EP0039313B1 - Process for the production of a photographic image by the silver-dye bleaching process and the photographic material intended for this process - Google Patents
Process for the production of a photographic image by the silver-dye bleaching process and the photographic material intended for this process Download PDFInfo
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- EP0039313B1 EP0039313B1 EP81810157A EP81810157A EP0039313B1 EP 0039313 B1 EP0039313 B1 EP 0039313B1 EP 81810157 A EP81810157 A EP 81810157A EP 81810157 A EP81810157 A EP 81810157A EP 0039313 B1 EP0039313 B1 EP 0039313B1
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- Prior art keywords
- dye
- silver halide
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- image
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- 239000000463 material Substances 0.000 title claims description 52
- 238000000034 method Methods 0.000 title claims description 32
- 238000004061 bleaching Methods 0.000 title claims description 27
- 230000008569 process Effects 0.000 title claims description 26
- 238000004519 manufacturing process Methods 0.000 title claims description 8
- 239000010410 layer Substances 0.000 claims description 138
- 239000000975 dye Substances 0.000 claims description 78
- 239000004332 silver Substances 0.000 claims description 75
- 229910052709 silver Inorganic materials 0.000 claims description 75
- 239000000839 emulsion Substances 0.000 claims description 62
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims description 44
- -1 silver halide Chemical class 0.000 claims description 33
- 238000009792 diffusion process Methods 0.000 claims description 9
- 238000012545 processing Methods 0.000 claims description 5
- 239000007844 bleaching agent Substances 0.000 claims description 4
- 239000011241 protective layer Substances 0.000 claims description 4
- 238000010521 absorption reaction Methods 0.000 claims description 3
- 239000003054 catalyst Substances 0.000 claims description 3
- 230000035945 sensitivity Effects 0.000 claims description 3
- 108010010803 Gelatin Proteins 0.000 description 7
- 239000008273 gelatin Substances 0.000 description 7
- 229920000159 gelatin Polymers 0.000 description 7
- 235000019322 gelatine Nutrition 0.000 description 7
- 235000011852 gelatine desserts Nutrition 0.000 description 7
- 230000000694 effects Effects 0.000 description 4
- AJDUTMFFZHIJEM-UHFFFAOYSA-N n-(9,10-dioxoanthracen-1-yl)-4-[4-[[4-[4-[(9,10-dioxoanthracen-1-yl)carbamoyl]phenyl]phenyl]diazenyl]phenyl]benzamide Chemical compound O=C1C2=CC=CC=C2C(=O)C2=C1C=CC=C2NC(=O)C(C=C1)=CC=C1C(C=C1)=CC=C1N=NC(C=C1)=CC=C1C(C=C1)=CC=C1C(=O)NC1=CC=CC2=C1C(=O)C1=CC=CC=C1C2=O AJDUTMFFZHIJEM-UHFFFAOYSA-N 0.000 description 4
- 239000001043 yellow dye Substances 0.000 description 4
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- 230000015572 biosynthetic process Effects 0.000 description 2
- ZEUDGVUWMXAXEF-UHFFFAOYSA-L bromo(chloro)silver Chemical compound Cl[Ag]Br ZEUDGVUWMXAXEF-UHFFFAOYSA-L 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
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- 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 1
- 229920002284 Cellulose triacetate Polymers 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- 229910021607 Silver chloride Inorganic materials 0.000 description 1
- 229910021612 Silver iodide Inorganic materials 0.000 description 1
- 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
- IEIREBQISNYNTN-UHFFFAOYSA-K [Ag](I)(Br)Cl Chemical compound [Ag](I)(Br)Cl IEIREBQISNYNTN-UHFFFAOYSA-K 0.000 description 1
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- 239000012790 adhesive layer Substances 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 238000000149 argon plasma sintering Methods 0.000 description 1
- OIPQUBBCOVJSNS-UHFFFAOYSA-L bromo(iodo)silver Chemical compound Br[Ag]I OIPQUBBCOVJSNS-UHFFFAOYSA-L 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 230000008878 coupling Effects 0.000 description 1
- 238000010168 coupling process Methods 0.000 description 1
- 238000005859 coupling reaction Methods 0.000 description 1
- 125000004093 cyano group Chemical group *C#N 0.000 description 1
- 238000000586 desensitisation Methods 0.000 description 1
- 125000005331 diazinyl group Chemical class N1=NC(=CC=C1)* 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000000499 gel Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 238000009434 installation Methods 0.000 description 1
- 229920001778 nylon Polymers 0.000 description 1
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- ZUNKMNLKJXRCDM-UHFFFAOYSA-N silver bromoiodide Chemical compound [Ag].IBr ZUNKMNLKJXRCDM-UHFFFAOYSA-N 0.000 description 1
- 229940045105 silver iodide Drugs 0.000 description 1
- HKZLPVFGJNLROG-UHFFFAOYSA-M silver monochloride Chemical compound [Cl-].[Ag+] HKZLPVFGJNLROG-UHFFFAOYSA-M 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 a photographic image by the silver color bleaching process, the use of the process for producing photographic images and a suitable photographic material.
- a common material for the silver color bleaching process contains at least one emulsion layer stained with an imagewise bleachable dye. Such a material is exposed, developed and finally processed into an image by bleaching the dye depending on the developed metallic silver and removing the excess silver halide and metallic silver from the material.
- multilayer materials for images in natural colors which contain a red-sensitive silver halide emulsion layer stained with cyan dye on a transparent or reflective support, above that a green-sensitive silver halide emulsion layer stained with magenta dye, and silver-halide emulsion layer stained too blue with yellow dye. Filter layers and other intermediate layers can also be located between these emulsion layers.
- the image dye and the silver halide emulsion assigned to this dye are each in the same layer.
- CH-A No. 383335 proposed to influence the gradation curve of a silver color bleaching material, especially in the shoulder part, by arranging an emulsion layer containing image dye and an emulsion layer free of image dye one above the other in such a way that the dye-free layer over the dye-containing layer faces the light source Side lies.
- the reverse arrangement in which the image dye-containing emulsion layer is arranged over a dye-free emulsion layer on the side facing the incidence of light, is described in CH-A No. 456434. With this arrangement, it is possible to favorably influence the gradation, especially in the foot part of the curve.
- a common feature of the layer structure in all of the aforementioned patents is the use of image-effective layers which contain either a light-sensitive silver halide emulsion layer alone or a silver halide emulsion layer with image dyes.
- GB-A No. 421727 describes a silver color bleaching material which contains in one layer a light-sensitive silver halide emulsion without dye and under, above or on both sides of this layer a silver-halide-free light-insensitive dye layer.
- the remote bleaching that occurs in the adjacent layer during the color bleaching process is due to the fact that the color bleaching catalysts used, e.g.
- Diazine compounds are reduced to dihydro compound on silver and are able to migrate in this state over the short distance to the neighboring dye layers.
