EP0039313B1 - Verfahren zur Herstellung eines photographischen Bildes nach dem Silberfarbbleichverfahren und das zu diesem Verfahren geeignete photographische Material - Google Patents

Verfahren zur Herstellung eines photographischen Bildes nach dem Silberfarbbleichverfahren und das zu diesem Verfahren geeignete photographische Material Download PDF

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Publication number
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
Authority
EP
European Patent Office
Prior art keywords
dye
silver halide
layers
layer
image
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired
Application number
EP81810157A
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German (de)
English (en)
French (fr)
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EP0039313A1 (de
Inventor
Armin Dr. Meyer
Carlo Dr. Boragine
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Cessione ilford AG
Original Assignee
Ciba Geigy AG
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Ciba Geigy AG filed Critical Ciba Geigy AG
Publication of EP0039313A1 publication Critical patent/EP0039313A1/de
Application granted granted Critical
Publication of EP0039313B1 publication Critical patent/EP0039313B1/de
Expired legal-status Critical Current

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    • 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)
EP81810157A 1980-04-30 1981-04-24 Verfahren zur Herstellung eines photographischen Bildes nach dem Silberfarbbleichverfahren und das zu diesem Verfahren geeignete photographische Material Expired EP0039313B1 (de)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
CH334480 1980-04-30
CH3344/80 1980-04-30

Publications (2)

Publication Number Publication Date
EP0039313A1 EP0039313A1 (de) 1981-11-04
EP0039313B1 true EP0039313B1 (de) 1984-03-07

Family

ID=4253936

Family Applications (1)

Application Number Title Priority Date Filing Date
EP81810157A Expired EP0039313B1 (de) 1980-04-30 1981-04-24 Verfahren zur Herstellung eines photographischen Bildes nach dem Silberfarbbleichverfahren und das zu diesem Verfahren geeignete photographische Material

Country Status (5)

Country Link
US (1) US4391884A (enrdf_load_stackoverflow)
EP (1) EP0039313B1 (enrdf_load_stackoverflow)
JP (1) JPS57649A (enrdf_load_stackoverflow)
CA (1) CA1178840A (enrdf_load_stackoverflow)
DE (1) DE3162485D1 (enrdf_load_stackoverflow)

Families Citing this family (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
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 (de) * 1986-02-11 1992-02-13 Ilford Ag Photographisches material fuer das silberfarbbleichverfahren.
JPS63210927A (ja) * 1987-02-27 1988-09-01 Fuji Photo Film Co Ltd ハロゲン化銀カラ−写真感光材料
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
US5275929A (en) * 1992-04-16 1994-01-04 Eastman Kodak Company Photographic silver halide material comprising tabular grains of specified dimensions
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
US5308747A (en) * 1992-04-16 1994-05-03 Eastman Kodak Company Photographic silver halide material comprising tabular grains and positioned absorber dyes
JPH0619075A (ja) * 1992-04-16 1994-01-28 Eastman Kodak Co 写真記録材料
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 (it) * 2002-07-29 2002-10-28 Ferrania Spa Emulsione di granuli straficati(core-shell) di argento bromoioduro.

Family Cites Families (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR757376A (fr) 1932-06-23 1933-12-26 Procédé de production d'images photographiques en couleurs
BE438456A (enrdf_load_stackoverflow) * 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 (de) * 1967-06-07 1970-06-15 Ciba Geigy Photographisches Material
CH526134A (de) * 1969-07-25 1972-07-31 Ciba Geigy Ag Verfahren zur Herstellung eines photographischen Farbbildes nach dem Silberfarbbleichverfahren
CH550423A (de) * 1970-07-07 1974-06-14 Ciba Geigy Ag Verfahren zur herstellung eines photographischen farbbildes nach dem silberfarbbleichverfahren.

Also Published As

Publication number Publication date
JPH0138298B2 (enrdf_load_stackoverflow) 1989-08-14
US4391884A (en) 1983-07-05
CA1178840A (en) 1984-12-04
JPS57649A (en) 1982-01-05
DE3162485D1 (en) 1984-04-12
EP0039313A1 (de) 1981-11-04

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