US3743506A - Photographic colour material - Google Patents

Photographic colour material Download PDF

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Publication number
US3743506A
US3743506A US00160561A US3743506DA US3743506A US 3743506 A US3743506 A US 3743506A US 00160561 A US00160561 A US 00160561A US 3743506D A US3743506D A US 3743506DA US 3743506 A US3743506 A US 3743506A
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layer
image
layers
emulsion
emulsion layer
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Expired - Lifetime
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US00160561A
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English (en)
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A Meyer
C Boragine
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Ilford Imaging Switzerland GmbH
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Individual
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Assigned to ILFORD AG, A CO. OF SWITZERLAND reassignment ILFORD AG, A CO. OF SWITZERLAND ASSIGNMENT OF ASSIGNORS INTEREST. Assignors: CIBA-GEIGY AG
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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

  • ABSTRACT OF THE DISCLOSURE A process for the manufacture of a photographic colour image which comprises exposing image-wise and processing in the presence of a dye bleach catalyst, a photographic material containing at least one silver halide emulsion layer containing a diffusion-resistant bleachable image dyestuff and immediately above and below said layer, two silver halide emulsion layers, free of image dyestuff, as well as a photographic material containing said layers are disclosed.
  • a customary material for the silver dye bleach process contains, on a transparent or reflecting support, an emulsion layer, dyed with a blue-green dyestuif, which is sensitive to red, on top of this an emulsion layer, dyed with a purple dyestuff, which is sensitive to green, and uppermost an emulsion layer, dyed with a yellow dyestuff, which is sensitive to blue. Additionally, filter layers and other intermediate layers can be present between these emulsion layers. Other layer sequences and other sensitiser arrangements are also possible. Such a material is exposed, developed and finally processed to give a coloured image by bleaching the image dyestuffs present as a function of the developed metallic silver, and removing the excess silver halide and metallic silver from the material.
  • the silver halide emulsion is frequently chemically desensitised by azo dyestuffs, and that the dyestuffs also cause optical desensitisation, that is to say absorb light in the spectral sensitivity range of the emulsion, so that the light is reduced in intensity in the layer, and no longer exerts an effect in the depth of the layer.
  • the gradation of the images produced by the silver dye bleach process is as a rule too steep, especially if, in the manner which has been indicated, an excess of silver which is only partially used for dye bleaching is employed.
  • This disadvantage was also recognised at an early stage and is, for example, counteracted according to German patent specification 733,728 by bleaching in the presence of an oxidising agent.
  • a further possibility is also, for example, to provide an additional emulsion layer, free of image dyestuff, underneath an emulsion layer containing a diffusion-resistant image dyestuif, to develop silver-images in both layers and to bleach the image dyestutf in the presence of a bleaching catalyst so that, in addition to bleaching by the silver present in the layer, an additional bleaching by the silver of the adjacent layer below it occurs.
  • an additional emulsion layer free of image dyestuff
  • the subject of the present invention is, accordingly, a process for the production of a photographic colour image by the silver dye bleach process, characterised in that a photographic material which contains, on a support, at least one silver halide emulsion layer containing a diffusion-resistant bleachable image dyestuff, and additionally on both sides, immediately above and below this layer, two silver halide emulsion layers free of image dyestuif which are of at least equally high sensitivity as the layer containing dyestutf, is exposed image-wise and is processed in the presence of a dye bleach catalyst to give a coloured image, the coloured image being produced exclusively by image dyestuffs present in the photographic material before exposure.
  • a further subject of the present invention is a photographic material which contains, on a support, at least one silver halide emulsion layer containing a diffusionresistant image dyestuff which is bleachable by the silver dye bleach process, between a silver halide emulsion layer above it, which is free of image dyestuff, and a silver halide emulsion layer below it, which is also free of image dyestuff, the two emulsion layers free of image dyestuff being of at least equally high sensitivity as the dyestuifcontaining layer, and preferably, all three layers being sensitive to the same spectral region.
  • the colourless emulsion layers are above and below the dyed emulsion layer.
  • the result of this is that the sensitivity of the colourless layers does not suffer the chemical desensitisation by the image dyestuif.
  • the sensitivities of the three layers must be so matched that the sensitivities of the colourless layers are as high, or preferably higher, than those of the dyed layer.
  • An equally high sensitivity is achieved in a simple fashion by dividing a single base emulsion into three parts, adding image dyestufi to one part and casting the three parts over the top of one another. It is however also possible to start from different emulsions (different gradation and different sensitivity) for the three layers.
  • the amount of silver halide cast per unit surface area is adjusted to be as high, or only a fraction of, that of the coloured layer, for example to 100% Amounts of silver halide higher than 100% can also be used.
