CA1259516A - Negative photographic silver dye bleach material - Google Patents
Negative photographic silver dye bleach materialInfo
- Publication number
- CA1259516A CA1259516A CA000422048A CA422048A CA1259516A CA 1259516 A CA1259516 A CA 1259516A CA 000422048 A CA000422048 A CA 000422048A CA 422048 A CA422048 A CA 422048A CA 1259516 A CA1259516 A CA 1259516A
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- Prior art keywords
- silver
- dye
- layer
- photographic material
- material according
- Prior art date
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Classifications
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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
Abstract
Negative photographic silver dye bleach material.
Abstract Negative photographic silver dye bleach material which contains on a support (a) a layer containing an image dye, a low sensitive silver halide emulsion, and colloidal nuclei onto which silver deposition may occur, and (b) a layer containing a highly sensitive iodide-containing silver halide emulsion. The material has increased sensitivity and yields photographic images of high quality by means of iodide ion diffusion.
Abstract Negative photographic silver dye bleach material which contains on a support (a) a layer containing an image dye, a low sensitive silver halide emulsion, and colloidal nuclei onto which silver deposition may occur, and (b) a layer containing a highly sensitive iodide-containing silver halide emulsion. The material has increased sensitivity and yields photographic images of high quality by means of iodide ion diffusion.
Description
~s~s a.~;
Case 8-13817/TEL 233/+
Negative photographic silver dye bleach material.
It is known that photographic silver dye bleach materials contain image dyes which are bleached imagewise, in the presence of silver, by strongly acidic solutions which contain a silver-complexing agent.
This reductive bleaching can be accelerated by bleaching catalysts.
The reducing action of silver on the image dyes can be used for converting photographically produced silver images into colour images.
In doing so, the silver image normally produced by the exposure of the material is negative, i.e. a counter-image of the original. The dye bleaching subsequent to the development then causes a positive colour image obtained from the negative silver image, which colour image corresponds to the original. Such positive silver dye bleach materials are therefore used primarily for producing positive colour images (colour prints) from (positive) colour slides. If a colour negative is used as original instead of a colour slide, then a negative colour image is obtained.
In order to obtain a positive colour image also from a colour negative with a silver dye bleach material, it is necessary to use a negative material in which a positive silver ima~e i9 producect by ttevelop-ment after exposure. The posi~ive silver image t~len leads, ater processing, to the formation of a colour image which is a counter-image of the original (colour negative) and is therefore a positive colour image. Using a negative silver dye bleach material, a (positive) colour slide as original would consequently lead to the formation of a negative colour image.
,; ~
5 ~ 5 Suitable processes for producing a positive silver image are based e.g. on the silver complex diffusion process described in DE
1 572 206 (published 1967) or in GB 656 131 (published 1951), or on the bromide ion diffusion process known e.g. from DE 859 711 (published 1952). If the silver complex diffusion process is chosen, then a developing solution which contains the silver complexing agents is used for developing the negative silver image.
The undeveloped unexposed silver halide areas dissolve in the developer to form silver complexes which diffuse imagewise into a receiving layercontaining development nuclei. Silver is deposited OlltO
these nuclei by physical development from the developing solution which contains the silver complex toform a positive image. For bromide ion diffusion, the photographic material must contain, in one and the same layer, development nuclei, a substantial amount of a weakly light-sensitive silver chloride emulsion, and a small amount of a highly sensitive silver bromide emulsion. After exposure, bro~ide ions are released imagewise during the development of the silver bromide and, in turn, inhibit the development of the silver chloride. In this process, there are formed simultaneously a weak negative image from the silver bromide emulsion and a strongly opaque, and therefore ultimately substantially positive, image from the silver chloride emulsion.
The use of these processes for obtaining silver reversal images with silver dye bleach materials is already known from US 2 673 800 (Meeussen et al, 3/1954). The material disclosed therein contains development nuclei in the dyestuff lsyer. The unexposet and unreducible salts in ~he light-sensitive siLver halide emulsion in the superposed layer diffuse as silver complexes into the layer containing develoFment nuclei and form a positive silver image which i8 converted into a negative colour image by dye bleaching. However, in this process it is difficult to control the reactions which take place during development, viz. the development of the exposed and the-resolution of the unexposed silver halide crystals, the diffusion of :
1:25~5~L~
the silver complexes formed into the lower layer and the physical development of the diffused complexes in the dyestuff layer, in such a manner that colour images with good white and adequate maximum density are formed. The bro~ide ion diffusion process is used in accordance with DE 20 53 751 (published 1972) to obtain the positive silver image necessary for the dye bleaching. In this process, it is proposed to use an interlayer containing fine-grained silver chloride to separate the layers provided for the individual colours. Incorrect colours in a multi-coloured material can be avoided by trapping bromide ions which diffuse in an unwanteddirection. This process, however, rules out any use of bromide or other conventional additives used as antifogging agents, e.g. benztriazole, in the developer solution. In practice, this requirement can be met only with the greatest difficulty.
Further, a positive silver image can also be produced in silver dye bleach materials by iodide ion diffusion, e.g. as described in EP 44813 (published January 1982). In this process, a masked core-shell emulsion is used for producing the positive silver image. ~evelopment is effected chemically, i.e. the developing solution contains no silver complexing agents. The composition of ehis developing solution therefore differs from that of solutions used for self-masking positive silver dye bleach materials, as these latter solutions contain e.~. silver complexing agents. This is, of course, a considerable drawback as regards achieving uniformity in the processing of positive and negative silver dye bleach materials.
Accordingly, it is the object of the present invention to provide a negative silver dye bleach material, which can be processed in developing solutions which contain silver complexing agents.
This object is accomplished by using a photographic material which, - ~L2~;~53~
by means of iodide ion diffusion, permits development in solutions which contain silver complexing agents and results in the fonmation of high-quality images which are couneer-images of the original.
~ccordingly, the invention provides a negative photographic silver dye bleach material, which contains on a support~
(a) at least one layer containing a bleachable image dye, a low-sensitive silver halide emulsion (of low sensitivity), and colloidal nuclei onto which silver deposition may occur, and (b) at least one layer containing a highly sensitive iodide-containing silver halide emulsion (of high sensitivity).
A further object of the invention is the use of the photographic material for producing photographic images.
Still further objects of the invention are a process for producing photographic ima~es with the aid of the said photographic material, the images produced with said material, and the composition for developing said material.
Suitable supports for the photographic material of the invention may be made of transparent or pigmented cellulose triacetate or poly-ester. If felt paper is used as support, it may be coated on both sides with a layer of varnish or polyethylene.
