EP0000511B1 - Procédé photographique en couleurs par diffusion-transfert - Google Patents

Procédé photographique en couleurs par diffusion-transfert Download PDF

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Publication number
EP0000511B1
EP0000511B1 EP78100382A EP78100382A EP0000511B1 EP 0000511 B1 EP0000511 B1 EP 0000511B1 EP 78100382 A EP78100382 A EP 78100382A EP 78100382 A EP78100382 A EP 78100382A EP 0000511 B1 EP0000511 B1 EP 0000511B1
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EP
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Prior art keywords
group
layer
dye
compounds
developer
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EP78100382A
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German (de)
English (en)
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EP0000511A1 (fr
Inventor
Rudolf Chem.-Ing.Grad. Stolzenburg
Paul Dr. Marx
Walter Dr. Püschel
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Agfa Gevaert AG
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Agfa Gevaert AG
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D209/00—Heterocyclic compounds containing five-membered rings, condensed with other rings, with one nitrogen atom as the only ring hetero atom
    • C07D209/02—Heterocyclic compounds containing five-membered rings, condensed with other rings, with one nitrogen atom as the only ring hetero atom condensed with one carbocyclic ring
    • C07D209/04—Indoles; Hydrogenated indoles
    • C07D209/30—Indoles; Hydrogenated indoles with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, directly attached to carbon atoms of the hetero ring
    • C07D209/42—Carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
    • C09B29/00—Monoazo dyes prepared by diazotising and coupling
    • C09B29/06—Monoazo dyes prepared by diazotising and coupling from coupling components containing amino as the only directing group
    • C09B29/08—Amino benzenes
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
    • C09B29/00—Monoazo dyes prepared by diazotising and coupling
    • C09B29/06—Monoazo dyes prepared by diazotising and coupling from coupling components containing amino as the only directing group
    • C09B29/08—Amino benzenes
    • C09B29/0805—Amino benzenes free of acid groups
    • C09B29/0807—Amino benzenes free of acid groups characterised by the amino group
    • C09B29/0809—Amino benzenes free of acid groups characterised by the amino group substituted amino group
    • C09B29/0811—Amino benzenes free of acid groups characterised by the amino group substituted amino group further substituted alkylamino, alkenylamino, alkynylamino, cycloalkylamino aralkylamino or arylamino
    • C09B29/0823—Amino benzenes free of acid groups characterised by the amino group substituted amino group further substituted alkylamino, alkenylamino, alkynylamino, cycloalkylamino aralkylamino or arylamino substituted by CN
    • 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
    • G03C8/00—Diffusion transfer processes or agents therefor; Photosensitive materials for such processes
    • G03C8/02—Photosensitive materials characterised by the image-forming section
    • G03C8/08—Photosensitive materials characterised by the image-forming section the substances transferred by diffusion consisting of organic compounds
    • G03C8/10—Photosensitive materials characterised by the image-forming section the substances transferred by diffusion consisting of organic compounds of dyes or their precursors

Definitions

  • the invention relates to a process for the production of color photographic images by the dye diffusion transfer process and to a photographic material suitable therefor which contains new diffusion-resistant, color-providing compounds which liberate yellow diffusing azo dyes having a cyanoalkylamino group.
  • the color-providing compounds suitable for this purpose include, for example, the non-diffusing color couplers described in DT-PS 1 095 115, which, during development, result from a reaction with the oxidation product of a color developer compound consisting of a primary aromatic amine, a pre-formed or at release the dye produced in a diffusing form.
  • the selection of the developer compound required is naturally limited to color developers.
  • non-diffusing coloring compounds described in DT-OS 1 930215 which contain a pre-formed latent diffusible dye residue linked to a diffusion-resistant residue via a cleavable hydrazone group.
  • These compounds are not to be called color couplers, and it has also been shown that the choice of developer compounds which are required to release the diffusing dye residue is in no way limited to the usual color developers, but also that black and white developers, e.g. Catechins are very useful.
  • DT-OS 1 772 929 also describes non-diffusing colored compounds with a special grouping which undergo an oxidative ring closure reaction during development and thereby release a pre-formed dye residue in diffusing form.
  • the connections presented there can be divided into two groups.
