as buffer substances, wetting agents etc. as active substances.
Als Farbbleicher - sofern die Farbbleichung als getrennte Behandlungsstufe durchgeführt wird - werden mit Vorteil solche verwendet, die neben einer starken Säure, einem wasserlöslichen Jodid und einem Oxydationsschutzmittel für das Jodid einen Farbbleichkatalysator enthalten. Kombinierte Farb-und Silberfarbbleichbäder enthalten neben den angegebenen Komponenten in der Regel noch ein wasserlösliches Oxydationsmittel. Geeignete Farbbleichkatalysatoren sind in erster Linie Diazinverbindungen, z. B. in den DE-B-2 010 280, 2 144 298 und 2 144 297, in der FR-A-1 489 460, in der US-A-2 270 118 sowie in der DE-A-2 448 443 beschrieben.As color bleachers - if the color bleaching is carried out as a separate treatment step - those are advantageously used which, in addition to a strong acid, a water-soluble iodide and an antioxidant for the iodide, contain a color bleaching catalyst. Combined color and silver color bleaching baths generally contain a water-soluble oxidizing agent in addition to the specified components. Suitable color bleaching catalysts are primarily diazine compounds, e.g. B. in DE-B-2 010 280, 2 144 298 and 2 144 297, in FR-A-1 489 460, in US-A-2 270 118 and in DE-A-2 448 443 .
Unter starken Säuren sind hier solche zu verstehen, welche dem Farbbleichbad bzw. dem kombinierten Farb- und Silberbleichbad einen pH-Wert von höchstens 2 verleihen. Es können also z. B. Salzsäure, Phosphorsäure und insbesondere Schwefelsäure oder Sulfaminsäure verwendet werden. Als wasserlösliches Jodid kann man Alkalijodide verwenden, wie beispielsweise Kaliumjodid oder Natriumjodid.Strong acids are to be understood here as those which give the color bleach bath or the combined color and silver bleach bath a pH value of at most 2. So it can. As hydrochloric acid, phosphoric acid and especially sulfuric acid or sulfamic acid can be used. Alkali iodides such as potassium iodide or sodium iodide can be used as the water-soluble iodide.
Geeignete Oxydationsmittel sind Nitrosoverbindungen, wie z. B. p-Nitrosodimethylanilin, Nitroverbindungen, wie z. B. aromatische Nitroverbindungen und vorzugsweise aromatische Mono- oder Dinitrobenzolsulfonsäuren, z. B. m-Nitrobenzolsulfonsäure.Suitable oxidizing agents are nitroso compounds, such as. B. p-nitrosodimethylaniline, nitro compounds such as. B. aromatic nitro compounds and preferably aromatic mono- or dinitrobenzenesulfonic acids, e.g. B. m-nitrobenzenesulfonic acid.
Als Oxydationsschutzmittel verwendet man insbesondere Reduktone oder wasserlösliche Mercaptoverbindungen. Geeignete Reduktonesind insbesondere aci-Reduktone mit einer 3-Carbonyl-endiol-(1,2)-Gruppierung wie Reduktin, Triose-Redukton oder vorzugsweise Ascorbinsäure.Reductones or water-soluble mercapto compounds are used in particular as antioxidants. Suitable reductones are especially aci-reductones with a 3-carbonyl-endiol (1,2) grouping such as reductin, triose reductone or preferably ascorbic acid.
Als Mercaptoverbindungen kommen solche der Formel HSA(B)m in Frage, worin A ein aliphatisches, cycloalphatisches, araliphatisches, aromatisches oder heterocyclisches Brückenglied, B ein wasserlöslichmachender Rest und m eine ganze Zahl von höchstens 4 ist (DE-A-2 258 076, 423 819).Suitable mercapto compounds are those of the formula HSA (B) m in which A is an aliphatic, cycloalphatic, araliphatic, aromatic or heterocyclic bridge member, B is a water-solubilizing radical and m is an integer of at most 4 (DE-A-2 258 076, 423 819).