- the processes described in the aforementioned citations CH-A Nos. 383335, 456434 and 465804 are based on the same principle.
- a silver color bleaching material in which at least one silver halide emulsion layer containing image dye is divided into two components in such a way that a silver halide-free image dye layer is arranged on the side facing the light directly above a silver halide emulsion layer containing image dye, compared to conventional materials and also opposite such materials in which the image dye and emulsion are part are separated wisely, but all layers, or at least the layers facing the incident light containing a silver halide emulsion, have surprising advantages: the silver halide-free dye layer arranged over the emulsion layer largely absorbs the scattered light originating from layers located further up the layer structure, and the stronger, the more this deviates from the vertical direction of incidence and therefore has to measure a greater layer thickness.
- the entire image dye used in a pair of layers can be incorporated into the upper, silver halide-free layer.
- part of the image dye is housed in the emulsion-containing layer.
- the present invention thus relates to a process for producing a photographic image by the silver color bleaching process by exposure, silver development, color bleaching, silver bleaching and fixing and using a photographic material which contains photosensitive silver halide and dye layers, the dye layers in each case immediately above the light-sensitive silver halide layers are arranged, characterized in that a photographic material with at least one light-sensitive silver halide emulsion layer, which contains a diffusion-resistant, bleachable image dye, and immediately above, on the side facing the light source, contains a silver halide-free, a diffusion-resistant, bleachable image dye Contains layer, exposed imagewise and processed in the presence of a color bleaching catalyst to a color image, the color image exclusively ch is produced by image dyes present in the photographic material before exposure.
- the invention further relates to the photographic material suitable for the process according to the invention and the use of this process for the production of photographic images.
- the diffusion-resistant, bleachable cyan, magenta or yellow dye contained in the light-sensitive silver halide emulsion layer and the dye contained in the silver halide-free layer are generally the same dye.
- the photographic material may contain one or more such a pair of layers, e.g. in a trichromatic material one for the two primary colors cyan and magenta.
- a trichromatic material one for the two primary colors cyan and magenta.
- the arrangement according to the invention has no effect, however, since no stray radiation can arrive from layers located further up.
- further layers can be contained in the photographic material, e.g. Protective layers, separating layers, filter layers, it being possible for individual of these layers, if they are adjacent to a silver halide emulsion layer, to also contain image dyes.
- the known bleachable azo dyes can be used as image dyes, in particular water-soluble, diffusion-resistant azo dyes, such as those e.g. are listed in CH-A No. 572230. Furthermore, oil-soluble dyes and pigments can also be used, provided that they are bleached sufficiently quickly and completely by the usual color bleaching baths.
- the layers C1 / C2 and M2 / M3 form layer pairs according to the present invention.
- the additional layer M1 containing magenta dye serves on the one hand as an image dye layer and on the other hand simultaneously as an additional separating layer between the two layers C2 and M2.
- the yellow colored layer Y1 acts in the same sense.
- the usual opaque or transparent materials such as glass, cellulose triacetate, polyester, coated paper or artificial papers made of polystyrene or nylon fibers serve as supports for the photographic layers.
- Silver halide-free, image dye-containing layers can optionally also serve as protective layers by protecting the emulsion layers underneath from scratching and other mechanical stress. In particular, they can also perform this function during the coating process, where they e.g. applied as the top layer of a multi-layer package, while drying it can protect the underlying pressure-sensitive emulsion layer from direct contact by rolling and the formation of pressure fog.
- Silver halide emulsions or mixed emulsions are preferably used as light-sensitive silver halide emulsions. Since part of the incident light is always absorbed by the existing image dyes in silver color bleaching materials, it is generally advantageous to to use sensitive silver halide emulsions. This applies in particular when, as with the usual materials for images in natural colors, the emulsions are sensitized in the spectral ranges which correspond to the respective absorption maximum of the assigned image dye. The optical desensitization, ie the loss of actinic light, is particularly strong in this case. The method can also be used for the production of so-called false color images by using emulsions which are not sensitized in the main absorption area of the assigned image dye.
- silver halide emulsions of the cubic monodisperse type as are known by known methods, e.g. can be generated by the double jet method, proven to be particularly suitable. This is particularly the case where the inherently steep gradation of the monodisperse emulsions does not interfere.
- the cubic monodisperse emulsions also have the advantage of providing particularly sharp images in the process according to the invention.
- polydisperse emulsions can be incorporated into the material according to the invention. This leads to a flattening of the gradation without, however, significantly affecting the resolving power of the material according to the invention.
- the known processes are used, which include the usual process stages such as silver development, color bleaching, silver bleaching and fixation, and optionally one or more washing stages, the silver bleaching optionally being combined with the color bleaching and / or the fixation to form a single processing stage can.
- Suitable processing methods are e.g. in DE-A Nos. 1924723, 2258076, 2423814, 2448433, 2547720 and 2651969.
- the photographic materials used according to the invention are particularly suitable for the production of microfilms.
- a microfilm, with which positive color images can be produced directly in one work step, can be produced as indicated in Example 1.
- a photographic material according to the present invention is produced by successively applying and drying the corresponding gelatin layers on a polyester support S.
- the following table shows the weight amounts of silver (Ag), gelatin (gel) and dye (FS) applied for each layer in milligrams per square meter.
- the silver halide emulsion used for the cyano emulsion layer 2 was previously sensitized to red light and that for the magenta emulsion layer to green light.
- a second photographic material with a conventional layer sequence is produced using the same silver halide emulsions and image dyes, the amount of silver and dye in the individual layers being selected such that approximately the same optical density results after exposure and processing:
- FIG. 1 This layer arrangement corresponds to FIG. 2.
- the numbers in FIGS. 1 and 2 indicate dry layer thicknesses in micrometers.
- the layer designated Z in FIG. 2 can additionally contain colloidal silver and / or a bleachable yellow azo dye. In this case, it acts as a yellow filter layer, which is intended to prevent the action of blue radiation on the green- and red-sensitive layers.
- the yellow filter layer is completely decolorized during color bleaching. The installation of the yellow filter layer is only necessary if the yellow layer on top does not have a sufficient filter effect.
- the resulting conventional material has a total layer thickness which is approximately 25% higher due to the use of larger amounts of gelatin. This increased value is necessary to give the material the desired sensitometric properties. However, the increased layer thickness has an unfavorable effect on the image sharpness, as can be seen from the results of the photographic evaluation.
- a strip of both materials is exposed and then processed as follows at a temperature of 24 ° C:
- both materials - as intended - show practically identical sensitometric values. However, there is a difference with regard to the photographic sharpness or the resolution.
- a sharp edge contact method is mapped onto the material.