  • the compounds of the one group require a customary color developer compound for development, with whose oxidation product they couple and in a subsequent ring closure reaction release the pre-formed dye residue in diffusing form.
  • the compounds of the other group are themselves silver halide developing agents and are therefore able, even in the absence of further developer compounds in the oxidized form, to undergo the aforementioned ring closure reaction with the release of the diffusing dyes.
  • non-diffusing coloring compounds of DT-OS 2 242 762 should also be mentioned at this point. These are sulfonamidophenols and sulfonamidoanilines which, after development during oxidation under the influence of developer alkali, cleave with the release of diffusing dyes with a free sulfamoyl group will.
  • the coloring compounds mentioned above work without exception negative, i.e. the image-wise distribution of the diffusing dye released arises when conventional (negative working) silver halide emulsions are used in accordance with the negative silver image produced during development. In order to generate positive dye images, it is therefore necessary to use direct-positive silver halide emulsions or else to use a suitable reversal process.
  • Non-diffusing coloring compounds are also known from DT-OSen 2 402 900 and 2 543 902, which in non-oxidized form are capable of a cleavage reaction under alkaline development conditions, whereby a diffusing dye is liberated, and in which on the other hand in oxidized form the above-mentioned cleavage reaction is made difficult or prevented.
  • Such compounds are suitable in combination with conventional negative emulsions for producing positive transfer color images.
  • the dyes can be set sufficiently in the image-receiving layer and that they also have excellent spectral properties and excellent stability against light and heat.
  • DT-OS 2 626 821 describes coloring compounds which provide yellow dyes for the color diffusion transfer process and which are to be distinguished by particularly advantageous absorption spectra and are said to have excellent color stability. However, it was found that the yellow dyes released from these color compounds left much to be desired in terms of their stability to light.
  • the invention is therefore based on the object of specifying new coloring compounds for the color diffusion transfer process, from which diffusing yellow dyes are set free during photographic processing, which have the desired spectral properties and good stain resistance, and which are furthermore distinguished by improved stability to light .
  • the coloring compounds according to the invention thus contain an azo dye residue of the formula which is connected to a diffusion-proofing oxidizable organic carrier residue either via the radical R 1 or via one of the two benzene rings shown.
  • This carrier residue is of such a type that it is split off from the coloring compounds either in oxidized form or in non-oxidized form under the conditions of photographic development by developer alkali, so that diffusing azo dyes are released.
  • Carrier residues A ', A 2 , A 3 with such functions are known.
  • DT-OSen 2 402 900 and 2 543 902 must also be mentioned here.
  • coloring compounds are described which release dyes which diffuse from the non-oxidized form in a cleavage reaction under alkaline development conditions and in which, on the other hand, the above-mentioned cleavage reaction is made more difficult or prevented in oxidized form.
  • Such compounds thus enable color transfer only at those points in which oxidation has not occurred due to development. They are therefore suitable for producing positive carry images.
  • the bivalent link X shown in general formulas I and II can, for example, be a residue of one of the following formulas: -CH 2 -CH 2 -SO 2 -C 6 H 12 - and -C 3 H 6 -NH-CO-C 2 H 4 -.
  • coloring compounds according to the invention should not diffuse as intact molecules in the layers of the photographic material.
  • they contain a diffusion-proofing residue, e.g. the rest Z.
  • Adequate diffusion resistance of the color-providing compounds can already be provided even if the color-providing compounds do not contain any longer alkyl residues, since the molecule can also have a sufficient size, depending on the dye residue. Otherwise it is possible to make the coloring compounds sufficiently diffusion-resistant by selecting residues of a suitable size.
  • organic radicals are preferably suitable which generally contain straight-chain or branched aliphatic groups and optionally also isocyclic or heterocyclic or aromatic groups with generally 8 to 20 C atoms. With the rest of the molecule these residues are either directly or indirectly, e.g. about one of the. the following groups: -NHCO-, -NHS02--, -NR-, where R is hydrogen or alkyl, -0- or -S-.
  • the diffusion-proofing residue may also contain water-solubilizing groups, e.g.
  • Sulfo groups or carboxyl groups which can also be in anionic form. Since the diffusion properties depend on the molecular size of the total compound used, it is sufficient in certain cases, e.g. if the total molecule used is large enough to use shorter-chain residues as "diffusion-proofing residues".