Das Silberfixierbad kann in bekannter und üblicher Weise zusammengesetzt sein. Als Fixiermittel geeignet ist z. B. Natriumthiosulfat oder vorzugsweise Ammoniumthiosulfat, gewünschtenfalls mit Zusätzen wie Natriumbisulfit, Natriummetabisulfit und/oder Ammoniumbisulfit sowie gegebenenfalls Komplexierungsmittel, wie Aethylendiamintetraessigsäure.The silver fixing bath can be composed in a known and customary manner. Suitable as a fixative is, for. B. sodium thiosulfate or preferably ammonium thiosulfate, if desired with additives such as sodium bisulfite, sodium metabisulfite and / or ammonium bisulfite and optionally complexing agents such as ethylenediaminetetraacetic acid.
Alle Behandlungsbäder können weitere übliche Zusätze wie z. B. Härtungsmittel, Netzmittel, optische Aufhalter oder UV-Schutzmittel enthalten.All treatment baths can contain other common additives such as. B. contain hardening agents, wetting agents, optical retainers or UV protection agents.
Im nachfolgenden Beispiel beziehen sich, sofern nicht anders angegeben, Teile und Prozente auf das Gewicht.Unless stated otherwise, parts and percentages in the following example relate to the weight.
Auf einen transparenten Polyesterträger werden in der angegebenen Reihenfolge folgende Schichten aufgetragen:
- 1. Eine Schicht, die eine chemisch verschleierte und mit einem Entwicklungsverzögerer (Inhibitor) behandelte Core-shell-Emulsion mit
einem Silbergehalt von 0,8 g/m2,sowie 0,3 g/m2 eines schwarzen bleichbaren Farbstoffs der Formel
Kantenlänge 0,55 µm) wird während einer Stunde bei 60°C miteiner Lösung von 0,01% Natriumformaldehydsulfoxylat (HOCH2SO2Na · 2H20) und 0,001% Goldchlorwasserstoffsäure (HAuC14) chemisch verschleiert. Durch Zugabe von 3 mg 1-Phenyl-5-mercaptotetrazol pro g Silber, in Form einer 1%igen Lösung, wird die verschleierte Emulsion inhibiert: Auf die so vorbehandelten Silberbromidkristalle wird eineSilberbromidschale von 0,02 µm Dicke aufgefällt. - 2. Eine Gelatine-Zwischenschicht mit einem Auftragsgewicht von 5 g/m2 Gelatine.
- 3. Eine grün sensibilisierte Silberjodobromidgelatineemulsionsschicht (95 Mol-% AgBr, 5 Mol-% AgJ) mit
einem Auftragsgewicht von 0,8 g Silber/m2.
- 1. A layer containing a chemically veiled and treated with a development retardant (inhibitor) core-shell emulsion with a silver content of 0.8 g / m 2 , and 0.3 g / m 2 of a black bleachable dye of the formula
- 2. A gelatin intermediate layer with an application weight of 5 g / m 2 gelatin.
- 3. A green sensitized silver iodobromide gelatin emulsion layer (95 mol% AgBr, 5 mol% AgJ) with an application weight of 0.8 g silver / m 2 .