- the density curve is measured with a microdensitometer in the vicinity of the transition from the exposed to the unexposed part. The sharper the better, the steeper the transition from the exposed to the unexposed area. The steepness of this transition is calculated according to a method described by the authors mentioned above and means, expressed in numbers, the increase in density per micrometer on a measurement line running perpendicular to the exposed edge.
- the material according to the invention gives a value of 14.3 -10 -3
- the comparison material with a conventional layer structure on the other hand, only a value of 10.6.10-3.
- This improvement in the sharpness performance is due to the lower layer thickness of the material according to the invention and to the reduction in light scattering due to the layer structure according to the invention.
- Example 2 The experiment described in Example 1 and the associated FIG. 1 is repeated, but using a polydisperse silver bromoiodide emulsion with an average particle diameter of 0.20 ⁇ m, the crystals of which contain 2.6 mol% of silver iodide, instead of the cubic monodisperse emulsion. Furthermore, instead of the cyan dye mentioned in Example 1, one of the formula The following proportions of silver, dye and gelatin are used in the cyan emulsion layer and cyan color layer: The images produced with this material also show a clear improvement in sharpness compared to images made from the conventional material according to FIG. 2.
- the intermediate layer Z2 is additionally formed into a bleachable yellow filter layer by incorporating 21 mg / m 2 of colloidal silver and 17 mg / m 2 of the yellow dye described in Example 1.
- This layer arrangement also results in a significant improvement in image sharpness compared to the conventional material according to FIG. 2.
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- Physics & Mathematics (AREA)
- General Physics & Mathematics (AREA)
- Silver Salt Photography Or Processing Solution Therefor (AREA)
Description
Die vorliegende Erfindung betrifft ein neues Verfahren zur Herstellung eines photographischen Bildes nach dem Silberfarbbleichverfahren, die Verwendung des Verfahrens zur Herstellung von photographischen Bildern sowie ein geeignetes photographisches Aufzeichnungsmaterial.The present invention relates to a new process for producing a photographic image by the silver color bleaching process, the use of the process for producing photographic images and a suitable photographic material.
Ein übliches Material für das Silberfarbbleichverfahren enthält mindestens eine mit einem bildmässig bleichbaren Farbstoff angefärbte Emulsionsschicht. Ein solches Material wird belichtet, entwickelt und schliesslich zu einem Bild verarbeitet, indem man den Farbstoff in Abhängigkeit vom entwickelten metallischen Silber bleicht und das überschüssige Silberhalogenid und metallische Silber aus dem Material entfernt. Besonders wichtig sind mehrschichtige Materialien für Bilder in natürlichen Farben, die auf einem transparenten oder reflektierenden Träger eine rotempfindliche mit Cyanfarbstoff angefärbte Silberhalogenidemulsionsschicht, darüber eine grünempfindliche mit Magentafarbstoff angefärbte Silberhalogenidemulsionsschicht und zu obersteine blauempfindliche mit Gelbfarbstoff angefärbte Silberhalogenidemulsionsschicht enthalten. Zwischen diesen Emulsionsschichten können sich ausserdem Filterschichten und andere Zwischenschichten befinden.A common material for the silver color bleaching process contains at least one emulsion layer stained with an imagewise bleachable dye. Such a material is exposed, developed and finally processed into an image by bleaching the dye depending on the developed metallic silver and removing the excess silver halide and metallic silver from the material. Of particular importance are multilayer materials for images in natural colors, which contain a red-sensitive silver halide emulsion layer stained with cyan dye on a transparent or reflective support, above that a green-sensitive silver halide emulsion layer stained with magenta dye, and silver-halide emulsion layer stained too blue with yellow dye. Filter layers and other intermediate layers can also be located between these emulsion layers.
Beim konventionellen Aufbau eines Silberfarbbleichmaterials befinden sich der Bildfarbstoff und die diesem Farbstoff zugeordnete Silberhalogenidemulsion jeweils in der gleichen Schicht.In the conventional construction of a silver color bleaching material, the image dye and the silver halide emulsion assigned to this dye are each in the same layer.
Es hat sich aber verschiedentlich als Vorteil erwiesen, von diesem Prinzip abzuweichen und wenigstens einen Teil der lichtempfindlichen Silberhalogenidemulsion in einer der Bildfarbstoff enthaltenden Schicht benachbarten Schicht unterzubringen.However, it has proven advantageous in various ways to deviate from this principle and to accommodate at least part of the light-sensitive silver halide emulsion in a layer adjacent to the layer containing the image dye.
So wird z.B. in CH-A Nr. 383335 vorgeschlagen, die Gradationskurve eines Silberfarbbleichmaterials, insbesondere im Schulterteil, dadurch zu beeinflussen, dass man eine Bildfarbstoff enthaltende und eine von Bildfarbstoff freie Emulsionsschicht derart übereinander anordnet, dass die farbstofffreie Schicht über der farbstoffhaltigen Schicht auf der der Lichtquelle zugewandten Seite liegt. Die umgekehrte Anordnung, bei welcher die Bildfarbstoff enthaltende Emulsionsschicht über einer farbstofffreien Emulsionsschicht auf der dem Lichteinfall zugewandten Seite angeordnet ist, wird in CH-A Nr. 456434 beschrieben. Es gelingt mit dieser Anordnung, die Gradation vor allem im Fussteil der Kurve günstig zu beeinflussen. In CH-A Nr. 465804 wird schliesslich noch eine Anordnung beschrieben, bei welcher eine Bildfarbstoff enthaltende Silberhalogenidemulsionsschicht zwischen zwei farbstofffreien lichtempfindlichen Emulsionsschichten angeordnet wird. Mit dieser Massnahme erreicht man eine speziell grosse Freiheit in der Beeinflussung der Gradationskurve des Silberfarbbleichmaterials.For example, in CH-A No. 383335 proposed to influence the gradation curve of a silver color bleaching material, especially in the shoulder part, by arranging an emulsion layer containing image dye and an emulsion layer free of image dye one above the other in such a way that the dye-free layer over the dye-containing layer faces the light source Side lies. The reverse arrangement, in which the image dye-containing emulsion layer is arranged over a dye-free emulsion layer on the side facing the incidence of light, is described in CH-A No. 456434. With this arrangement, it is possible to favorably influence the gradation, especially in the foot part of the curve. Finally, in CH-A No. 465804 an arrangement is described in which an image dye-containing silver halide emulsion layer is arranged between two dye-free photosensitive emulsion layers. With this measure, a particularly great freedom is achieved in influencing the gradation curve of the silver color bleaching material.