  • the carrier residue is split off from the non-diffusing coloring compounds according to the invention together with the diffusion-proofing residue with the liberation of a diffusing azo dye.
  • chemical conversion can take place in the split off carrier residue, e.g. an intramolecular rearrangement in the form of a ring closure reaction.
  • the released diffusing azo dyes have, for example in the case of the non-diffusing coloring compounds of the formula 11, a free sulfamoyl group and correspond to the following formula III where R 1 , R 2 , R 3 , R 5 , R 6 , r and s have the meaning already given.
  • Examples of suitable coloring compounds according to the present invention are the following: Compound No. 10
  • the other coloring compounds of the present invention can also be prepared in an analogous manner.
  • the diffusing dyes split off from the color-providing compounds according to the invention are used for the absorption measurement and light-fastness test (see Example 2).
  • the preparation of the dye released from compound 2 is described here as an example.
  • the compounds according to the invention are colored yellow. They are incorporated into the casting solutions for the layers of the photographic material using one of the usual methods.
  • the amount of coloring compound used per liter of casting solution varies within relatively wide limits, the most favorable concentration being determined on the basis of simple experiments. For example, 5 to 80 g, preferably 20 to 40 g, of coloring compound are used per liter of casting solution.
  • the association between diffusion-resistant coloring compound and silver halide required to achieve the desired effect can be produced, for example, by introducing the diffusion-resistant compounds into the casting solutions from aqueous-alkaline solutions using existing water-solubilizing groups.
  • the non-diffusing coloring compounds can also be incorporated into the layers by one of the known emulsification processes. Such methods are described, for example, in English Patents 791 219 and 1 099 414 to 1 099 417. It is also possible to prepare aqueous dispersions of the color compounds and to add them to the respective casting solutions.
  • aqueous slurries of the coloring compound are finely ground, for example by intensive stirring with the addition of sharp-edged sand or by using ultrasound.
  • the non-diffusing coloring compounds can be accommodated in a light-sensitive layer itself or in a neighboring layer.
  • the red-sensitive layer is associated with a compound that cleaves off a cyan dye
  • the green-sensitive layer is associated with a compound that cleaves off a purple dye
  • the blue-sensitive layer is associated with a coloring compound that cleaves off a yellow dye according to the invention.
  • the selection of developer substances in the process according to the invention is not limited to color developers, but that conventional black white developers can also be used, which is to be regarded as an advantage because of the lower tendency to discoloration of the latter.
  • the developers can already be contained in the layers of the color photographic material, where they are activated by the alkaline activator liquid, or in the alkaline processing liquid or paste. Since the coloring compounds according to the invention themselves have developer properties, the use of auxiliary developer compounds can be dispensed with in individual cases. In this case, the coloring compound is immediately oxidized by developable silver halide.
  • the diffusing dye released during development matches the developed silver image, as is the case with the coloring compounds of the type as described in DT-OSen 2 242 762, 2, 505 248 and also DT-OS 1 772 929, the use of direct positive silver halide emulsions or, if conventional negative emulsions are used, the use of a suitable reversal process is required to generate positive colored transfer images.
  • the diffusing dyes are not released as a result of an alkali cleavage, but rather as a result of an intramolecular displacement reaction with ring closure.
  • the dyes released also do not have a free sulfaemoyl group like the dyes split off from the coloring compounds used according to the invention, but a sulfinic acid group.
  • the invention is in no way limited to those coloring compounds in which the cleavage is carried out by alkali.
  • Such a reversal process is available in the silver salt diffusion process.
  • the photographic reversal using the silver salt diffusion process to produce positive color images using conventional color couplers is described, for example, in US Pat. No. 2,763,800.
  • a light-sensitive element is obtained which is suitable for the dye diffusion transfer process.
  • Such a photosensitive element has, for example, at least one combination of a photosensitive silver halide emulsion layer and a binder layer assigned to it, which contains development nuclei for physical development and a coloring compound.
  • the exposed portion of the silver halide is chemically developed in the light-sensitive silver halide emulsion layer; the unexposed portion is transferred by means of a silver halide solvent into the binder layer containing the associated development nuclei and is physically developed there. If a developer is used for the physical development, which is able to release a diffusing dye in oxidized form as a result of a reaction with the coloring compound present in this layer, then an imagewise distribution of diffusing dyes occurs, which is applied to an image receiving layer can be transferred and form a positive colored image there.