  • the sensitivities of the colourless emulsion layers are so adjusted that the colour gradation curve is linearised through correction of the shoulder part and of the bottom part, that is to say approaches a straight line. This must be determined empirically.
  • the shoulder sensitivity of the coloured layer is increased by remote-bleaching by the upper layer, which is free of image dyestufi. As a result of remote bleaching by the lower layer which is free of image dyestuif, an increase in the bottom sensitivity of the coloured layer is achieved.
  • the optical sensitisation of the three layers which belong together preferably lies in the same spectral range. It is however not necessary to use the same optical sensitiser for the three layers. Thus, for example, the maximum of the sensitisations can be displaced by a few nm., or the maxima of the sensitisation ranges can differ from one another. Additional sensitivities in other spectral ranges can be desirable for producing certain masking effects.
  • the three layers are sensitised in each range in which the image dyestuif also absorbs, it is advisable to choose an emulsion of extremely high sensitivity for the lower, undyed, layer, and/or to sensitise this layer towards shorter wavelengths of preferably towards longer wavelengths (relative to the absorption maximum of the image dyestuff).
  • the process according to the invention is suitable for monochromatic and polychromatic material. It is of particular importance in producing polychromatic images, because the requirement that the gradations and sensitivities of the individual coloured layers should be matched to one another reduces the number of possible variations.
  • a polychromatic material according to the invention contains at least two silver halide emulsion layers containing image dyestuffs, the two image dyestuffs being different from one another, and can, according to the invention, contain one or more three-layer systems. These three-layer systems can, if desired, be separated from other emulsion layers by intermediate layers, and these intermediate layers can also contain customary additives, such as filter dyestuffs, UV-absorbers or oxidising agents.
  • each dyed emulsion layer possesses a colourless emulsion layer immediately above it and a colourless emulsion layer immediately below it, so that the dyed emulsion layers are separated from one another by two colourless intermediate layers and optionally by an intermediate layer lying between them.
  • Suitable pyrazines, quinoxalines or phenazines are preferably used as dye bleach catalysts.
  • the catalysts can be present either in a photographic processing bath or in any desired layer of the photographic material which is to be processed.
  • the image dyestuffs are, as a rule, azo dyestuffs.
  • the process according to the invention is particularly suitable for photographic transparency material having a colour density of 2.4 to 2.8, preferably 2.6.
  • the material according to the invention is advantageously used in building up a false colour film for infrared photography.
  • By invoking the presentinvention it is possible to produce an infrared exposure material of sufliciently high sensitivity.
  • a preferred material has, for example, the following construction:
  • a photographic material having the following layer arrangement is manufactured: Water to make up to 1000 3. Colourless emulsion layer 2 mmutes soakmg' 2. Coloured emulsion layer 4 minutes fixing bath 1. Colourless emulsion layer Substrate transparent Composition as for stop fixing bath.
  • the coloured emulsion layer contains 6.5 mg./kg. of the as m e W 0g m a m I 2 1.09 -6 compound of the Formula 1 as the optical sensitizer, and H 1+2+3 0. 62 2o 13 g./kg. of the compound of the formula as the image dyestufi.
  • the sensitizer of the Formula 1 The gradation curves of the cast materials I and H are shows a sensitisation maximum at 760 nm.
  • the wedge densities of dyestufi of the Formula 2 showsan absorption maximum the exposure wedge (exposure increases from left to right) at 650 nm. are plotted on the abscissa and the density on the ordinate.
  • Example 7 The procedure indicated in Example 1 is followed. However, the layer 2 is a coloured emulsion layer, which is sensitised with 2.3 mg./-kg. of the compound of the Formula 3:
  • the coloured emulsion layer contains 80 mg./ kg. of the compound (4) as the optical sensitiser and 15 g./kg. of the compound (5) as the image dyestufi:
  • the sensitiser of the Formula 4 shows a sensitisation maximum at 640 mm.
  • the image dyestuif of the Formula 5 shows an absorption maximum at 535 nm.
  • Two cast materials I and II are prepared on a transparent support, in the manner of Example 1, applying 1.5 g. of silver/m They are exposed behind a grey wedge, using a red filter, and are processed as in Example 1.
  • Example 4 The procedure of Example 3 is followed. The layers are however cast on an opaque white support, applying 1.0 g. of silver/mf The two cast materials are exposed, processed and measured. The results are summarised in the table below.
  • the cast material II distinctly shows a gain in the sensitivity and a flattening of the gradation as compared to the cast material 1.
  • the three layers sensitised to infrared correspond to those of Example 2.
  • the intermediate layers and the protective layer are gelatine layers wherein 2 g. of gelatine are applied per m
  • the purple emulsion layer contains 80 mg./kg. of the compound of the Formula 4 as the optical sensitiser and 15 g./kg. of the compound of the Formula 5 as the image dyestuff.
  • the yellow emulsion layer contains mg./ kg. of the compound of the Formula 6 as the optical sensitiser and 15.4 g./kg. of the compound of the Formula 7 as the image dyestutf.
  • the sensitiser of the Formula 6 shows a sensitisation maximum at 550 nm.
  • the image dyestuif of the Formula 7 shows an absorption maximum at 416 um.
