US3650739A - Silver dye bleach photographic elements and processes for their use - Google Patents

Silver dye bleach photographic elements and processes for their use Download PDF

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Publication number
US3650739A
US3650739A US56597A US3650739DA US3650739A US 3650739 A US3650739 A US 3650739A US 56597 A US56597 A US 56597A US 3650739D A US3650739D A US 3650739DA US 3650739 A US3650739 A US 3650739A
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United States
Prior art keywords
dyestuff
layer
image
silver halide
halide emulsion
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Expired - Lifetime
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US56597A
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English (en)
Inventor
Max Marthaler
Alfred Oetiker
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BASF Schweiz AG
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Ciba 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
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03C—PHOTOSENSITIVE MATERIALS FOR PHOTOGRAPHIC PURPOSES; PHOTOGRAPHIC PROCESSES, e.g. CINE, X-RAY, COLOUR, STEREO-PHOTOGRAPHIC PROCESSES; AUXILIARY PROCESSES IN PHOTOGRAPHY
    • G03C1/00—Photosensitive materials
    • G03C1/005—Silver halide emulsions; Preparation thereof; Physical treatment thereof; Incorporation of additives therein
    • G03C1/46—Silver halide emulsions; Preparation thereof; Physical treatment thereof; Incorporation of additives therein having more than one photosensitive layer