The image dyes must be bleachable under the conditions oE conventional processing baths for the silver dye bleach process. Suitable dyes are described e.g. in US 3 454 402 (Anterau et al, 7/1969), US 3 443 952 (Andersau et al, 5/1969), US 3 804 630 (LoefEel et al, 4/1974), US 3 931 142 (Lenoir et al, L/1976) and US 4 051 123 (Piller et al, 9/1977)-~ 25~S~
The customary photographic silver halide emulsions may be used forthe photographic material of this i~vention. Suitable silver halides are silver chloride, silver ~romide or silver iodide7 as well as mixtures of these halides. The concentrations of the diEferent halides may vary within wide limits. The low-sensitive silver halide emu]sions should essentially be free from iodide or should have an iodide content of less than 1, preferably 0.9 (inclusive) mole percent. Higher concentrations of iodide are generally not suitable, as they may hamper the control of the development necessary for the process of the invention through the presence of diffusing iodide ions. silver chloride, silver bromide or silver chlorobromide are therefore suitable Eor the low-sensitive silver halide emulsions. The highly sensitive silver halide emulsions used in the process of the invention contain more than 1 (inclusive) mole percent of silver iodide in addition to silver chloride and/or silver bromide. It is preferred to use 1 to 10 mole percent of silver iodide.
It is preferred to use gelatin as protective colloid for the silver halides. However, other water-soluble protective colloids such as polyvinyl alcohol or polyvinyl pyrrolidinone are also suitable.
A portion of the gelatin may also be replaced by dispersions of water- insoluble high molecular compounds. It is customary to use e.g. dispersion polymers of a,~-unsaturated compounds such as acrylic acid esters, vinyl esters, vinyl ethers, vinyl chloride, vinylidene chloride, as well as those of otler mixtures ~Ind copolymers.
The nuclei present in the lowly sensitive silver halide emulsion layers and onto which deposition of metallic silver occurs, are colloidal hydrosols or sulfides of heavy metals and noble metals.
For example, silver and nickel sulEide or hydrosois of gold, silver and palladium may be used. The nuclei are incorporated in very small amounts, e.g. 0.1 to 100 mg/m , in the layer.
~ `
For controlling the development kinetics, the low-sensitive layer may contain developing retarders. In principle, all known developing retarders which satisfy this condition are suitable. However, those compounds which can be stored in a diffusion-resistant form in the photographic layers are preferably suitable. These are primarily compounds containing ballast groups, which are sparingly soluble or virtually insolub]e in water.
Examples of suitable compounds of this type are S-mercaptotetrazoles which are substituted in the l-position by aryl groups, preferably by polynuclear aryl groups such as naphthyl or diphenyl, or aryl groups which may also be substituted preferably by long chain ~C13-C18)-alkyl, especially phenyl, or also by aralkyl or alkyl, each containing preferably at least 3, most preferably 3 to 18, carbon atoms.
Examples of particularly suitable developing retarders are 5-mercaptotetrazoles which are substituted in the l-position by one of the following groups: n-propyl, i-propyl, n-butyl, i-butyl, t-butyl, i-amyl, i-octyl, t-octyl, nonyl, decyl, lauryl, myristyl, palmityl, stearyl, di-t-butyl-phenyl, octylphenyl, dodecylphenyl, naphthyl, ~- or ~-naphthyl or diphenyl. It is also possible to use mercaptotetrazoleswhich do not contain trueballast groups and which are not diffusion-resistant. However, in this case, it must be ensured that the developing retarder does not diffuse in an unwanted direction into an adjacënt lnyer and, ~or exan~ple, retard the developin~ of the ~mul~iolls wllich supply iodide ions. This can be prevented, Eor example, by inserting an interlayer. Under this condition, it is also possible, for example, to use mercaptotetrazoles which are substituted in the l-position by the following groups: phenyl, phenyl substituted by hydroxyl, halogen (chlorine or bromine) or lower alkyl (C2-C3), methyl or ethyl benæoate, methyl or ethyl. In general, however, the use of dif-=~
~S~*~
fusion-resistant developing r~tarders is to be preferred because the layer assembly, especially the assembly of materials having a multiplicity of colour layers and emulsion layers, is thereby substantially simplified. The developing retarders may be used in amounts of 0.2 to 10 millimoles, preferably of 0.5 to 2 millimoles, per mole of silver in the emulsion.
The low-sensitive layer is preferably directly adjacent to the highly sensitive layer. Both layers form a pair, of which the highly sensitive layer is usually positioned above the low-sensitive layer in the direction of incident light. This arrangement brings about the high sensitivit7 of the photographic material. It is therefore possibLe to produce a highly sensitive blac~ and white negative e.g. by incorporating a black bleachable dye into the low-sensitive layer, and in doing so to recover the silver employed as silver halide almost completely from the processing solutions.
However, the two layers may also be separated from each other by an interlayer in which preferably a bleaching inhibitor is stored in a diffusion-resistant form.Such bleaching inhibitors are described e.g.
in DE- 1 547 725 (published 1970).
Image dye and colour sensitivity of the iodide-containing silver halide emulsion of a pair of layers are usually so adjusted that the emulsion reaches the greatest degree of sensitivity precisely in that area of the spectrum in which the assigned image dye has its adsorption maximum. For example, a yellow dye will be assign~d to a blue-sensitive emulsion.
The photographic material of this invention may contain several such pairs of layers; It is preferred to use a material which contains three pairs of layers: on a support a first pair containing a cyan dye, then a second pair containing a magenta dye, and finally a third pair containing a yellow dye. The photographic material thus covers the entire rangeof the spectrum. So-called false colour negative material, with which special effects can be :, ' , ~ 2~95~
obtained, is produced by selecting other combinations of the sensi-tivity maximum of the (highly sensitive) silver halide emulsion and of the absorption maximum of the image dye.
Barrier layers may also be present between the individual pairs of layers. These barrier layers contain a diffusion-resistant substance which absorbs iodide ions so as to prevent undesirable interactions between the pairs of layers.
Further, the photographic material of the invention may also contain additional interlayers which, in addition to gelatin, may also contain further additives such as bleaching inhibitors, light stabilisers, fluorescent whitening agents, filter dyes or plasti-cisers.
Processing of the exposed and developed silver dye bleach materials is carried out in conventional manner and comprises silver developing, dye bleaching, silver bleaching and Eixing, and subsequent washing which may also be carried out between the individual steps.
The dye bleaching and the silver bleaching, and optionally also the fixing, can be combined in a single treatment step.