  • the photosensitive element When reversed using compounds which release imagewise development inhibitors, the photosensitive element consists of at least one layer combination of a photosensitive silver halide emulsion layer and a second, unexposed, developable emulsion layer which contains the coloring compound.
  • the light-sensitive silver halide emulsion layer is developed, for example, with color developers in the presence of certain compounds which release development-inhibiting substances on reaction with oxidized color developers.
  • the development-inhibiting substances which are imagewise set free in the light-sensitive layer, diffuse into the neighboring, unexposed, developable emulsion layer and visually inhibit development there.
  • the uninhibited (positive) portions of the unexposed developable emulsion layer are developed by the remaining developer, whose oxidation products then react with the non-diffusing coloring compounds according to the invention with the release of diffusing dyes, which are transferred imagewise to the image-receiving element.
  • DIR couplers are described, for example, in US Pat. No. 3,227,554.
  • all direct positive silver halide emulsions are suitable as direct positive silver halide emulsions which, with simple development, produce a positive silver image and a corresponding image-wise distribution of developer oxidation products.
  • those silver halide emulsions are suitable in which a veil that can be developed has been generated by exposure or by chemical treatment, which veil is destroyed imagewise under certain conditions during the imagewise exposure.
  • the fog remains in the unexposed areas, so that a directly positive silver image is obtained in the subsequent development, and in accordance therewith an imagewise distribution of diffusing dye if the colorant compound according to the invention is assigned to the directly positive silver halide emulsion.
  • Another group of direct positive silver halide emulsions which are preferably used according to the present invention comprises the so-called unveiled direct positive silver halide emulsions, which have a photosensitivity predominantly inside the silver halide grains. When these emulsions are exposed imagewise, a latent image is formed predominantly inside the silver halide grains.
  • the development of such unveiled, directly positive silver halide emulsions is carried out under hazing conditions, a veil being produced predominantly at the unexposed areas and a positive silver image being developed during the development.
  • the unveiled direct positive silver halide emulsions are characterized in that exposed samples are developed using a typical surface developer of the following composition: preferably no silver image, or only one with very low density, while using an inner winder of the following composition: a silver image with sufficient density is created.
  • the selective fogging of the imagewise exposed, unveiled direct positive emulsions can be carried out before or during development by treatment with a fogging agent.
  • Suitable fogging agents are reducing agents such as hydrazine or substituted hydrazines.
  • the obscuring agent can also be stored diffusion-resistant.
  • Unveiled direct-positive emulsions are, for example, those which have defects in the interior of the silver halide grains (US Pat. No. 2,592,250) or silver halide emulsions with a layered grain structure (DT-OS 2,308,239).
  • coloring compounds according to the invention are used with a non-diffusing oxidizable carrier residue of the type described in DT-OSs 2 402 900 and 2 543 902, i.e. a carrier residue which is only split off by alkali in the non-oxidized form, while in the oxidized form the removal is difficult or prevented, of course no direct positive emulsions and no reversal processes are required to produce positive transfer images, but conventional negative emulsions are sufficient.
  • the emulsions can also be chemically sensitized, e.g. by adding sulfur-containing compounds during chemical ripening, for example allyl isothiocyanate, allyl thiourea, sodium thiosulfate and the like.
  • Reducing agents e.g. the tin compounds described in Belgian patents 493,464 and 568,687, also polyamines, such as diethylenetriamine, or aminomethanesulfinic acid derivatives, e.g. be used according to Belgian patent 547 323.
  • Precious metals or noble metal compounds such as gold, platinum, palladium, iridium, ruthenium or rhodium are also suitable as chemical sensitizers. This method of chemical sensitization is described in the article by R. Koslowsky, Z. Wiss. Phot. 46, 65-72 (1951).
  • polyalkylene oxide derivatives e.g. with polyethylene oxide with a molecular weight between 1000 and 20,000
  • condensation products of alkylene oxides and aliphatic alcohols, glycols, cyclic dehydration products of hexitols, with alkyl-substituted phenols, aliphatic carboxylic acids, aliphatic amines, aliphatic diamines and amides The condensation products have a molecular weight of at least 700, preferably more than 1000.