  • the cast material is exposed and processed as in Example 1, except that the dye bleach bath does not contain a dye bleach catalyst.
  • the intermediate layers and the protective layer are gelatine layers wherein 2 g. of gelatine/m. are applied.
  • the yellow emulsion layer contains 100 mg./ kg. of the compound of the Formula 6, indicated in Example 5, as the optical sensitizer, and 2.0.5 g./kg. of the compound of the Formula 7, indicated in Example 5, as the image dyestuff. This emulsion layer is cast so as to apply 1 g. of silver/m.
  • the blue-green emulsion layer which shows the intrinsic spectral sensitivity of the emulsion, contains, as the image dyestuif, 9 g./kg. of the compound of the formula Oz 503 OCH;
  • This emulsion layer is cast so as to apply 1.2 g. of silver/m3.
  • the two colourless emulsion layers contain mg. /kg. of the compound of the Formula 6, indicated in Example 5, as the optical sensitizer.
  • the blue-green emulsion layer contains 100 mg./kg. of the compound of the Formula 6, indicated in Example 5, as the optical sensitiser, and 13 g./ kg. of the compound of the Formula 2, indicated in Example 1, as the image dyestuif.
  • the yellow emulsion layer contains 80 mg./:kg. of the compound of the Formula 4, indicated in Example 3, as the optical sensitiser, and 15.4 g./kg. of the compound of the Formula 7, indicated in Example 5, as the image dyestufi.
  • the purple emulsion layer which shows the intrinsic spectral sensitivity of the emulsion, contains 15 g./kg. of the compound of the Formula 5, indicated in Example 3, as the image dyestulf.
  • this second material B the sensitivity of which corresponds to that of a photographic positive material, it is possible to obtain true-to-nature copies directly from the exposure material A described above.
  • the visual density of an unexposed area of this copying material corresponds to 2.6 density units.
  • a photographic colour image by the silver dye bleach process characterised in that a photographic material which contains, on a support, at least one silver halide emulsion layer containing a diffusion-resistant bleachable azo dyestuif, and additionally on each side, immediately adjacent this layer, a silver halide emulsion layer, free of azo dyestulf, which are of at least equally high sensitivity as the layer containing dyestuif, is exposed image-wise and is processed, in the presence of a dye bleach catalyst, to give a coloured image, the coloured image being produced exclusively by image dyestuffs present in the photographic material before exposure.
  • the false-colour exposure material contains, on a transparent support, a purple silver halide emulsion layer which is sensitive to red, over this a yellow silver halide emulsion layer which is sensitive to green and over this a blue-green silver halide emulsion layer which is sensitive to blue, with at least one of these coloured layers being adjoined on both sides by a silver halide emulsion layer which is free of dyestuff.
  • the false-colour copying material contains, on a support, a blue-green silver halide emulsion layer which is sensitive to green, over this a yellow silver halide emulsion layer which is sensitive to red and over this a purple silver halide emulsion layer which is sensitive to blue, with at least one of these coloured layers being adjoined on both sides by a silver halide emulsion layer which is free of dyestuiT.
  • the infrared exposure material contains, on a transparent support, a blue-green silver halide emulsion layer which is sensitive to infrared, over this a purple silver halide emulsion layer which is sensitive to red, and over this a yellow silver halide emulsion layer which is sensitive to green, with at least one of these coloured layers being adjoined on both sides by a silver halide emulsion layer which is free of dyestutf.
  • Photographic material for the silver dye bleach process characterised in that it contains, on a support, at least one silver halide emulsion layer containing a diifusion-resistant bleachable azo 'dyestufi, between a silver halide emulsion layer free of azo dyestuff below it and a silver halide emulsion layer, free of azo dyestuif, above it, the two layers free of azo dyestutf being at least of equally high sensitivity as the layer containing image dyestuif.
  • Photographic material according to claim 15 characterised in that it has the construction of a false colour exposure material.
  • Photographic material according to claim 15 characterised in that it has the construction of a false colour copying material.
  • Photographic material according to claim 16 characterised in that it has the construction of an infrared exposure material.
  • Photographic material according to claim 16 characterised in that it contains, on a transparent support, a purple silver halide emulsion layer which is sensitive to red, over this a yellow silver halide emulsion layer which is sensitive to green, and over this a blue-green silver halide emulsion layer which is sensitive to blue, with at least one of these coloured layers being adjoined, on both sides, by a silver halide emulsion layer which is free of dyestutf.
  • Photographic material according to claim 18 characterised in that it contains, on a support, a blue-green silver halide emulsion layer which is sensitive to green, over this a yellow silver halide emulsion layer'which is sensitive to red, and over this a purple silver halide emulsion layer which is sensitive to blue, with at least one of these coloured layers being adjoined on both sides by a silver halide emulsion layer which is free of dyestufi.
  • Photographic material according to claim 19 characterised in that it contains, on a transparent support, a blue-green silver halide emulsion layer which is sensitive to infrared, over this a purple silver halide emulsion layer which is sensitive to red, and over this a yellow silver halide emulsion layer which is sensitive to green, with at least one of these coloured layers being adjoined on both sides by a silver halide emulsion layer which is free of dyestulf.