For silver developing, it is possible to use baths of conventional composition, for example baths which contain hydroquinone as the developer substance, or additionally l-phenyl-3-pyrazolidone.
The developing solutions must ~Idclition~Lly cont~lin tt~e silver complexing agetlt which is necess.lry for lnitiating the spontaneous development in the low-sensitive layer. 5uitable complexing agents are e.g. the alkali meta] salts, such as the sodium and potassium salts or ammonium salts, of thiosulfuric acid, and also salts of thiocyanic acid. However, sodium thiosulfate is preferred.
One litreof developmentbath willcontain e.g. fromO.3 to 60 millimoles 5~
of sodium thiosulfate, but the optimum amount can vary within the indicated limits depending on the n~ture of the material, the temperature of the development bath and of the desired duration of action. It is also possible to incorporate developer compounds or developer precursors into the emulsion layers, while at the same time ensuring by appropriate buffering that these substances remain inactive in the dry layer during storage. In this case, solely an activator bath having a high pH value and which may contain no developer compounds is required for initiating the development.
If the dye bleaching is carried out as a separate treatmen~ step, the dye bleach baths used preferably contain a dye bleach catalyst in addition to a strong acid, a water-soluble iodide and an anti-oxidant for the iodide. Combined dye bleach and silver bleach baths as a rule also contain a water-soluble oxidising agent in addition to the specified components. Suitable dye bleach catalysts are pri-marily diazine compounds, for example derivatives of pyrazine, quinoxaline or phenazine, which are described for example in DE
Case 8-13817/TEL 233/+
Negative photographic silver dye bleach material.
It is known that photographic silver dye bleach materials contain image dyes which are bleached imagewise, in the presence of silver, by strongly acidic solutions which contain a silver-complexing agent.
This reductive bleaching can be accelerated by bleaching catalysts.
The reducing action of silver on the image dyes can be used for converting photographically produced silver images into colour images.
In doing so, the silver image normally produced by the exposure of the material is negative, i.e. a counter-image of the original. The dye bleaching subsequent to the development then causes a positive colour image obtained from the negative silver image, which colour image corresponds to the original. Such positive silver dye bleach materials are therefore used primarily for producing positive colour images (colour prints) from (positive) colour slides. If a colour negative is used as original instead of a colour slide, then a negative colour image is obtained.
In order to obtain a positive colour image also from a colour negative with a silver dye bleach material, it is necessary to use a negative material in which a positive silver ima~e i9 producect by ttevelop-ment after exposure. The posi~ive silver image t~len leads, ater processing, to the formation of a colour image which is a counter-image of the original (colour negative) and is therefore a positive colour image. Using a negative silver dye bleach material, a (positive) colour slide as original would consequently lead to the formation of a negative colour image.
,; ~
5 ~ 5 Suitable processes for producing a positive silver image are based e.g. on the silver complex diffusion process described in DE
1 572 206 (published 1967) or in GB 656 131 (published 1951), or on the bromide ion diffusion process known e.g. from DE 859 711 (published 1952). If the silver complex diffusion process is chosen, then a developing solution which contains the silver complexing agents is used for developing the negative silver image.
The undeveloped unexposed silver halide areas dissolve in the developer to form silver complexes which diffuse imagewise into a receiving layercontaining development nuclei. Silver is deposited OlltO
these nuclei by physical development from the developing solution which contains the silver complex toform a positive image. For bromide ion diffusion, the photographic material must contain, in one and the same layer, development nuclei, a substantial amount of a weakly light-sensitive silver chloride emulsion, and a small amount of a highly sensitive silver bromide emulsion. After exposure, bro~ide ions are released imagewise during the development of the silver bromide and, in turn, inhibit the development of the silver chloride. In this process, there are formed simultaneously a weak negative image from the silver bromide emulsion and a strongly opaque, and therefore ultimately substantially positive, image from the silver chloride emulsion.
The use of these processes for obtaining silver reversal images with silver dye bleach materials is already known from US 2 673 800 (Meeussen et al, 3/1954). The material disclosed therein contains development nuclei in the dyestuff lsyer. The unexposet and unreducible salts in ~he light-sensitive siLver halide emulsion in the superposed layer diffuse as silver complexes into the layer containing develoFment nuclei and form a positive silver image which i8 converted into a negative colour image by dye bleaching. However, in this process it is difficult to control the reactions which take place during development, viz. the development of the exposed and the-resolution of the unexposed silver halide crystals, the diffusion of :
1:25~5~L~
the silver complexes formed into the lower layer and the physical development of the diffused complexes in the dyestuff layer, in such a manner that colour images with good white and adequate maximum density are formed. The bro~ide ion diffusion process is used in accordance with DE 20 53 751 (published 1972) to obtain the positive silver image necessary for the dye bleaching. In this process, it is proposed to use an interlayer containing fine-grained silver chloride to separate the layers provided for the individual colours. Incorrect colours in a multi-coloured material can be avoided by trapping bromide ions which diffuse in an unwanteddirection. This process, however, rules out any use of bromide or other conventional additives used as antifogging agents, e.g. benztriazole, in the developer solution. In practice, this requirement can be met only with the greatest difficulty.
Further, a positive silver image can also be produced in silver dye bleach materials by iodide ion diffusion, e.g. as described in EP 44813 (published January 1982). In this process, a masked core-shell emulsion is used for producing the positive silver image. ~evelopment is effected chemically, i.e. the developing solution contains no silver complexing agents. The composition of ehis developing solution therefore differs from that of solutions used for self-masking positive silver dye bleach materials, as these latter solutions contain e.~. silver complexing agents. This is, of course, a considerable drawback as regards achieving uniformity in the processing of positive and negative silver dye bleach materials.
Accordingly, it is the object of the present invention to provide a negative silver dye bleach material, which can be processed in developing solutions which contain silver complexing agents.
This object is accomplished by using a photographic material which, - ~L2~;~53~
by means of iodide ion diffusion, permits development in solutions which contain silver complexing agents and results in the fonmation of high-quality images which are couneer-images of the original.
~ccordingly, the invention provides a negative photographic silver dye bleach material, which contains on a support~
(a) at least one layer containing a bleachable image dye, a low-sensitive silver halide emulsion (of low sensitivity), and colloidal nuclei onto which silver deposition may occur, and (b) at least one layer containing a highly sensitive iodide-containing silver halide emulsion (of high sensitivity).
A further object of the invention is the use of the photographic material for producing photographic images.
Still further objects of the invention are a process for producing photographic ima~es with the aid of the said photographic material, the images produced with said material, and the composition for developing said material.