In US-A Nr. 2391198 wird vorgeschlagen, zwischen zwei Bildfarbstoff enthaltenden Silberhalogenidemulsionsschichten eine dritte, farbstofffreie Emulsionsschicht anzuordnen, wobei diese farblose Schicht dazu dient, aus den Nachbarschichten durch Diffusion eingewanderte Farbstoffe bei der späteren Farbbleichung auszubleichen, um so einerseits unerwünschte Farbkopplungen zwischen den gefärbten Emulsionsschichten, andererseits aber auch die Bildung eines zurückbleibenden Farbschleiers zu unterbinden.In US-A No. 2391198 it is proposed to arrange a third, dye-free emulsion layer between two image dye-containing silver halide emulsion layers, this colorless layer being used to bleach dyes which have migrated from the neighboring layers by diffusion during the later color bleaching, in order to avoid undesired color couplings between the dyed ones Emulsion layers, on the other hand to prevent the formation of a residual color haze.
In US-A Nr. 2183394 und in GB-A Nr. 483464 werden Anordnungen beschrieben, in welchen gefärbte und ungefärbte Silberhalogenidemulsionsschichten nebeneinander verwendet werden, wobei die ungefärbten Emulsionsschichten nach der Silberentwicklung mit weiteren Farbstoffen angefärbt werden, um damit bestimmte Farbeffekte zu erzielen.In US-A No. 2183394 and in GB-A No. 483464 arrangements are described in which colored and uncolored silver halide emulsion layers are used side by side, the uncolored emulsion layers being colored with further dyes after silver development in order to achieve certain color effects.
Gemeinsames Merkmal des Schichtaufbaus in all diesen vorerwähnten Patentschriften ist die Verwendung von bildwirksamen Schichten, die entweder eine lichtempfindliche Silberhalogenidemulsionsschicht allein oder eine Silberhalogenidemulsionsschicht mit Bildfarbstoffen enthalten. Im Gegensatz dazu wird in GB-A Nr. 421727 ein Silberfarbbleichmaterial beschrieben, welches in einer Schicht eine lichtempfindliche Silberhalogenidemulsion ohne Farbstoff und unter, über oder zu beiden Seiten dieser Schicht eine silberhalogenidfreie lichtunempfindliche Farbstoffschicht enthält. Die beim Farbbleichprozess eintretende Fernbleichung in die benachbarte Schicht kommt dadurch zustande, dass die dabei verwendeten Farbbleichkatalysatoren, z.B. Diazinverbindungen, am Bildsilber zur Dihydroverbindung reduziert werden und in diesem Zustand über die kurze Strecke bis zu den benachbarten Farbstoffschichten zu wandern vermögen. Auf dem gleichen Prinzip beruhen auch die in den vorerwähnten Zitaten CH-A Nrn. 383335, 456434 und 465804 beschriebenen Verfahren.A common feature of the layer structure in all of the aforementioned patents is the use of image-effective layers which contain either a light-sensitive silver halide emulsion layer alone or a silver halide emulsion layer with image dyes. In contrast, GB-A No. 421727 describes a silver color bleaching material which contains in one layer a light-sensitive silver halide emulsion without dye and under, above or on both sides of this layer a silver-halide-free light-insensitive dye layer. The remote bleaching that occurs in the adjacent layer during the color bleaching process is due to the fact that the color bleaching catalysts used, e.g. Diazine compounds are reduced to dihydro compound on silver and are able to migrate in this state over the short distance to the neighboring dye layers. The processes described in the aforementioned citations CH-A Nos. 383335, 456434 and 465804 are based on the same principle.
Die oben beschriebenen photographischen Materialien zeigen jedoch hinsichtlich Bildschärfe und Auflösungsvermögen noch gewisse Nachteile, die verbesserungsbedürftig sind.The photographic materials described above, however, still have certain disadvantages in terms of image sharpness and resolution, which need to be improved.
Aufgabe der vorliegenden Erfindung ist es deshalb, ein Verfahren zurHerstellung eines photographischen Bildes nach dem Silberfarbbleichverfahren bereitzustellen, welches diese Nachteile überwindet und photographische Bilder von z.B. besonders hoher Bildschärfe liefert.It is therefore an object of the present invention to provide a method for producing a photographic image according to the silver color bleaching process which overcomes these disadvantages and provides photographic images of e.g. delivers particularly high image sharpness.
Es wurde nun gefunden, dass ein Silberfarbbleichmaterial, bei welchem mindestens eine Bildfarbstoff enthaltende Silberhalogenidemulsionsschicht derart in zwei Komponenten aufgeteilt ist, dass eine silberhalogenidfreie Bildfarbstoffschicht auf der dem Lichteinfall zugekehrten Seite unmittelbar über einer ihr zugeordneten Bildfarbstoff enthaltenden Silberhalogenidemulsionsschicht angeordnet ist, gegenüber konventionellen Materialien und auch gegenüber solchen Materialien, bei denen Bildfarbstoff und Emulsion zwar teilweise getrennt sind, wobei aber alle Schichten, oder zumindest die dem einfallenden Licht zugekehrten Schichten eine Silberhalogenidemulsion enthalten, überraschende Vorteile aufweist: Durch die über die Emuulsionsschicht angeordnete silberhalogenidfreie Farbstoffschicht wird nämlich das von innerhalb des Schichtverbandes weiter oben liegenden Schichten stammende Streulicht weitgehend absorbiert, und zwar um so stärker, je mehr dieses von der senkrechten Einfallsrichtung abweicht und deshalb eine grössere Schichtdicke zu durchmessen hat. Daraus resultiert ein grosser Gewinn an Bildschärfe. Grundsätzlich kann dabei der gesamte, in einem Schichtpaar verwendete Bildfarbstoff der oberen, silberhalogenidfreien Schicht einverleibt werden. Da eine solche Anordnung die Gradation des photographischen Materials jedoch ungünstig beeinflusst, wird ein Teil des Bildfarbstoffs in der emulsionshaltigen Schicht untergebracht.It has now been found that a silver color bleaching material in which at least one silver halide emulsion layer containing image dye is divided into two components in such a way that a silver halide-free image dye layer is arranged on the side facing the light directly above a silver halide emulsion layer containing image dye, compared to conventional materials and also opposite such materials in which the image dye and emulsion are part are separated wisely, but all layers, or at least the layers facing the incident light containing a silver halide emulsion, have surprising advantages: the silver halide-free dye layer arranged over the emulsion layer largely absorbs the scattered light originating from layers located further up the layer structure, and the stronger, the more this deviates from the vertical direction of incidence and therefore has to measure a greater layer thickness. This results in a large gain in sharpness. In principle, the entire image dye used in a pair of layers can be incorporated into the upper, silver halide-free layer. However, since such an arrangement adversely affects the gradation of the photographic material, part of the image dye is housed in the emulsion-containing layer.