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  • Physics & Mathematics (AREA)
  • General Physics & Mathematics (AREA)
  • Silver Salt Photography Or Processing Solution Therefor (AREA)
  • Plural Heterocyclic Compounds (AREA)
US00160561A 1970-07-07 1971-07-07 Photographic colour material Expired - Lifetime US3743506A (en)

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CH1026670A CH550423A (de) 1970-07-07 1970-07-07 Verfahren zur herstellung eines photographischen farbbildes nach dem silberfarbbleichverfahren.

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US3743506A true US3743506A (en) 1973-07-03

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US00160561A Expired - Lifetime US3743506A (en) 1970-07-07 1971-07-07 Photographic colour material

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US (1) US3743506A (enExample)
JP (1) JPS543619B1 (enExample)
BE (1) BE769546A (enExample)
CA (1) CA945798A (enExample)
CH (1) CH550423A (enExample)
DE (1) DE2132835A1 (enExample)
FR (1) FR2100279A5 (enExample)
GB (1) GB1329057A (enExample)
NL (1) NL7109329A (enExample)
SU (1) SU465804A3 (enExample)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4391884A (en) * 1980-04-30 1983-07-05 Ciba-Geigy Ag Process for the production of a photographic color image by the silver dye bleach process and suitable color photographic material therefor
US4879203A (en) * 1987-04-06 1989-11-07 Ciba-Geigy Ag Process for producing masked positive color images by the silver dye bleach process

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4391884A (en) * 1980-04-30 1983-07-05 Ciba-Geigy Ag Process for the production of a photographic color image by the silver dye bleach process and suitable color photographic material therefor
US4879203A (en) * 1987-04-06 1989-11-07 Ciba-Geigy Ag Process for producing masked positive color images by the silver dye bleach process

Also Published As

Publication number Publication date
NL7109329A (enExample) 1972-01-11
CH550423A (de) 1974-06-14
FR2100279A5 (enExample) 1972-03-17
JPS543619B1 (enExample) 1979-02-24
CA945798A (en) 1974-04-23
GB1329057A (en) 1973-09-05
SU465804A3 (ru) 1975-03-30
DE2132835A1 (de) 1972-01-20
BE769546A (fr) 1972-01-06

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Date Code Title Description
AS Assignment

Owner name: ILFORD AG, A CO. OF SWITZERLAND, SWITZERLAND

Free format text: ASSIGNMENT OF ASSIGNORS INTEREST.;ASSIGNOR:CIBA-GEIGY AG;REEL/FRAME:005319/0226

Effective date: 19900502