Suitable supports for the photographic material of the invention may be made of transparent or pigmented cellulose triacetate or poly-ester. If felt paper is used as support, it may be coated on both sides with a layer of varnish or polyethylene.
The image dyes must be bleachable under the conditions oE conventional processing baths for the silver dye bleach process. Suitable dyes are described e.g. in US 3 454 402 (Anterau et al, 7/1969), US 3 443 952 (Andersau et al, 5/1969), US 3 804 630 (LoefEel et al, 4/1974), US 3 931 142 (Lenoir et al, L/1976) and US 4 051 123 (Piller et al, 9/1977)-~ 25~S~
The customary photographic silver halide emulsions may be used forthe photographic material of this i~vention. Suitable silver halides are silver chloride, silver ~romide or silver iodide7 as well as mixtures of these halides. The concentrations of the diEferent halides may vary within wide limits. The low-sensitive silver halide emu]sions should essentially be free from iodide or should have an iodide content of less than 1, preferably 0.9 (inclusive) mole percent. Higher concentrations of iodide are generally not suitable, as they may hamper the control of the development necessary for the process of the invention through the presence of diffusing iodide ions. silver chloride, silver bromide or silver chlorobromide are therefore suitable Eor the low-sensitive silver halide emulsions. The highly sensitive silver halide emulsions used in the process of the invention contain more than 1 (inclusive) mole percent of silver iodide in addition to silver chloride and/or silver bromide. It is preferred to use 1 to 10 mole percent of silver iodide.
It is preferred to use gelatin as protective colloid for the silver halides. However, other water-soluble protective colloids such as polyvinyl alcohol or polyvinyl pyrrolidinone are also suitable.
A portion of the gelatin may also be replaced by dispersions of water- insoluble high molecular compounds. It is customary to use e.g. dispersion polymers of a,~-unsaturated compounds such as acrylic acid esters, vinyl esters, vinyl ethers, vinyl chloride, vinylidene chloride, as well as those of otler mixtures ~Ind copolymers.
The nuclei present in the lowly sensitive silver halide emulsion layers and onto which deposition of metallic silver occurs, are colloidal hydrosols or sulfides of heavy metals and noble metals.
For example, silver and nickel sulEide or hydrosois of gold, silver and palladium may be used. The nuclei are incorporated in very small amounts, e.g. 0.1 to 100 mg/m , in the layer.
~ `
For controlling the development kinetics, the low-sensitive layer may contain developing retarders. In principle, all known developing retarders which satisfy this condition are suitable. However, those compounds which can be stored in a diffusion-resistant form in the photographic layers are preferably suitable. These are primarily compounds containing ballast groups, which are sparingly soluble or virtually insolub]e in water.
Examples of suitable compounds of this type are S-mercaptotetrazoles which are substituted in the l-position by aryl groups, preferably by polynuclear aryl groups such as naphthyl or diphenyl, or aryl groups which may also be substituted preferably by long chain ~C13-C18)-alkyl, especially phenyl, or also by aralkyl or alkyl, each containing preferably at least 3, most preferably 3 to 18, carbon atoms.
Examples of particularly suitable developing retarders are 5-mercaptotetrazoles which are substituted in the l-position by one of the following groups: n-propyl, i-propyl, n-butyl, i-butyl, t-butyl, i-amyl, i-octyl, t-octyl, nonyl, decyl, lauryl, myristyl, palmityl, stearyl, di-t-butyl-phenyl, octylphenyl, dodecylphenyl, naphthyl, ~- or ~-naphthyl or diphenyl. It is also possible to use mercaptotetrazoleswhich do not contain trueballast groups and which are not diffusion-resistant. However, in this case, it must be ensured that the developing retarder does not diffuse in an unwanted direction into an adjacënt lnyer and, ~or exan~ple, retard the developin~ of the ~mul~iolls wllich supply iodide ions. This can be prevented, Eor example, by inserting an interlayer. Under this condition, it is also possible, for example, to use mercaptotetrazoles which are substituted in the l-position by the following groups: phenyl, phenyl substituted by hydroxyl, halogen (chlorine or bromine) or lower alkyl (C2-C3), methyl or ethyl benæoate, methyl or ethyl. In general, however, the use of dif-=~
~S~*~
fusion-resistant developing r~tarders is to be preferred because the layer assembly, especially the assembly of materials having a multiplicity of colour layers and emulsion layers, is thereby substantially simplified. The developing retarders may be used in amounts of 0.2 to 10 millimoles, preferably of 0.5 to 2 millimoles, per mole of silver in the emulsion.
The low-sensitive layer is preferably directly adjacent to the highly sensitive layer. Both layers form a pair, of which the highly sensitive layer is usually positioned above the low-sensitive layer in the direction of incident light. This arrangement brings about the high sensitivit7 of the photographic material. It is therefore possibLe to produce a highly sensitive blac~ and white negative e.g. by incorporating a black bleachable dye into the low-sensitive layer, and in doing so to recover the silver employed as silver halide almost completely from the processing solutions.
However, the two layers may also be separated from each other by an interlayer in which preferably a bleaching inhibitor is stored in a diffusion-resistant form.Such bleaching inhibitors are described e.g.
in DE- 1 547 725 (published 1970).
Image dye and colour sensitivity of the iodide-containing silver halide emulsion of a pair of layers are usually so adjusted that the emulsion reaches the greatest degree of sensitivity precisely in that area of the spectrum in which the assigned image dye has its adsorption maximum. For example, a yellow dye will be assign~d to a blue-sensitive emulsion.
The photographic material of this invention may contain several such pairs of layers; It is preferred to use a material which contains three pairs of layers: on a support a first pair containing a cyan dye, then a second pair containing a magenta dye, and finally a third pair containing a yellow dye. The photographic material thus covers the entire rangeof the spectrum. So-called false colour negative material, with which special effects can be :, ' , ~ 2~95~
obtained, is produced by selecting other combinations of the sensi-tivity maximum of the (highly sensitive) silver halide emulsion and of the absorption maximum of the image dye.
Barrier layers may also be present between the individual pairs of layers. These barrier layers contain a diffusion-resistant substance which absorbs iodide ions so as to prevent undesirable interactions between the pairs of layers.
Further, the photographic material of the invention may also contain additional interlayers which, in addition to gelatin, may also contain further additives such as bleaching inhibitors, light stabilisers, fluorescent whitening agents, filter dyes or plasti-cisers.