Gegenstand der vorliegenden Erfindung ist somit ein Verfahren zur Herstellung eines photographischen Bildes nach dem Silberfarbbleichverfahren durch Belichtung, Silberentwicklung, Farbbleichung, Silberbleichung und Fixierung und unter Verwendung eines photographischen Materials, das auf einem Träger lichtempfindliche Silberhalogenid- und Farbstoffschichten enthält, wobei die Farbstoffschichten jeweils unmittelbar über den lichtempfindlichen Silberhalogenidschichten angeordnet sind, dadurch gekennzeichnet, dass man ein photographisches Material mit mindestens einer lichtempfindlichen Silberhalogenidemulsionsschicht, welche einen diffusionsfesten, bleichbaren Bildfarbstoff enthält, und ummittelbar darüber, auf der der Lichtquelle zugewandten Seite, eine von Silberhalogenid freie, einen diffusionsfesten, bleichbaren Bildfarbstoff enthaltende Schicht enthält, bildmässig belichtet und in Anwesenheit eines Farbbleichkatalysators zu einem Farbbild verarbeitet, wobei das Farbbild ausschliesslich durch vorder Belichtung im photographischen Material vorhandene Bildfarbstoffe erzeugt wird.The present invention thus relates to a process for producing a photographic image by the silver color bleaching process by exposure, silver development, color bleaching, silver bleaching and fixing and using a photographic material which contains photosensitive silver halide and dye layers, the dye layers in each case immediately above the light-sensitive silver halide layers are arranged, characterized in that a photographic material with at least one light-sensitive silver halide emulsion layer, which contains a diffusion-resistant, bleachable image dye, and immediately above, on the side facing the light source, contains a silver halide-free, a diffusion-resistant, bleachable image dye Contains layer, exposed imagewise and processed in the presence of a color bleaching catalyst to a color image, the color image exclusively ch is produced by image dyes present in the photographic material before exposure.
Ein weiterer Gegenstand der Erfindung betrifft das für das erfindungsgemässe Verfahren geeignete photographische Material und die Verwendung dieses Verfahrens zur Herstellung von photographischen Bildern.The invention further relates to the photographic material suitable for the process according to the invention and the use of this process for the production of photographic images.
Bei dem in der lichtempfindlichen Silberhalogenidemulsionsschicht enthaltenen diffusionsfesten, bleichbaren Cyan-, Magenta- oder Gelbfarbstoff und bei dem in der silberhalogenidfreien Schicht enthaltenen Farbstoff handelt es sich im allgemeinen um denselben Farbstoff.The diffusion-resistant, bleachable cyan, magenta or yellow dye contained in the light-sensitive silver halide emulsion layer and the dye contained in the silver halide-free layer are generally the same dye.
Das photographische Material kann ein einziges solches Schichtenpaar oder mehrere solcher Schichtenpaare enthalten, z.B. in einem trichromatischen Material je eines für die zwei Grundfarben Cyan und Magenta. Für die zuoberst angeordnete Grundfarbe, d.h. also die Gelbschicht, ist die erfindungsgemässe Anordnung allerdings ohne Effekt, da hier keine Streustrahlung aus weiter oben gelegenen Schichten eintreffen kann. Ausser den die Silberhalogenidemulsion und/oder den Bildfarbstoff enthaltenden Schichten können im photographischen Material noch weitere Schichten enthalten sein, z.B. Schutzschichten, Trennschichten, Filterschichten, wobei gegebenenfalls einzelne dieser Schichten, sofern sie einer Silberhalogenidemulsionsschicht benachbart sind, ebenfalls Bildfarbstoffe enthalten können.The photographic material may contain one or more such a pair of layers, e.g. in a trichromatic material one for the two primary colors cyan and magenta. For the top color, i.e. that is, the yellow layer, the arrangement according to the invention has no effect, however, since no stray radiation can arrive from layers located further up. In addition to the layers containing the silver halide emulsion and / or the image dye, further layers can be contained in the photographic material, e.g. Protective layers, separating layers, filter layers, it being possible for individual of these layers, if they are adjacent to a silver halide emulsion layer, to also contain image dyes.
Als Bildfarbstoffe sind die bekannten bleichbaren Azofarbstoffe verwendbar, insbesondere wasserlösliche, diffusionsfeste Azofarbstoffe, wie sie z.B. in CH-A Nr. 572230 aufgezählt sind. Weiterhin lassen sich auch öllösliche Farbstoffe und Pigmente verwenden, sofern sie durch die üblichen Farbbleichbäder genügend rasch und vollständig ausgebleicht werden.The known bleachable azo dyes can be used as image dyes, in particular water-soluble, diffusion-resistant azo dyes, such as those e.g. are listed in CH-A No. 572230. Furthermore, oil-soluble dyes and pigments can also be used, provided that they are bleached sufficiently quickly and completely by the usual color bleaching baths.
Eine günstige Anordnung ergibt sich z.B. gemäss Fig. 1, bei der auf einem Träger S nacheinander eine Gelatinehaftschicht G, eine rotempfindliche Emulsionsschicht mit einem Cyanfarbstoff C1, eine emulsionsfreie Schicht mit einem Cyanfarbstoff C2, eine silberhalogenidfreie Schicht mit einem Magentafarbstoff M1, eine grünsensibilisierte Emulsionsschicht mit einem Magentafarbstoff M2, eine Schicht mit Magentafarbstoff M3, eine silberhalogenidfreie Schicht mit gelbem Bildfarbstoff Y1, eine blauempfindliche Emulsionsschicht mit gelbem Bildfarbstoff Y2 und eine aus Gelatine bestehende Schutzschicht übereinander angeordnet sind. Die Schichten C1 /C2 und M2/M3 bilden Schichtpaare gemäss der vorliegenden Erfindung. Die zusätzliche, Magentafarbstoff enthaltende Schicht M1 dient einerseits als Bildfarbstoffschicht, andererseits gleichzeitig als zusätzliche Trennschicht zwischen den beiden Schichten C2 und M2. Im gleichen Sinne wirkt die gelb gefärbte Schicht Y1.A favorable arrangement results e.g. 1, in which a gelatin adhesive layer G, a red-sensitive emulsion layer with a cyan dye C1, an emulsion-free layer with a cyan dye C2, a silver-halide-free layer with a magenta dye M1, a green-sensitive emulsion layer with a magenta dye M2, one layer on a carrier S one after the other with magenta dye M3, a silver halide-free layer with yellow image dye Y1, a blue-sensitive emulsion layer with yellow image dye Y2 and a protective layer consisting of gelatin are arranged one above the other. The layers C1 / C2 and M2 / M3 form layer pairs according to the present invention. The additional layer M1 containing magenta dye serves on the one hand as an image dye layer and on the other hand simultaneously as an additional separating layer between the two layers C2 and M2. The yellow colored layer Y1 acts in the same sense.
Die Zahlenwerte in Fig. 1, wie auch in den darauffolgenden Fig. 2 und 3, bedeuten die jeweiligen Trockenschichtdicken in Mikrometer.The numerical values in FIG. 1, as in the subsequent FIGS. 2 and 3, mean the respective dry layer thicknesses in micrometers.