  • these sensitizers can of course be used in combination, as described in Belgian patent 537 278 and British patent 727 982.
  • the emulsions can also be spectrally sensitized, e.g. by the usual mono- or polymethine dyes, such as acidic or basic cyanines, hemicyanines, streptocyanines, merocyanines, oxonols, hemioxonols, styryl dyes or other, also trinuclear or polynuclear methine dyes, for example rhodacyanines or neocyanines.
  • mono- or polymethine dyes such as acidic or basic cyanines, hemicyanines, streptocyanines, merocyanines, oxonols, hemioxonols, styryl dyes or other, also trinuclear or polynuclear methine dyes, for example rhodacyanines or neocyanines.
  • sensitizers are described, for example, in F. M. Hamer's work "The
  • the emulsions can contain the usual stabilizers, e.g. homeopolar or salt-like compounds of mercury with aromatic or heterocyclic rings, such as mercaptotriazoles, simple mercury salts, sulfonium mercury double salts and other mercury compounds.
  • stabilizers e.g. homeopolar or salt-like compounds of mercury with aromatic or heterocyclic rings, such as mercaptotriazoles, simple mercury salts, sulfonium mercury double salts and other mercury compounds.
  • azaindenes preferably tetra- or penta-azaindenes, in particular those which are substituted by hydroxyl or amino groups. Such connections are in the Birr article. Z. Wiss. Phot. 47, 2-27 (1952).
  • Other suitable stabilizers include heterocyclic mercapto compounds, e.g. Phenyl mercaptotetrazole, quaternary benzothiazole derivatives, benzotriazole and the like.
  • Gelatin is preferably used as the binder for the photographic layers. However, this can be replaced in whole or in part by other natural or synthetic binders.
  • natural binders e.g. Alginic acid and its derivatives such as salts, esters or amides, cellulose derivatives such as carboxymethyl cellulose, alkyl cellulose such as hydroxyethyl cellulose, starch or their derivatives such as ethers or esters or caragenates are suitable.
  • synthetic binders are polyvinyl alcohol, partially saponified polyvinyl acetate, polyvinyl pyrrolidone and the like.
  • the layers can be cured in the customary manner, for example using formaldehyde or halogen-substituted aldehydes which contain a carboxyl group, such as mucobromic acid, diketones, methanesulfonic acid esters, dialdehydes.
  • formaldehyde or halogen-substituted aldehydes which contain a carboxyl group, such as mucobromic acid, diketones, methanesulfonic acid esters, dialdehydes.
  • a photosensitive element which contains one or more silver halide emulsion layers and the associated non-diffusing, coloring compounds, and an image-receiving element in which the desired color image is obtained by means of the imagewise transferred, diffusing dyes is produced.
  • This requires that there be firm contact between the photosensitive member and the image-receiving member for at least a finite period within the development time, so that the imagewise distribution of diffusing dyes generated in the photosensitive member as a result of development can be transferred to the image-receiving member.
  • the contact can be made after development has started or it can have been made before development begins.
  • the mono-sheet material can be composed in such a way that two different parts are produced separately from one another, namely the light-sensitive part (layer elements 1-4) and the cover sheet (layer elements 5-7), which are then placed on one another on the layer side and connected to one another, if appropriate using spacer strips so that a space for receiving a precisely measured amount of a working fluid is formed between the two parts.
  • the layer elements 5 and 6, which together form the neutralization system, can also be arranged, albeit in the opposite order, between the layer support and the image-receiving layer of the light-sensitive part.
  • Means may be provided to introduce a working fluid between the photosensitive member and the cover sheet, e.g. in the form of a laterally arranged, splitable container which, when subjected to mechanical forces, pours its contents between two adjacent layers of the mono-sheet material.
  • An essential part of the photographic material according to the present invention is the photosensitive element which, in the case of a single dye transfer process, contains a photosensitive silver halide emulsion layer and associated with it, a non-diffusing coloring compound.
  • the non-diffusing compound can be located in a layer adjacent to the silver halide emulsion layer, or in the silver halide emulsion layer itself, in the latter case the color of the image dye is preferably selected such that the predominant absorption range of the coloring compound does not match the predominant sensitivity range of the silver halide emulsion layer.