Processing of the exposed and developed silver dye bleach materials is carried out in conventional manner and comprises silver developing, dye bleaching, silver bleaching and Eixing, and subsequent washing which may also be carried out between the individual steps.
The dye bleaching and the silver bleaching, and optionally also the fixing, can be combined in a single treatment step.
For silver developing, it is possible to use baths of conventional composition, for example baths which contain hydroquinone as the developer substance, or additionally l-phenyl-3-pyrazolidone.
The developing solutions must ~Idclition~Lly cont~lin tt~e silver complexing agetlt which is necess.lry for lnitiating the spontaneous development in the low-sensitive layer. 5uitable complexing agents are e.g. the alkali meta] salts, such as the sodium and potassium salts or ammonium salts, of thiosulfuric acid, and also salts of thiocyanic acid. However, sodium thiosulfate is preferred.
One litreof developmentbath willcontain e.g. fromO.3 to 60 millimoles 5~
of sodium thiosulfate, but the optimum amount can vary within the indicated limits depending on the n~ture of the material, the temperature of the development bath and of the desired duration of action. It is also possible to incorporate developer compounds or developer precursors into the emulsion layers, while at the same time ensuring by appropriate buffering that these substances remain inactive in the dry layer during storage. In this case, solely an activator bath having a high pH value and which may contain no developer compounds is required for initiating the development.
If the dye bleaching is carried out as a separate treatmen~ step, the dye bleach baths used preferably contain a dye bleach catalyst in addition to a strong acid, a water-soluble iodide and an anti-oxidant for the iodide. Combined dye bleach and silver bleach baths as a rule also contain a water-soluble oxidising agent in addition to the specified components. Suitable dye bleach catalysts are pri-marily diazine compounds, for example derivatives of pyrazine, quinoxaline or phenazine, which are described for example in DE
2 OlO 280 (published 1970).
Strong acids will be understood as meaning in this context acids which impart a pH value of at most 2 to the dye bleach bath or combined dye bleach and silver bleach bath. Thus, for example, it is possible possible to use hydrochloric acid, phosphoric acid and especially sulfuric acid, p-toluenesulfonic acid or sulfamic acid.
An alkali metal iodide, for example potassium iodid~ or sodium iodide, can be uset as water-soluble iodide.
Suitable oxidising agents are nitroso compounts, for example p-nitrosodimethylaniline, and nitro compounds, for example aromatic nitro compounds and preferably aromatic mono- or di-nitrobenzene-sulfonic acids, for example m-nitrobenzenesulfonic acid.
;- ' .
The antioxidants used are advancageously reductones or water-soluble mercapto compounds, as well as tertiary water-soluble phosphines.
These la~ter compounds are also effective bleaching catalysts as described in DE-2 651 969 (published 1977). Suitable reductones are, in particular> acireductones which have a 3-carbonyl-ene-1,2-diol grouping, such as reduction, triose-reductone or, preferably, ascorbic acid.
Possible mercapto compounds are those of the formula HSA(B) , in which A is an aliphatic, cycloaliphatic, araliphatic, aromatic or heterocyclic bridge member, B is a water-solubilising radical and m is an integer of at most 4 (DE-2 258 076, published 1973 and DE-2 423 814, published 1974).
The thiolactones disclosed in DE-3 045 059 (published 1981) are also suitable antioxidants.
The fixing bath can be formulated in known and conventional manner.
A suitable fixing agent is e.g. sodium thiosulfate or, advantageously, ammonium thiosulfate, optionally together with additives such as sodium bisulfite, sodium metabisulfite and/or ammonium bisulfite, and optionally a chelating agent such as ethylenediaminetetraacetic acid.
All treatment baths can contain further conventional additives, for example hardeners, wetting agents, fluorescent whitening agents or UV stabilisers.
Exposure of the yhotograpbic material of this invention results in the formation of a latent image only in the highly sensitive iodide-containing silver halide omulsion layer. This latent image is con-verted by the subsequent development into a negative silver image.
In the first layer, which contains the low-sensitive iodide-free silver halide emulsion and development nuclei, a spontaneous physical development on the development nuclei is induced under the reducing ~s~
conditions prevailing in ~he developer and through the combined action with the silver halide complexing agent. Simultaneously, however, iodide ions are set free imagewise in the superimposed second layer in tlle course of the development of the silver iodide containing emulsion to form the negative silver image. These released iodide ions then diffuse into the adjacent first layer and there inhibit depo sition of silver onto the nuclei. Thus, controlled by the diffusing iodide ions, a positive silver image is formed in this dyestuff layer, since at unexposed areas where in the second layer no iodide ions are set free, the physical development proceeds until complete density is attained, whereas physical development is suppressed at areas of strongest exposure by the released iodide ions. To delay the physical development in the nuclei containing layer until sufficient iodide ions have diffused thereinto from the adjacent layer, the crystal size as well as the content of silver chloride and silver bromide of the lowly sensitive emulsion in this first layer may be varied. In addition, the rate of development can be controlled by retarding additives, e.g. phenylmercaptotetrazole. By these measures it is possible to adjust the development kinetics of both layers in such a manner that a positive silver image is formed which, in the dye bleaching, produces a colour image with good white, the desired contrast, and high maximum density.
In the further process steps, the silver image is converted in known manner in the dyestuff layer into a coloured counter-image.
Both the negative silver image of the second layer which contains silver iodide and the positive si]ver ima~e oE ~h~ ~irst dyes~uEE
layer dlsappear during processillg, so ~hat, finally, otlly ~he colour image produced by colour bleaching remains.
' ' '' ' :
- l2 -Example 1: The following layers are coated in succession on a white-. . _ opaque paper support coated with polyethylene:
(13 a gelatin layer (coating weight 2 g/m ) which contains 200 mg/m of the magenta dye of the formula ! . . 1 OH HO--~ ~-N=N--~ ~-NHCO-~-NHCONH--~ ~--CONH--~ ~--N=N~
NH2 SO3H ~103S H2N
(I) 10 mg/m of colloidal silver, a low-sensitive monodisperse silver bromide emulsion (250 mg of silver per m ; edge length of the cryst-als 0.2 ~m) and, as developmént retarder, 0.2 mg/m2 of phenyl-mercaptotetrazole, (2) a silver iodobromide gelatin emulsion green-sensitised with a symmetrical oxacarbocyanine (95 mole % of silver bromide, 5 mole % of silver iodide; 0.2 g of silver/m ), and
Strong acids will be understood as meaning in this context acids which impart a pH value of at most 2 to the dye bleach bath or combined dye bleach and silver bleach bath. Thus, for example, it is possible possible to use hydrochloric acid, phosphoric acid and especially sulfuric acid, p-toluenesulfonic acid or sulfamic acid.