Definitions

  • ABSTRACT A process for the manufacture of a photographic color image by the silver dyestuff bleaching process is provided.
  • the photographic material used in this process comprises on a support at least one silver halide emulsion layer containing a diffusion-resistant bleachable image dyestuff and immediately on top of said layer on the side facing the light source, a silver halide emulsion layer free of image dyestuff. After imagewise exposure this material is processed in the presence of a dyestuff bleaching catalyst to give a color image. The color image is produced exclusively through image dyestuffs present in the photographic material prior to the exposure.
  • color images are obtained wherein the gradation, sensitivity and spectral distribution of the sensitivity have been favorably influenced.
  • This invention relates to color photography, especially to processes for the production of color images by the silver dyestuff bleaching process.
  • a customary material for the silver dyestuff bleaching process contains, on a transparent or reflecting support, a redsensitive emulsion layer dyed with blue-green dye-stuff, on top of this a green-sensitive emulsion layer dyed with a purple dyestuff, and at the very top a blue-sensitive emulsion layer dyed with a yellow dyestuff. Filter layers and other intermediate layers can furthermore be present between these emulsion layers. Such a material is exposed to light, developed and finally processed to give a colored image by bleaching the image dyestuffs which are present as a function of the developed metallic silver and removing the excess silver halide and metallic silver from the material.
  • optical desensitisation has a disadvantageous effect particularly if the sensitivity range of the emulsion and the absorption range of the dyestuff, whilst lying in the same spectral region, do not fully overlap. If, for example, a layer sensitized with a sensitiser is dyed with an image dyestuff of which the absorption maximum lies at somewhat shorter or longer wavelengths than the sensitising maximum of the sensitiser, the spectral sensitivity distribution is not merely uniformly reduced, but two sensitisation maxima result, with a sensitivity gap lying between them, leading to color distortions.
  • Processes are furthermore also known (U.S. Pat. No. 2,183,394 and British Patent specification 483,464) which start from colored emulsion layers and colorless emulsion layers which serve to record various color impressions.
  • the colorless layers after undergoing black and white development, are dyed with image dyestuffs which then assist in the production of the image.
  • the present invention is based upon the observation that the disadvantages mentioned .above can surprisingly be avoided if an emulsion layer containing a diffusion-resistant image dyestuff and an emulsion layer free of image dyestuff are combined, silver images are developed in both layers, and the image dyestuff is bleached in the presence of a bleaching catalyst, so that in addition to the bleaching by the silver intrinsically present in the layer an additional bleaching through the silver of the adjacent layer occurs.
  • a bleaching catalyst so that in addition to the bleaching by the silver intrinsically present in the layer an additional bleaching through the silver of the adjacent layer occurs.
  • the present invention provides a process for the manufacture of a photographic color image by the silver dyestuff bleaching process, wherein a photographic material which comprises, on a support at least one silver halide emulsion layer containing a diffusion-resistant bleachable image dyestuff and immediately on top of said layer on the side facing the light source, a silver halide emulsion layer free of image dyestuff the sensitivity of which latter layer is at least as high as that of the layer containing dyestuff, is exposed imagewise and processed in the presence of a dyestuff bleaching catalyst to give a color image, the color image being produced exclusively through the image dyestuffs present in the photographic material prior to the exposure.
  • the sensitivities of both layers should be such that the sensitivity of the colorless layer is higher than that of the colored layer.
  • This may be achieved in a simpler manner by dividing a single base emulsion into two parts, adding image dyestuff to one part, and casting the two parts on top of one another.
  • the starting point for the two layers can however also be different emulsions (different gradation and different sensitivity).
  • the higher sensitivity of the colorless emulsion layer may be so adjusted that the color gradation curve is linearised by correction of the shoulder part, that is to say it is made to approach a straight line. The necessary adjustment may be established empirically.
  • thecolor gradation may be corrected without loss of sensitivity or even with a gain in effective sensitivity.
  • Material A tion effect it sufiices in most casesif, in the colorless emulsion contains Silver id i h lower layer l i l B y the amount of Silver halide Cast in P unit r iS contains silver bromide in the upper layer only, and material C justed to be equally high as, or preferably only a fraction of, contains silver bromide in both layers. that in the colored layer, for example 10 to 100 percent.
  • the dyestuff has the formula H0 8 (1)0113 H300 SIO H optical sensitisation of the two layers which belong together and is used in a transmission density of 2.0.
  • the silver bromide preferably lies in the same spectral region.
  • the maximum of the two sensitisations can g. of Ag/m. in the upper layers (B and C).
  • the amount of be displaced by a few nm, for example up to i nm, or the gelatine used is such that all layers have a thickness of 2.5 width of the sensitisation ranges can differ from one another. each.
  • the colorless layer can optionally be sensitized with a
  • the three materials are exposed to blue light behind a step sensitiser which displays a very narrow band in the region of 25 wedge and are processed as follows: 6 minutes developer the absorption maximum of the image dyestuff, in order to p-methylarninophenol sulphate 2g. compensate the sensitivity gap, caused optical desensitizaanhydrous sodium mph": 50 tion, which has been mentioned. Additional sensitivities in hydroquinone 6g. other spectral regions can be desirable for the production of anhy f s z Carbonale E- POKaSSIUm l'Ol'nl e g. certain mask ng effects Preferably, however, the same sen wmrsumciemfor 1000 mL sitiser is used in both ad acent layers.
  • the process according to the invention is suitable for single color and multicolor material. It is however of particular im- 1; (96 q su p Ul'lC ucl strengt m portance in the manufacture of multicolor images, because crymmnesodium hypophosphm Is the requirement of matching the gradations and sensitivities of potassium io i 10 the individual color layers to one another reduces the scope -h x y for variations.
  • a multicolor material contains at least two l ff th water sufl'icient for 1000 ml.
  • silver halide emulsion layers containing image dyestu W1 2 mmutes soakmg the image dyestuffs in the layers being different from one 6minutes silver bleaching bath another, and can contain one or more double layers according to the invention.
  • These double layers can optionally be '2; 96 g? su p uric act strcngl n1 separated from other emulsion layers by intermediate layers, crystalline coppersulphm 20 and these intermediate layers can also contain customary adpotassium bromide 60 ditives such as filter dyestuffs, UV absorbers or oxidizing wfllersumciemfor 1000 agems. 2 minutes soaking.
  • Photographic transparent material of high color density is of 4 mmutes fi f bath particular interest Composition as for stop-fixing bath.
  • a preferred three-color material according to the present 8 mmutes Soakmg- I invention has the f ll i Structure; Three color wedges A, B and C, running in the same direction as the original, are obtained and these are measured blluwensmve, colourless behind blue filters.
  • the gradation curves A, B and C are shown in the graphs in FIG. 1.
  • the wedge densities of the exposure wedge (exyellow posure increases from left to right) are plotted on the abscisgmemensime' colourless sac and the density is plotted on the ordinate. This is also the case for the curves in FIGS. 2 to 4.
  • Wedge A is too steep.
  • Wedge B is too flat and only inintemmdiatfllayer (g completely bleached.
  • Wedge C has the desired gradation.
  • the material C has the same threshold sensitivity as the material A, that the gradations A and C follow a very similar course in the bottom sections, and that the image s pp p q or preferably transparent C above all follows a flatter course relative to image A, as a result of a shoulder correction, and has a linearised gradation.
  • Suitable pyrazines, quinoxalines or phenazines are preferably used as dyestuff bleaching catalysts.
  • the image EXAMPLE 2 dyestuffs are as a rule azo dyestuffs.
  • the silver bromide used is sensitized with a green-sensitizer 1Q sitizer/lOO g. of Ag. After the same processing as in Example and the exposure is carried out with green light. The three resulting color gradations can be seen from the graphs in FIG. 2.
  • EXAMPLE 3 A 2.5 a thick layer with silver bromide (1.5 g. of Ag/m?) sensitized towards red light and a blue-green dyestuff of formula H 0 5 -5 0 B H; 0
  • a 2.5 [1. thick gelatine layer is cast onto a part of the material.
  • EXAMPLE 4 The procedure of Example 3 is adopted, but with the difference that the silver bromide of the color layer and the silver bromide of the covering layer are sensitized in different ways, with the same sensitizer being employed in different amounts.
  • a red-sensitizer of formula is used for sensitising the silver bromide in all layers, and in particular the silver bromide of the color layer is sensitized with 80 mg. of sensitiser/ 100 g. of Ag, and the silver bromide of the colorless layer is sensitized with only 40 mg. of senemulsion layer which is free of image dyestuff has a higher 3, the three images A, B and C are obtained. It can be seen from the gradation curves of FIG. 4 that compared to the control experiment ('A) both a gain in sensitivity and a linearisation effect are achieved through a covering layer with 0.5 g. of Ag/m. (B) and even more so by a covering layer with 1.0 g. of Ag/m? (C).
  • EXAMPLE 5 A material is cast using the following layer arrangement: 9 protective layer 8 AgBr, blue-sensitive 7 AgBr, blue-sensitive yellow dyestuff as in Example I 6 intermediate layer 5 AgBr, green-sensitive 4 AgBr, green-sensitive purple dyestuff as in Example 2 3 intermediate layer 2 AgBr, red-sensitive 1 AgBr, red-sensitive blue-green dyestuff as in Example 3 support, transparent.
  • the layer support is not transparent but opaque white.
  • the image dyestuff has the formula (3) and is used at a reflection density of 2.0.
  • the silver bromide used is sensitized with a red sensitizer; it is used in an amount of 0.9 g. of Ag/m. in the lower layers (material A and C) and in an amount of 0.45 g. of Ag/m. in the upper layers (material B and C).
  • the exposure is carried out with red light.
  • the three color gradations obtained can be seen from the graph in FIG. 5.
  • a process for the manufacture of a photographic color image by the silver dyestuff bleaching process wherein a photographic material which comprises on a support at least one silver halide emulsion layer containing a diffusion-resistant bleachable image dyestuff and immediately on top of said layer on the side facing the light source, a silver halide emulsion layer free of image dyestuff, the sensitivity of which latter layer is at least as high as that of the layer containing dyestuff, is exposed imagewise and processed in the presence of a dyestuff bleaching catalyst to give a color image, the color image being produced exclusively through image dyestuffs present in the photographic material prior to the exposure.
  • a process as claimed in claim 1 whe reiri the silver halide emulsion layer which contains image dyestuff and the adjacent silver halide emulsion layer above it which is free of image dyestuff are optically sensitized in the same spectral region.
  • the photo graphic material contains at least two silver halide emulsion layers containing image dyestuff, the image dyestuffs being different from one another,
  • the photographic material comprises. in order, a support layer; a redsensitive layer with a blue green image dyestuff; a red-sensitive layer free of image dyestuff; an intermediate layer; a greensensitive layer with a purple image dyestufi; a green-sensitive layer free of image dyestuff; a yellow filter layer; a blue-sensitive layer with a yellow image dyestuff; a blue-sensitive layer free of image dyestufi.