  • the photosensitive element contains three such assignments of coloring compound and light-sensitive silver halide emulsion layer, the absorption range of the coloring compound generally matching the range of spectral sensitivity of the associated silver halide emulsion layer.
  • the prerequisite for the highest possible sensitivity is that the color-providing combination is arranged in a separate binder layer (seen in the direction of the light incident during the exposure) behind the silver halide emulsion layer.
  • the silver halide emulsion layers can also be arranged in a different order, but the assigned layers must also be interchanged with the coloring systems so that the assignment is retained.
  • the opaque layer arranged under the photosensitive element is permeable to aqueous alkaline treatment solutions and thus to the diffusing dyes. It has two main functions.
  • Layers with sufficient opacity, but sufficient permeability for diffusing dyes can, for example, with suspensions of inorganic or organic dark, preferably black pigments, for example with suspensions of carbon black in suitable binders e.g. be made in gelatin solutions.
  • suitable binders e.g. be made in gelatin solutions.
  • 0.5 to 2 g thick layers containing 10 to 90% by weight (based on the total dry weight) of carbon black in gelatin are sufficient in order to ensure sufficient exclusion of light during development.
  • the particle size of the pigments used is relatively uncritical as long as it does not significantly exceed ⁇ , 5 ⁇ .
  • the opaque layer preferably also comprises a white pigment layer arranged underneath.
  • a white pigment layer arranged underneath. This has the task of covering the black layer and creating a white background for the picture. All white pigments are suitable for this, provided that their opacity is sufficiently high for layers that are not too large. Examples include barium sulfate, oxides of zinc, titanium, silicon, aluminum and zircon, and also barium stearate or kaolin. Titanium dioxide is preferred as the white pigment. The same information applies to the binder, the concentration and the particle size as for the black pigments.
  • the thickness of the white pigment layer can be varied depending on the desired whiteness of the substrate. Thicknesses between 5-20 f1 are preferably used.
  • means for producing such an opaque layer may also be arranged in the monosheet material according to the present invention between the photosensitive element and the image-receiving layer, e.g. in the form of a laterally arranged container with a working fluid containing an opacifying agent (pigment) which, when subjected to mechanical forces, pours its contents between the layers mentioned, so that such a pigment layer forms there.
  • an opacifying agent pigment
  • the image-receiving layer essentially consists of a binder which contains dye mordants for fixing the diffusing dyes.
  • the dye mordants are dispersed in the receiving layer in one of the usual hydrophilic binders, e.g. in gelatin, polyvinylpyrrolidone, wholly or partially hydrolyzed cellulose residues and the like. Of course, some binders can also act as mordants, e.g.
  • Further usable binders are, for example, gyanylhydrazone derivatives of acylstyrene polymers, as described, for example, in DT-OS 2 009 498. In general, however, the last-mentioned pickling binders other binders, for example Add gelatin.
  • the transparent layer support for the monosheet material As the transparent layer support for the monosheet material according to the invention, the usual transparent support materials used in photographic practice, e.g. Films made of cellulose esters, polyethylene terephthalate, polycarbonate or other film-forming polymers can be used.
  • Films made of cellulose esters, polyethylene terephthalate, polycarbonate or other film-forming polymers can be used.
  • the alkaline processing composition sets a relatively high pH in the light-sensitive material (about 11 to 14), which triggers the development and the imagewise dye diffusion. It has been shown that at this high pH the dyes and thus the images obtained are not particularly stable. It is therefore necessary that the material is made almost neutral or weakly acidic after development is complete. This can be achieved in a known manner in that the material additionally contains an acidic polymer layer which is only gradually accessible to the alkaline processing composition in the course of development.
  • An acidic polymer layer is understood to mean a binder layer which contains polymeric compounds with acid groups, preferably sulfo or carboxyl groups. These acidic groups react with the cations of the processing mass to form salt and lower the pH of the mass.
  • the polymeric compounds and thus the acidic groups are embedded in the layer mentioned in a diffusion-resistant manner.
  • the acidic polymers are derivatives of cellulose or derivatives of polyvinyl compounds, but other polymeric compounds can also be used.