An alkali metal iodide, for example potassium iodid~ or sodium iodide, can be uset as water-soluble iodide.
Suitable oxidising agents are nitroso compounts, for example p-nitrosodimethylaniline, and nitro compounds, for example aromatic nitro compounds and preferably aromatic mono- or di-nitrobenzene-sulfonic acids, for example m-nitrobenzenesulfonic acid.
;- ' .
The antioxidants used are advancageously reductones or water-soluble mercapto compounds, as well as tertiary water-soluble phosphines.
These la~ter compounds are also effective bleaching catalysts as described in DE-2 651 969 (published 1977). Suitable reductones are, in particular> acireductones which have a 3-carbonyl-ene-1,2-diol grouping, such as reduction, triose-reductone or, preferably, ascorbic acid.
Possible mercapto compounds are those of the formula HSA(B) , in which A is an aliphatic, cycloaliphatic, araliphatic, aromatic or heterocyclic bridge member, B is a water-solubilising radical and m is an integer of at most 4 (DE-2 258 076, published 1973 and DE-2 423 814, published 1974).
The thiolactones disclosed in DE-3 045 059 (published 1981) are also suitable antioxidants.
The fixing bath can be formulated in known and conventional manner.
A suitable fixing agent is e.g. sodium thiosulfate or, advantageously, ammonium thiosulfate, optionally together with additives such as sodium bisulfite, sodium metabisulfite and/or ammonium bisulfite, and optionally a chelating agent such as ethylenediaminetetraacetic acid.
All treatment baths can contain further conventional additives, for example hardeners, wetting agents, fluorescent whitening agents or UV stabilisers.
Exposure of the yhotograpbic material of this invention results in the formation of a latent image only in the highly sensitive iodide-containing silver halide omulsion layer. This latent image is con-verted by the subsequent development into a negative silver image.
In the first layer, which contains the low-sensitive iodide-free silver halide emulsion and development nuclei, a spontaneous physical development on the development nuclei is induced under the reducing ~s~
conditions prevailing in ~he developer and through the combined action with the silver halide complexing agent. Simultaneously, however, iodide ions are set free imagewise in the superimposed second layer in tlle course of the development of the silver iodide containing emulsion to form the negative silver image. These released iodide ions then diffuse into the adjacent first layer and there inhibit depo sition of silver onto the nuclei. Thus, controlled by the diffusing iodide ions, a positive silver image is formed in this dyestuff layer, since at unexposed areas where in the second layer no iodide ions are set free, the physical development proceeds until complete density is attained, whereas physical development is suppressed at areas of strongest exposure by the released iodide ions. To delay the physical development in the nuclei containing layer until sufficient iodide ions have diffused thereinto from the adjacent layer, the crystal size as well as the content of silver chloride and silver bromide of the lowly sensitive emulsion in this first layer may be varied. In addition, the rate of development can be controlled by retarding additives, e.g. phenylmercaptotetrazole. By these measures it is possible to adjust the development kinetics of both layers in such a manner that a positive silver image is formed which, in the dye bleaching, produces a colour image with good white, the desired contrast, and high maximum density.
In the further process steps, the silver image is converted in known manner in the dyestuff layer into a coloured counter-image.
Both the negative silver image of the second layer which contains silver iodide and the positive si]ver ima~e oE ~h~ ~irst dyes~uEE
layer dlsappear during processillg, so ~hat, finally, otlly ~he colour image produced by colour bleaching remains.
' ' '' ' :
- l2 -Example 1: The following layers are coated in succession on a white-. . _ opaque paper support coated with polyethylene:
(13 a gelatin layer (coating weight 2 g/m ) which contains 200 mg/m of the magenta dye of the formula ! . . 1 OH HO--~ ~-N=N--~ ~-NHCO-~-NHCONH--~ ~--CONH--~ ~--N=N~
NH2 SO3H ~103S H2N
(I) 10 mg/m of colloidal silver, a low-sensitive monodisperse silver bromide emulsion (250 mg of silver per m ; edge length of the cryst-als 0.2 ~m) and, as developmént retarder, 0.2 mg/m2 of phenyl-mercaptotetrazole, (2) a silver iodobromide gelatin emulsion green-sensitised with a symmetrical oxacarbocyanine (95 mole % of silver bromide, 5 mole % of silver iodide; 0.2 g of silver/m ), and
(3) a gelatin protective layer (1.5 g/m ~.
The material is exposed with green light throu&h a step wedge nnd processed at 30C as rolLowtl 1. Silver developing bath 1 1/2 mi.nutes ethylenediamine tetraacetic acid, tetrasodium ~salt 2 g/l potass:ium carbonate 30 g/l potassium metabisulfite 10 g/l 125~5~
- 1.3 -sodium suliite, anhydrous 30 g/l l.-phellyl-3-pyrazolidone 0.4 g/l hydroquinone 6 g/l benztriazole 0.6 g/l potassium bromide 2.0 g/l sodium thiosulfate, anhydrous 1 g/l 2. Washing 30 seconds 3. Bleaching bath 2 minutes sulfuric acid 40 g/l sodium m-nitrobenzenesulfonate 8 g/l sodium bis(~-cyanoethyl)sulfo-ethylphosphine 3 g/l potassium iodide 6 g/l 2,3,6-trimethylquinoxaline 1.3 g/l
The material is exposed with green light throu&h a step wedge nnd processed at 30C as rolLowtl 1. Silver developing bath 1 1/2 mi.nutes ethylenediamine tetraacetic acid, tetrasodium ~salt 2 g/l potass:ium carbonate 30 g/l potassium metabisulfite 10 g/l 125~5~
- 1.3 -sodium suliite, anhydrous 30 g/l l.-phellyl-3-pyrazolidone 0.4 g/l hydroquinone 6 g/l benztriazole 0.6 g/l potassium bromide 2.0 g/l sodium thiosulfate, anhydrous 1 g/l 2. Washing 30 seconds 3. Bleaching bath 2 minutes sulfuric acid 40 g/l sodium m-nitrobenzenesulfonate 8 g/l sodium bis(~-cyanoethyl)sulfo-ethylphosphine 3 g/l potassium iodide 6 g/l 2,3,6-trimethylquinoxaline 1.3 g/l
4. Washing 30 seconds
5. Fixing solution 2 minutes ammonium thiosulfate 200 g/l potassium metabisulfite 25 g/l potassium hydroxide (85 %) 10 g/l