Eine Probe des so beschichteten Materials wird unter einem Verlaufskeil mit grünem Licht belichtet und wie folgt verarbeitet:
In der nachfolgenden Tabelle 1 sind die gemessenen Transmissionsdichten wiedergegeben:
Claims (11)
that the photographic material, where it consists of more than one layer assembly, optionally contains intermediate layers d) between the layer assemblies, and
that the developing is carried out in a developer solution which is free of silver-complexing agent.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CH558980 | 1980-07-22 | ||
| CH5589/80 | 1980-07-22 |
Publications (3)
| Publication Number | Publication Date |
|---|---|
| EP0044813A2 EP0044813A2 (en) | 1982-01-27 |
| EP0044813A3 EP0044813A3 (en) | 1982-11-17 |
| EP0044813B1 true EP0044813B1 (en) | 1985-06-19 |
Family
ID=4296115
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| EP81810291A Expired EP0044813B1 (en) | 1980-07-22 | 1981-07-16 | Process for the formation of negative colour images according to the silver dye-bleaching process, and the silver dye-bleaching material used in this process |
Country Status (4)
| Country | Link |
|---|---|
| US (1) | US4374914A (en) |
| EP (1) | EP0044813B1 (en) |
| JP (1) | JPH0151180B2 (en) |
| DE (1) | DE3171015D1 (en) |
Families Citing this family (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE3366751D1 (en) * | 1982-02-22 | 1986-11-13 | Ciba Geigy Ag | Negative working photographic silver dye-bleach material |
| JPS59133542A (en) * | 1983-01-21 | 1984-07-31 | Fuji Photo Film Co Ltd | Method for developing silver halide photosensitive material |
| JPS6024546A (en) * | 1983-07-20 | 1985-02-07 | Konishiroku Photo Ind Co Ltd | Color photographic sensitive silver halide material |
| US4568189A (en) * | 1983-09-26 | 1986-02-04 | The United States Of America As Represented By The Secretary Of The Navy | Apparatus and method for aligning a mask and wafer in the fabrication of integrated circuits |
| JPS60162252A (en) * | 1984-02-02 | 1985-08-24 | Konishiroku Photo Ind Co Ltd | Silver halide color photosensitive material |
| JPS62261251A (en) * | 1986-05-07 | 1987-11-13 | Matsushita Electric Ind Co Ltd | Ring-off method for bidirectional communication equipment |
| US4995185A (en) * | 1989-03-02 | 1991-02-26 | Cheng Chiang Ming | Picture plate using both transpiercing light and reflection light |
| JP3427212B2 (en) * | 1992-11-13 | 2003-07-14 | 松下電工株式会社 | Reciprocating electric razor |
Family Cites Families (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CH564795A5 (en) * | 1970-11-03 | 1975-07-31 | Mitsubishi Paper Mills Ltd | Silver dye bleach material - of colour negative type with low-sensitivity prefogged/high sensitivity emulsions |
| US3708300A (en) * | 1970-11-19 | 1973-01-02 | Eastman Kodak Co | Silver-dye-bleach photographic materials |
| JPS5121579A (en) * | 1974-08-17 | 1976-02-20 | Freunt Ind Co Ltd | Zoryumataha koochinguekitono teiryokyusosochi |
| CA1057109A (en) * | 1975-04-10 | 1979-06-26 | Nicholas H. Groet | Enhancement of interimage effects |
| CH633641A5 (en) * | 1977-07-21 | 1982-12-15 | Ciba Geigy Ag | METHOD FOR PRODUCING MASKED POSITIVE COLOR IMAGES BY THE SILVER COLORING METHOD. |
| DE3066277D1 (en) * | 1979-08-01 | 1984-03-01 | Ciba Geigy Ag | Process for the production of masked positive colour images by the silver dye bleach process and the photographic silver dye bleach material for use therein |
-
1981
- 1981-07-13 US US06/282,777 patent/US4374914A/en not_active Expired - Fee Related
- 1981-07-16 DE DE8181810291T patent/DE3171015D1/en not_active Expired
- 1981-07-16 EP EP81810291A patent/EP0044813B1/en not_active Expired
- 1981-07-22 JP JP56113798A patent/JPH0151180B2/ja not_active Expired
Also Published As
| Publication number | Publication date |
|---|---|
| EP0044813A2 (en) | 1982-01-27 |
| DE3171015D1 (en) | 1985-07-25 |
| US4374914A (en) | 1983-02-22 |
| JPS5753748A (en) | 1982-03-30 |
| EP0044813A3 (en) | 1982-11-17 |
| JPH0151180B2 (en) | 1989-11-01 |
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