Als Träger für die photographischen Schichten dienen die üblichen opaken oder transparenten Materialien wie Glas, Cellulosetriacetat, Polyester, beschichtetes Papier oder künstliche Papiere aus Polystyrol oder Nylonfasern.The usual opaque or transparent materials such as glass, cellulose triacetate, polyester, coated paper or artificial papers made of polystyrene or nylon fibers serve as supports for the photographic layers.
Silberhalogenidfreie, Bildfarbstoff enthaltende Schichten können gegebenenfalls auch als Schutzschichten dienen, indem sie darunter befindliche Emulsionsschichten vor Verkratzen und anderweitiger mechanischer Beanspruchung schützen. Insbesondere können sie diese Funktion auch während des Beschichtungsvorganges erfüllen, wo sie, z.B. als oberste Schicht eines Mehrfachschichtpaketes aufgetragen, während der Trocknung die darunter liegende druckempfindliche Emulsionsschicht vor direkter Berührung durch Walzen und Bildung von Druckschleier zu schützen vermögen.Silver halide-free, image dye-containing layers can optionally also serve as protective layers by protecting the emulsion layers underneath from scratching and other mechanical stress. In particular, they can also perform this function during the coating process, where they e.g. applied as the top layer of a multi-layer package, while drying it can protect the underlying pressure-sensitive emulsion layer from direct contact by rolling and the formation of pressure fog.
Als lichtempfindliche Silberhalogenidemulsionen werden vorzugsweise Silberhalogenidemulsionen oder Mischemulsionen, wie z.B. solche aus Silberchloridbromid, Silberbromidjodid oder Silberchloridbromidjodid verwendet. Da in Silberfarbbleichmaterialien stets ein Teil des einfallenden Lichtes durch die vorhandenen Bildfarbstoffe absorbiert wird, ist es im allgemeinen vorteilhaft, möglichst empfindliche Silberhalogenidemulsionen zu verwenden. Dies gilt insbesondere dann, wenn, wie bei den üblichen Materialien für Bilder in natürlichen Farben, die Emulsionen in den Spektralbereichen sensibilisiert sind, die dem jeweiligen Absorptionsmaximum des zugeordneten Bildfarbstoffs entsprechen. Die optische Desensibilisierung, d.h. der Verlust an aktinischem Licht, ist in diesem Fall besonders stark. Das Verfahren kann durch Verwendung von Emulsionen, die nicht im Hauptabsorptionsbereich deszugeordneten Bildfarbstoffs sensibilisiert sind, auch für die Herstellung von sog. Falschfarbenbildern verwendet werden.Silver halide emulsions or mixed emulsions, such as, for example, those composed of silver chloride bromide, silver bromide iodide or silver chloride bromide iodide, are preferably used as light-sensitive silver halide emulsions. Since part of the incident light is always absorbed by the existing image dyes in silver color bleaching materials, it is generally advantageous to to use sensitive silver halide emulsions. This applies in particular when, as with the usual materials for images in natural colors, the emulsions are sensitized in the spectral ranges which correspond to the respective absorption maximum of the assigned image dye. The optical desensitization, ie the loss of actinic light, is particularly strong in this case. The method can also be used for the production of so-called false color images by using emulsions which are not sensitized in the main absorption area of the assigned image dye.
Wegen ihrer hohen Empfindlichkeit haben sich Silberhalogenidemulsionen vom kubisch-monodispersen Typ, wie sie nach bekannten Methoden, z.B. nach der Doppelstrahlmethode erzeugt werden können, als besonders geeignet erwiesen. Dies ist insbesondere dort der Fall, wo die inhärent steile Gradation der monodispersen Emulsionen nicht störend wirkt. Neben ihrer hohen Empfindlichkeit haben die kubisch-monodispersen Emulsionen auch den Vorteil, im erfindungsgemässen Verfahren besonders scharfe Bilder zu liefern.Because of their high sensitivity, silver halide emulsions of the cubic monodisperse type, as are known by known methods, e.g. can be generated by the double jet method, proven to be particularly suitable. This is particularly the case where the inherently steep gradation of the monodisperse emulsions does not interfere. In addition to their high sensitivity, the cubic monodisperse emulsions also have the advantage of providing particularly sharp images in the process according to the invention.
Der bereits vorhandene Vorteil eines erhöhten Auflösungsvermögens kann damit noch weiter verstärkt und insbesondere für die Herstellung von Mikrofilmen und dergleichen nutzbar gemacht werden.The already existing advantage of an increased resolving power can thus be further increased and made usable in particular for the production of microfilms and the like.
Für die Fälle, in denen eine steile Gradation nicht erwünscht ist, können dem erfindungsgemässen Material polydisperse Emulsionen eingearbeitet werden. Dies führt zu einer Abflachung der Gradation, ohne dass jedoch das Auflösungsvermögen des erfindungsgemässen Materials wesentlich beeinträchtigt wird.For the cases in which a steep gradation is not desired, polydisperse emulsions can be incorporated into the material according to the invention. This leads to a flattening of the gradation without, however, significantly affecting the resolving power of the material according to the invention.
Zur Verarbeitung der erfindungsgemässen photographischen Materialien dienen die bekannten Verfahren, welche die üblichen Prozessstufen wie Silberentwicklung, Farbbleichung, Silberbleichung und Fixierung, sowie gegebenenfalls eine oder mehrere Wässerungsstufen umfassen, wobei die Silberbleichung gegebenenfalls mit der Farbbleichung und/oder der Fixierung zu einer einzigen Verarbeitungsstufe zusammengefasst sein kann. Geeignete Verarbeitungsverfahren sind z.B. in DE-A Nrn. 1924723, 2258076, 2423814, 2448433, 2547720 und 2651969 beschrieben.For the processing of the photographic materials according to the invention, the known processes are used, which include the usual process stages such as silver development, color bleaching, silver bleaching and fixation, and optionally one or more washing stages, the silver bleaching optionally being combined with the color bleaching and / or the fixation to form a single processing stage can. Suitable processing methods are e.g. in DE-A Nos. 1924723, 2258076, 2423814, 2448433, 2547720 and 2651969.
Wegen ihres erhöten Auflösungsvermögens eignen sich die erfindungsgemäss verwendeten photographischen Materialien insbesondere für die Herstellung von Mikrofilmen. Ein Mikrofilm, mit welchem sich in einem Arbeitsgang direkt positive farbige Abbildungen herstellen lassen, kann, wie in Beispiel 1 angegeben, hergestellt werden.Because of their increased resolving power, the photographic materials used according to the invention are particularly suitable for the production of microfilms. A microfilm, with which positive color images can be produced directly in one work step, can be produced as indicated in Example 1.