6. Washing 2 minutes The magenta image obtnined is a counter-.image of the e~posurc wetlge.
Example 2: The following layers are applied to a white-opaque paper support coated with polyethylene:
(1) A dyestuff layer containing per m :
..:
., , ~ . , lZ~
1 g of gelatin, 0.3 g of the dye of the formula ~ '=N\ ~ ;=N j ~ rI) 0.6 g of silver in the form of a lowly sensitive silver bromide emulsion in which the edge length of the crystals is about 0.2 pm, and 0.2 mg of red colloidal gold;
(2) a gelatin layer containing 1 g/m of gelatin and 0,5 g/m2 of finelydispersed 2,5-bis-(5-n-hexyloxycarbony1-2-methylpent-2-yl)-1,4-benzo-quinone as bleaching inhibitor;
(3) a highly sensitive silver bromoiodide layer containing 2.5 g/m2 of gelatin, O.S g/m of silver and 5 mole % of iodide; and (4) a gelatin protective layer containing 1 g/m of gelatin and 85 mg/m of l-amino-3-hydroxy-5-methylmorpholinium-triazine-tetra-fluoroborate as hardener.
The material is exposed in an sensitometer and processed as described in Example 1. The image obtained is a counter-image of the exposure wedge, i.e. a negative blnck dye image Witll a maxlm~m density oE
2.0, a minimum density oE O.l.S flnd n contr~st oE 1.5 (measured between 20 % and 80 ~ of the maximum density).
Example 3: The following layers are coated on a transparent polyester support:
1;;~5~5~
(1) a dyestuff layer containing 2.5 g/m of gelatin, 0.13 g/m of the ye].low dye of the formula (:[II) /OC?I.
N=N~ NIIC0-~ OC~3 O~tl 3 ~./ \.~' ~ 03K
200 mg/m of silver in the form of a low -sensitive, cubic-monodis-perse silver bromide emulsion in which the edge length of the crystals is 0.2 ~m, and 0.14 mg/m of red, colloidal gold;
(2) a gelati.n interlayer containing 1 g/m of gelatin and 0.5 g/m of finely ~dispersed 2,5-bis-(5-n-hexyloxycarbonyl-2-methylpent-2-yl)-1,4-benzoquinone as bleaching inhibitor; and (3) a silver bromoiodide layer containing S mole % of iodide and 2 g/m2 of gelatin, 0.25 g/m2 of silver (as silver halide with an iodide content of 5 mole %) and 1 g/m of the above bleaching inhibitor;
(4) a gelatin protective layer according to Example 2.
The material is exposed in a sellsi~ome~r und pro.essed as deseribed in Example l, to give a negative yellow dye image with a maximum density of 0.8, a minimum density of 0.1 and a contrast of 0.5 (measured between 20 % and 80 % of the maximum density).
~2~
1.xample 4: The following layers are coated on a transparent polyester support:
(1) a dyestuff layer which contains 1.8 g/m of gelatin7 0.135 g/m2 of the cyan clye of the formula ~C~3 ~3~ /S03K
co i~ \il/ ~N/i~
1 !H ~ 1H ~
3 S03K ,_.
\
(IV) S2CH3 0.3 g/m of silver in the form of a low-sensitive, cubic-monodispersed silver bromide emulsion in which the edge length of the crystals is 0.2 ~um, and 1 mg~m2 of colloidal silver sulfide;
(2) a silver bromoiodide layer which correspollds to layer(3)in Example 3 and wherein the iodide ions are uniformly distributed in the crystal, and (3) a gelatin protective layer corresporldin~ to layer~4)ill ~xanlpl~ 2.
The materlal is exposed in a sells:itolmeter and processed as described in Example 1, to give a negative cyan dye image with a maximum density of 0.5, a minimum density of 0.02 and a contrast of 0.5.
Example 5: If a silver bromoiodide emulsion which contains the iodide ;.ons in the interior of the crystals is used in the material of Example 4, then a contrast of 2~0 is obtained.
Example 2: The following layers are applied to a white-opaque paper support coated with polyethylene:
(1) A dyestuff layer containing per m :
..:
., , ~ . , lZ~
1 g of gelatin, 0.3 g of the dye of the formula ~ '=N\ ~ ;=N j ~ rI) 0.6 g of silver in the form of a lowly sensitive silver bromide emulsion in which the edge length of the crystals is about 0.2 pm, and 0.2 mg of red colloidal gold;
(2) a gelatin layer containing 1 g/m of gelatin and 0,5 g/m2 of finelydispersed 2,5-bis-(5-n-hexyloxycarbony1-2-methylpent-2-yl)-1,4-benzo-quinone as bleaching inhibitor;
(3) a highly sensitive silver bromoiodide layer containing 2.5 g/m2 of gelatin, O.S g/m of silver and 5 mole % of iodide; and (4) a gelatin protective layer containing 1 g/m of gelatin and 85 mg/m of l-amino-3-hydroxy-5-methylmorpholinium-triazine-tetra-fluoroborate as hardener.
The material is exposed in an sensitometer and processed as described in Example 1. The image obtained is a counter-image of the exposure wedge, i.e. a negative blnck dye image Witll a maxlm~m density oE
2.0, a minimum density oE O.l.S flnd n contr~st oE 1.5 (measured between 20 % and 80 ~ of the maximum density).
Example 3: The following layers are coated on a transparent polyester support:
1;;~5~5~
(1) a dyestuff layer containing 2.5 g/m of gelatin, 0.13 g/m of the ye].low dye of the formula (:[II) /OC?I.
N=N~ NIIC0-~ OC~3 O~tl 3 ~./ \.~' ~ 03K
200 mg/m of silver in the form of a low -sensitive, cubic-monodis-perse silver bromide emulsion in which the edge length of the crystals is 0.2 ~m, and 0.14 mg/m of red, colloidal gold;
(2) a gelati.n interlayer containing 1 g/m of gelatin and 0.5 g/m of finely ~dispersed 2,5-bis-(5-n-hexyloxycarbonyl-2-methylpent-2-yl)-1,4-benzoquinone as bleaching inhibitor; and (3) a silver bromoiodide layer containing S mole % of iodide and 2 g/m2 of gelatin, 0.25 g/m2 of silver (as silver halide with an iodide content of 5 mole %) and 1 g/m of the above bleaching inhibitor;
(4) a gelatin protective layer according to Example 2.
The material is exposed in a sellsi~ome~r und pro.essed as deseribed in Example l, to give a negative yellow dye image with a maximum density of 0.8, a minimum density of 0.1 and a contrast of 0.5 (measured between 20 % and 80 % of the maximum density).