  • useful acidic polymers are: cellulose derivatives with a free carboxyl group, for example cellulose dicarboxylic acid semiesters with a free carboxyl group, such as cellulose acetathydrogenphthalat, Celluloseacetathydrogenglutarat, Athylcelluloseacetathydrogensuccinat, Celluloseacetathydrogensuccinathydrogenphthalat, ethers and esters of cellulose, which are modified with other dicarboxylic acid anhydrides or sulfonic acid anhydrides, such as o-sulfobenzoic anhydride, carboxymethylcellulose, furthermore polystyrene, polyvinyl, Polyvinylacetathydrogenphthalat, polyacrylic acid, acetals of poly
  • the acidic polymer layer must contain sufficient acid groups in order to lower the pH of the processing mass from the beginning 11 to 14 to such an extent that the material is finally almost neutral or slightly acidic (pH 5 to 8).
  • the time delay of the lowering of the pH value is achieved in a known manner in that the acidic polymer layer is coated with a so-called delay layer.
  • This delay layer is an alkali-permeable layer, which preferably consists of an alkali-inert polymer, for example of polyvinyl alcohol or a partially acetalized polyvinyl alcohol.
  • the time delay of the lowering of the pH value can be adjusted in the desired manner.
  • a brake layer with polymers of a novel permeability behavior is described, for example, in DT-OS 2 455 762.
  • Neutralization systems which are understood to mean a combination of an acidic polymer layer and a retardation layer, are described, for example, in DT-PS 1 285 310.
  • Such layer combinations can be present in the material according to the invention, for example in the light-sensitive part between the transparent layer support and the image-receiving layer.
  • Another possibility is to arrange the neutralization system from the acidic polymer layer and a delay layer on the cover sheet.
  • these two layers must be arranged in such a sequence that the alkali of the processing composition must first penetrate the retardation layer in order to get into the acidic polymer layer.
  • the dye diffusion transfer process according to the invention can advantageously be carried out in or by means of a suitable self-developing camera.
  • a suitable self-developing camera This can e.g. be provided with devices which, after exposure of the photosensitive element, make it possible to distribute a working solution between the latter and the cover sheet and to cover the photosensitive material in an opaque manner.
  • Such a camera is preferably provided with two nip rollers mounted against one another, between which the mono-sheet material is pulled out, the laterally arranged containers being split up and releasing their contents between the layers of the mono-sheet material.
  • the exposed material can be pulled out of the camera immediately after development has started.
  • the photosensitive element is brought into contact with the aqueous alkaline working solution.
  • the imagewise exposed silver halide emulsion layers are developed in the presence of the developer compound, an imagewise distribution of oxidation products of the developer compound being produced in accordance with the positive silver image thereby formed, which oxidizes the assigned coloring compound, whereupon these react the diffusing dye with the alkali of the activator splits off.
  • the aqueous alkaline working solution can contain viscosity-increasing additives, e.g. Hydroxyethyl cellulose. Development accelerators, stabilizers, silver salt solvents, fogging agents, antioxidants and other additives can also be contained in the working solution in a known manner.
  • the image set was passed through a pair of squeeze rollers, the developer paste being distributed between the photosensitive element and the cover sheet.
  • the paste thickness was 110 ⁇ . To adjust this, spacer strips of appropriate thickness were attached to the side of the image between the photosensitive element and the cover sheet.
  • the Dmax and Dmin values of the image-receiving layers listed in the following table were determined using a reflection densitometer using a blue filter.
  • the dye to be investigated was pickled by continuously immersing a transparent layer support with a pickling layer which corresponds to layer 1 from Example 1 in an aqueous dye solution. It was then washed and dried for 2 minutes.
  • the absorption measurement was carried out with a spectrophotometer.