Unter Verwendung einer kubisch-monodispersen Silberchloridbromidemulsion mit 20 Mol-% Silberchlorid, deren Kristalle eine Kantenlänge von 0,20 µm besitzen, sowie der folgenden Bildfarbstoffe: des Cyanfarbstoffs:
In der nachfolgenden Tabelle sind die für jede Schicht aufgetragenen Gewichtsmengen Silber (Ag), Gelatine (Gel) und Farbstoff (FS) in Milligramm pro Quadratmeter angegeben.
Die für die Cyanemulsionsschicht 2 verwendete Silberhalogenidemulsion wurde zuvor für rotes Licht und diejenige für die Magentaemulsionsschicht für grünes Licht sensibilisiert.The silver halide emulsion used for the
Die Anordnung der Schichten entspricht der Fig. 1.The arrangement of the layers corresponds to FIG. 1.
Zum Vergleich wird unter Verwendung der gleichen Silberhalogenidemulsionen und Bildfarbstoffe ein zweites photographisches Material mit konventioneller Schichtfolge hergestellt, wobei die Silber- und Farbstoffmenge in den einzelnen Schichten so gewählt wird, dass nach Belichtung und Verarbeitung etwa die gleiche optische Dichte resultiert:For comparison, a second photographic material with a conventional layer sequence is produced using the same silver halide emulsions and image dyes, the amount of silver and dye in the individual layers being selected such that approximately the same optical density results after exposure and processing:
Diese Schichtanordnung entspricht der Fig. 2. Die Zahlen in den Fig. 1 und 2 geben Trockenschichtdicken in Mikrometer an.This layer arrangement corresponds to FIG. 2. The numbers in FIGS. 1 and 2 indicate dry layer thicknesses in micrometers.
Die in der Fig. 2 mit Z bezeichnete Schicht kann zusätzlich kolloidales Silber und/oder einen bleichbaren gelben Azofarbstoff enthalten. Sie wirkt in diesem Fall als Gelbfilterschicht, welche die Einwirkung von blauer Strahlung auf die grün-und rotempfindlichen Schichten verhindern soll. Bei der Farbbleichung wird die Gelbfilterschicht völlig entfärbt. Der Einbau der Gelbfilterschicht ist nur dann notwendig, wenn die zuoberst liegende Gelbschicht keine genügende Filterwirkung besitzt.The layer designated Z in FIG. 2 can additionally contain colloidal silver and / or a bleachable yellow azo dye. In this case, it acts as a yellow filter layer, which is intended to prevent the action of blue radiation on the green- and red-sensitive layers. The yellow filter layer is completely decolorized during color bleaching. The installation of the yellow filter layer is only necessary if the yellow layer on top does not have a sufficient filter effect.
Aus dem Vergleich der Fig. 1 und 2 ist ersichtlich, dass das resultierende konventionelle Material wegen Verwendung grösserer Mengen von Gelatine eine um ca. 25% höhere Gesamtschichtdicke aufweist. Dieser erhöhte Wert ist notwendig, um dem Material die erwünschten sensitometrischen Eigenschaften zu verleihen. Die erhöhte Schichtdicke wirkt sich jedoch ungünstig auf die Abbildungsschärfe aus, wie aus den Resultaten der photographischen Auswertung hervorgeht.It can be seen from the comparison of FIGS. 1 and 2 that the resulting conventional material has a total layer thickness which is approximately 25% higher due to the use of larger amounts of gelatin. This increased value is necessary to give the material the desired sensitometric properties. However, the increased layer thickness has an unfavorable effect on the image sharpness, as can be seen from the results of the photographic evaluation.
Je ein Streifen beider Materialien wird belichtet und anschliessend wie folgt bei einer Temperatur von 24°C verarbeitet:
Vergleicht man die belichteten und verarbeiteten Stufenkeile, so zeigen beide Materialien - wie beabsichtigt - praktisch identische sensitometrische Werte. Ein Unterschied ergibt sich jedoch hinsichtlich der photographischen Schärfeleistung bzw. des Auflösungsvermögens.If you compare the exposed and processed step wedges, both materials - as intended - show practically identical sensitometric values. However, there is a difference with regard to the photographic sharpness or the resolution.
Zur Messung der Abbildungsschärfe (Acutance) wird das Verfahren von G. C. Higgins und R. N. Wolfe in "J. of the SMPTE", 65, 26 (Jan. 1965) und in "J. of the Opt. Soc. of America", 45, 121 (Febr. 1955) benutzt.To measure the image sharpness (acutance), the method by GC Higgins and RN Wolfe is described in " J. of the SMPTE", 65, 26 (Jan. 1965) and in " J. of the Opt. Soc. Of America", 45, 121 (Feb. 1955) used.
Dazu wird eine scharfe Kante Kontaktverfahren auf das Material abgebildet. Nach Verarbeitung wird in der Umgebung des Übergangs vom belichteten zum unbelichteten Teil der Dichteverlauf mit einem Mikrodensitometer gemessen. Die Schärfeleistung ist dabei um so besser, je steiler der Übergang vom belichteten zum unbelichteten Gebiet verläuft. Die Steilheit dieses Übergangs wird nach einer von den oben erwähnten Autoren beschriebenen Methode berechnet und bedeutet, zahlenmässig ausgedrückt, die Dichtezunahme pro Mikrometer auf einer senkrecht zur belichteten Kante verlaufenden Messlinie.To do this, a sharp edge contact method is mapped onto the material. After processing, the density curve is measured with a microdensitometer in the vicinity of the transition from the exposed to the unexposed part. The sharper the better, the steeper the transition from the exposed to the unexposed area. The steepness of this transition is calculated according to a method described by the authors mentioned above and means, expressed in numbers, the increase in density per micrometer on a measurement line running perpendicular to the exposed edge.
Das erfindungsgemässe Material ergibt bei dieser Messung einen Wert von 14,3 -10-3, das Vergleichsmaterial mit konventionellem Schichtaufbau dagegen nur einen Wert von 10,6.10-3. Diese Verbesserung der Schärfeleistung ist auf die geringere Schichtdicke des erfindungsgemässen Materials und auf die Verminderung der Lichtstreuung durch den erfindungsgemässen Schichtaufbau zurückzuführen.In this measurement, the material according to the invention gives a value of 14.3 -10 -3 , the comparison material with a conventional layer structure, on the other hand, only a value of 10.6.10-3. This improvement in the sharpness performance is due to the lower layer thickness of the material according to the invention and to the reduction in light scattering due to the layer structure according to the invention.