~2~
1.xample 4: The following layers are coated on a transparent polyester support:
(1) a dyestuff layer which contains 1.8 g/m of gelatin7 0.135 g/m2 of the cyan clye of the formula ~C~3 ~3~ /S03K
co i~ \il/ ~N/i~
1 !H ~ 1H ~
3 S03K ,_.
\
(IV) S2CH3 0.3 g/m of silver in the form of a low-sensitive, cubic-monodispersed silver bromide emulsion in which the edge length of the crystals is 0.2 ~um, and 1 mg~m2 of colloidal silver sulfide;
(2) a silver bromoiodide layer which correspollds to layer(3)in Example 3 and wherein the iodide ions are uniformly distributed in the crystal, and (3) a gelatin protective layer corresporldin~ to layer~4)ill ~xanlpl~ 2.
The materlal is exposed in a sells:itolmeter and processed as described in Example 1, to give a negative cyan dye image with a maximum density of 0.5, a minimum density of 0.02 and a contrast of 0.5.
Example 5: If a silver bromoiodide emulsion which contains the iodide ;.ons in the interior of the crystals is used in the material of Example 4, then a contrast of 2~0 is obtained.
Claims (19)
1. A negative photographic silver dye bleach material, which contains on a support (a) at least one layer containing a bleachable image dye, a low-sensitive silver halide emulsion, and colloidal nuclei onto which silver deposition may occur, and (b) at least one layer containing a highly sensitive iodide-containing silver halide emulsion.
2. A photographic material according to claim 1, wherein the low-sensitive silver halide emulsion is a silver chloride, silver bromide or silver chlorobromide emulsion.
3. A photographic material according to claim 1, wherein the colloid-al nuclei are colloidal hydrosols or sulfides of heavy metals or noble metals.
4. A photographic material according to claim 1, wherein the silver halide emulsions are silver halide gelatin emulsions.
5. A photographic material according to claim 1, wherein the low-sensitive layer (a) and the highly sensitive layer (b) form a pair of layers such that layer (b) is positioned above layer (a) in the direction of incident light.
6. A photographic material according to claim 5, wherein the layer (a) contains a developing retarder.
7. A photographic material according to claim 5, wherein the layer (a) contains a bleachable black image dye.
8. A photographic material according to claim 1, which contains several pairs of layers consisting of layer (a) and (b), between which pairs barrier layers are provided.
9. A photographic material according to claim 1 which contains on a support a first pair of layers containing a cyan dye, a second pair of layer containing a magenta dye and a third pair of layers containing a yellow dye, between which pairs of layers barrier layer are provided.
10. A photographic material according to either of claims 8 or 9, wherein the barrier layers contain a diffusion-resistant reagent which absorbs iodide ions.
11. A photographic material according to claim 1, which contains interlayers containing bleaching inhibitors, filter dyes, light stabilisers, fluorescent whitening agents, plasticisers or wetting agents.
12. Use of the photographic material according to claim 1 for the production of photographic images.
13. The photograhic images produced with the photographic material claimed in claim 1.
14. A process for the production of photographic images with a negative silver dye bleach material, which process comprises exposing a material which contains on a support, (a) at least one layer containing a bleachable image dye, a low-sensitive silver halide emulsion, and colloidal nuclei onto which silver deposition may occur, and (b) at least one layer containing a highly sensitive iodide-containing silver halide emulsion, developing with a developing solution which contains a silver halide complexing agent, carrying out dye and silver bleaching, and subse-quently fixing.
15. A process according to claim 14, wherein the silver halide com-plexing agent is an alkali metal salt or ammonium salt of thio-sulfuric acid or a salt of thiocyanic acid.
16. A process according to claim 14, wherein the silver bleaching, the dye bleaching and the fixing are carried out in separate pro-cessing baths or in a single combined processing bath.
17. A process according to claim 16, wherein the silver bleaching and dye bleaching are carried out in a single processing bath.
18. A process according to claim 14, wherein the exposed and devel-oped material may be washed between each of the developing, dye bleaching, silver bleaching and fixing steps, as well as at the end of processing.
19. A conventional composition for developing the photographic material according to claim 1, which composition contains 0.3 to 60 millimoles per litre of a silver complexing agent.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CH107982 | 1982-02-22 | ||
| CH1079/82-8 | 1982-02-22 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1259516A true CA1259516A (en) | 1989-09-19 |
Family
ID=4201969
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA000422048A Expired CA1259516A (en) | 1982-02-22 | 1983-02-21 | Negative photographic silver dye bleach material |
Country Status (4)
| Country | Link |
|---|---|
| EP (1) | EP0087390B1 (en) |
| JP (1) | JPS58156931A (en) |
| CA (1) | CA1259516A (en) |
| DE (1) | DE3366751D1 (en) |
Family Cites Families (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3436219A (en) * | 1965-02-26 | 1969-04-01 | Mitsubishi Paper Mills Ltd | Color photographic material |
| DE2053751C3 (en) * | 1970-11-02 | 1979-08-02 | Mitsubishi Paper Mills, Ltd., Tokio | Color photographic material for the silver dye bleaching process and process for its manufacture |
| CH633641A5 (en) * | 1977-07-21 | 1982-12-15 | Ciba Geigy Ag | METHOD FOR PRODUCING MASKED POSITIVE COLOR IMAGES BY THE SILVER COLORING METHOD. |
| DE3066277D1 (en) * | 1979-08-01 | 1984-03-01 | Ciba Geigy Ag | Process for the production of masked positive colour images by the silver dye bleach process and the photographic silver dye bleach material for use therein |
| US4374914A (en) * | 1980-07-22 | 1983-02-22 | Ciba-Geigy Ltd. | Process for the production of negative color images by the silver dye bleach process, and the silver dye bleach material used in this process |
-
1983
- 1983-02-16 EP EP19830810064 patent/EP0087390B1/en not_active Expired
- 1983-02-16 DE DE8383810064T patent/DE3366751D1/en not_active Expired
- 1983-02-21 CA CA000422048A patent/CA1259516A/en not_active Expired
- 1983-02-22 JP JP2709983A patent/JPS58156931A/en active Pending
Also Published As
| Publication number | Publication date |
|---|---|
| EP0087390B1 (en) | 1986-10-08 |
| EP0087390A2 (en) | 1983-08-31 |
| JPS58156931A (en) | 1983-09-19 |
| DE3366751D1 (en) | 1986-11-13 |
| EP0087390A3 (en) | 1984-04-25 |
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