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  • Chemical & Material Sciences (AREA)
  • Physics & Mathematics (AREA)
  • General Physics & Mathematics (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Silver Salt Photography Or Processing Solution Therefor (AREA)
US56597A 1969-07-25 1970-07-20 Silver dye bleach photographic elements and processes for their use Expired - Lifetime US3650739A (en)

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CH1144169A CH526134A (de) 1969-07-25 1969-07-25 Verfahren zur Herstellung eines photographischen Farbbildes nach dem Silberfarbbleichverfahren

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US3650739A true US3650739A (en) 1972-03-21

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US (1) US3650739A (ja)
JP (1) JPS4911571B1 (ja)
BE (1) BE753861A (ja)
CA (1) CA940363A (ja)
CH (1) CH526134A (ja)
DE (1) DE2036918C3 (ja)
FR (1) FR2055578A5 (ja)
GB (1) GB1315385A (ja)
NL (1) NL163634C (ja)
SU (1) SU383335A3 (ja)

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4197123A (en) * 1977-07-21 1980-04-08 Ciba-Geigy Ag Process for the production of masked positive color images by the silver dye bleach process
US4386144A (en) * 1980-08-23 1983-05-31 Fuji Photo Film Co., Ltd. Process for the production of multicolor optical filters
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

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS5422362U (ja) * 1977-07-18 1979-02-14
JPS5422363U (ja) * 1977-07-18 1979-02-14

Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2397452A (en) * 1940-08-01 1946-03-26 Du Pont Photographic element

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2397452A (en) * 1940-08-01 1946-03-26 Du Pont Photographic element

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4197123A (en) * 1977-07-21 1980-04-08 Ciba-Geigy Ag Process for the production of masked positive color images by the silver dye bleach process
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
US4386144A (en) * 1980-08-23 1983-05-31 Fuji Photo Film Co., Ltd. Process for the production of multicolor optical filters
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
NL7011007A (ja) 1971-01-27
NL163634C (nl) 1980-09-15
DE2036918A1 (de) 1971-02-04
GB1315385A (en) 1973-05-02
CA940363A (en) 1974-01-22
JPS4911571B1 (ja) 1974-03-18
BE753861A (fr) 1971-01-25
SU383335A3 (ja) 1973-05-25
NL163634B (nl) 1980-04-15
CH526134A (de) 1972-07-31
DE2036918C3 (de) 1980-08-07
DE2036918B2 (de) 1979-10-31
FR2055578A5 (ja) 1971-05-07

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