Der im Beispiel 1 und der zugehörigen Fig. 1 beschriebene Versuch wird wiederholt, wobei jedoch anstelle der kubisch-monodispersen Emulsion eine polydisperse Silberbromojodidemulsion mit einem mittleren Teilchendurchmesser von 0,20 µm verwendet wird, deren Kristalle 2,6 Mol-% Silberjodid enthalten. Ferner wird anstelle des im Beispiel 1 genannten Cyanfarbstoffes ein solcher der Formel
Mit den im Beispiel 1 verwendeten Komponenten wird ein photographisches Material hergestellt, das sich von demjenigen des Beispiels 1 durch die Anzahl und Reihenfolge der verwendeten Schichten unterscheidet:
- Die Schichten Y2 und Y1 des Materials aus
Beispiel 1, Fig. 1, werden zu einer einzigen Schicht Y zusammengelegt, ebenso die in Fig. 1 mit M1 und M3 bezeichneten Schichten, die nunmehr, wie in Fig. 3 gezeigt, zu einer einzigen emulsionsfreien Farbstoffschicht M2 oberhalb der grünsensibilisierten Emulsionsschicht M1 zusammengelegt werden.
- Layers Y2 and Y1 of the material from Example 1, FIG. 1, are combined to form a single layer Y, as are the layers designated M1 and M3 in FIG. 1, which now, as shown in FIG. 3, form a single emulsion-free layer Dye layer M2 are put together above the green-sensitized emulsion layer M1.
Die fehlenden, gemäss Beispiel 1 als Trennschichten wirkenden Schichten M1 und Y1 der Fig. 1, werden, wie in Fig. 3 dargestellt, durch Gelatinezwischenschichten ersetzt: Z1 zwischen dem Cyan- und dem Magentaschichtpaket und Z2 zwischen dem Gelb- und dem Magentaschichtpaket.The missing layers M1 and Y1 of FIG. 1, which act as separating layers according to Example 1, are replaced, as shown in FIG. 3, by intermediate gelatin layers: Z1 between the cyan and magenta layer pack and Z2 between the yellow and magenta layer pack.
Die Zwischenschicht Z2 wird dabei zusätzlich durch Einarbeitung von 21 mg/m2 kolloidalem Silber und 17 mg/m2 des im Beispiel 1 beschriebenen gelben Farbstoffs zu einer bleichbaren Gelbfilterschicht ausgebildet.The intermediate layer Z2 is additionally formed into a bleachable yellow filter layer by incorporating 21 mg / m 2 of colloidal silver and 17 mg / m 2 of the yellow dye described in Example 1.
Auch diese Schichtanordnung ergibt gegenüber dem konventionellen Material gemäss Fig. 2 eine deutliche Verbesserung der Bildschärfe.This layer arrangement also results in a significant improvement in image sharpness compared to the conventional material according to FIG. 2.
Claims (8)
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CH334480 | 1980-04-30 | ||
| CH3344/80 | 1980-04-30 |
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| EP0039313A1 EP0039313A1 (en) | 1981-11-04 |
| EP0039313B1 true EP0039313B1 (en) | 1984-03-07 |
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| Application Number | Title | Priority Date | Filing Date |
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| EP81810157A Expired EP0039313B1 (en) | 1980-04-30 | 1981-04-24 | Process for the production of a photographic image by the silver-dye bleaching process and the photographic material intended for this process |
Country Status (5)
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| US (1) | US4391884A (en) |
| EP (1) | EP0039313B1 (en) |
| JP (1) | JPS57649A (en) |
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| EP0149978A3 (en) * | 1984-01-20 | 1988-08-31 | Ciba-Geigy Ag | Process for the production of photographic images by the silver dye-bleaching process |
| DE3775573D1 (en) * | 1986-02-11 | 1992-02-13 | Ilford Ag | PHOTOGRAPHIC MATERIAL FOR THE SILVER COLORING METHOD. |
| JPS63210927A (en) * | 1987-02-27 | 1988-09-01 | Fuji Photo Film Co Ltd | Silver halide color photographic sensitive material |
| US4855220A (en) * | 1988-01-14 | 1989-08-08 | Eastman Kodak Company | Photographic element having layer for increasing image sharpness comprising a non-diffusible DIR compound |
| EP0566077B1 (en) * | 1992-04-16 | 1999-06-23 | Eastman Kodak Company | Photographic silver halide material comprising tabular silver halide grains plus distributed absorber dyes |
| US5302499A (en) * | 1992-04-16 | 1994-04-12 | Eastman Kodak Company | Photographic silver halide material comprising tabular grains of specified dimensions in several color records |
| US5275929A (en) * | 1992-04-16 | 1994-01-04 | Eastman Kodak Company | Photographic silver halide material comprising tabular grains of specified dimensions |
| US5308747A (en) * | 1992-04-16 | 1994-05-03 | Eastman Kodak Company | Photographic silver halide material comprising tabular grains and positioned absorber dyes |
| US5399469A (en) * | 1993-10-13 | 1995-03-21 | Eastman Kodak Company | Spatially fixed absorber dyes in less sensitive layers |
| US5576159A (en) * | 1995-02-17 | 1996-11-19 | Eastman Kodak Company | Photographic element with color enhancing layer adjacent to an emulsion layer and an oxidized developer scavenger layer |
| US5939246A (en) * | 1997-03-17 | 1999-08-17 | Eastman Kodak Company | Color photographic silver halide negative imaging material and process |
| ITSV20020034A1 (en) * | 2002-07-29 | 2002-10-28 | Ferrania Spa | EMULSION OF BRAIDED SILVER (CORE-SHELL) GRANULES (CORE-SHELL). |
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| FR757376A (en) | 1932-06-23 | 1933-12-26 | Method for producing color photographic images | |
| BE438456A (en) * | 1939-03-29 | |||
| US3498787A (en) * | 1965-08-20 | 1970-03-03 | Eastman Kodak Co | Rapid dye-bleach photographic process and element comprising dye-developers |
| CH492234A (en) * | 1967-06-07 | 1970-06-15 | Ciba Geigy | Photographic material |
| CH526134A (en) * | 1969-07-25 | 1972-07-31 | Ciba Geigy Ag | A method for producing a color photographic image by the silver dye bleaching process |
| CH550423A (en) * | 1970-07-07 | 1974-06-14 | Ciba Geigy Ag | PROCESS FOR PRODUCING A PHOTOGRAPHICAL COLOR IMAGE BY THE SILVER COLOR BLADE PROCESS. |
-
1981
- 1981-04-17 US US06/255,069 patent/US4391884A/en not_active Expired - Fee Related
- 1981-04-24 DE DE8181810157T patent/DE3162485D1/en not_active Expired
- 1981-04-24 CA CA000376219A patent/CA1178840A/en not_active Expired
- 1981-04-24 EP EP81810157A patent/EP0039313B1/en not_active Expired
- 1981-04-30 JP JP6435881A patent/JPS57649A/en active Granted
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0138298B2 (en) | 1989-08-14 |
| JPS57649A (en) | 1982-01-05 |
| EP0039313A1 (en) | 1981-11-04 |
| US4391884A (en) | 1983-07-05 |
| DE3162485D1 (en) | 1984-04-12 |
| CA1178840A (en) | 1984-12-04 |
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