  • the measurement was carried out in the density range (before exposure) from 1.0 to 1.5.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Physics & Mathematics (AREA)
  • General Physics & Mathematics (AREA)
  • Silver Salt Photography Or Processing Solution Therefor (AREA)
  • Plural Heterocyclic Compounds (AREA)

Claims (2)

1. Procédé photographique couleur de diffusion-transfert pour la fabrication d'images en couleur, dans lequel un matériau photographique comportant au moins une couche d'émulsion d'halogénure d'argent sensible à la lumière et un composé non diffusible libérant un colorant et associé à cette couche est exposé suivant une image et développé au moyen d'un révélateur de l'halogénure d'argent, un colorant diffusible étant libéré suivant l'image par le composé chromogène sous l'action de l'alcali du révélateur et transféré dans une couche réceptrice d'image, ledit procédé étant caractérisé en ce que l'on utilise comme composé chromogène non diffusible un composé de formule générale:
Figure imgb0030
dans laquelle:
A1 représente un reste organique de support oxydable en position o- m- ou p- par rapport au groupe azo, contenant un reste conférant la résistance à la diffusion et éventuellement lié par un élément de liaison X, dont au moins une portion est scindée dans les conditions du développement photographique, soit sous forme oxydée soit sous forme non oxydée, sous l'action de l'alcali du révélateur, conjointement avec le reste conférant la résistance à la diffusion, avec libération simultanée. suivant l'image d'un colorant azoïque diffusible;
A2 représente un reste organique de support oxydable contenant un reste qui confère la résistance à la diffusion et lié éventuellement par un élément de liaison X, ce reste de support étant relié soit directement soit par l'intermédiaire des substituants R2 et R3 en position o- ou m- au noyau phényle portant le groupe cyanoalkylamino, et au moins une portion est scindée dans les conditions du développement photographique, soit sous forme oxydée, soit sous forme non oxydée, sous l'action de l'alcali du révélateur, conjointement avec le reste conférant la résistance à la diffusion, avec libération simultanée suivant l'image d'un colorant azïque diffusible;
A3 représente un reste organique de support oxydable contenant un reste conférant la résistance à la diffusion et lié, éventuellement par un groupe de liaison X, qui est lié au substituant R1, dont au moins une portion est scindée dans les conditions du développement photographique, soit sous forme oxydée, soit sous forme non oxydée, sous l'action de l'alcali du révélateur, conjointement avec le reste conférant la résistance à la diffusion, avec libération simultanée suivant l'image d'un colorant azoïque diffusible;
R1 représente l'hydrogène ou un groupe alkyle en C1―C5, arylalkyle ou aryle,
R2, R3, R5, et RB (identiques ou différents) représentent chacun un des restes mentionnés sous R1, un halogène ou un groupe sulfo, -COOR4, trihalogénométhyle, acylamino, acyloxy, carbamoyle, sulfamoyl, ―OR4, -SR4, -SOR4, -SO2R4 (où R4 représente l'un des réstes indiqués pour R1) -N02 ou -CN,
X représente un élément de liaison bivalent de formule ―R―(L)p―(R)q―, dans laquelle R représente un reste alkylène en C1―C6 ou un reste phénylène éventuellement substitué et les deux restes R peuvent être identiques ou différents;
L représente -0-, -CO-, -CONR7, -SO2NR7, -0-CO-NR7, -S-, ―SO2―, -SO-(R7 = hydrogène ou alkyle)
p = 0 ou 1
q = 0 ou 1, et q = 1 si p = 1
I, m et n sont chacun égal à 0 ou à 1 avec la condition que I + m + n = 1,
r est égal à 2 ou 3,
s est égal à 0 ou 1.
2. Procédé selon la revendication 1, caractérisé en ce que l'on utilise comme composé chromogène non diffusible un composé de formule suivante:
Figure imgb0031
dans laquelle
R1 représente l'hydrogène ou un groupe alkyle en C1―C5,
R2, R3, R5 et R6 (identiques ou différents) représentent l'hydrogène ou le chlore ou un groupe méthyle, méthoxy, acylamino, ou nitro,
A4 représente le reste substitué par au moins un reste conférant la résistance à la diffusion, répondant à l'une des formules suivantes:
Figure imgb0032
dans lesquelles
Z représente un reste conférant la résistance à la diffusion,
Y' représente un reste nécessaire pour compléter un noyau benzénique ou naphthalénique
Y" représente un reste nécessaire pour compléter un noyau carbocyclique ou hétérocyclique condensé, éventuellement substitué, et
RB représente l'hydrogène ou un groupe alkyle, alcoxy, aryle, un groupe hétérocyclique ou un groupe carboxy, carbamoyle ou alcoxycarbonyle,
X représente un élément de liaison bivalent de formule ―R―(L)p―(R)q―, dans laquelle R représente un reste alkylène en C1―C6 ou un reste phénylène éventuellement substitué et les deux restes R peuvent être identiques ou différents;
L représente ―O― -CO-, -CONR7, -SO2NR7, ―O―CO―NR7, ―S―, ―SO2―, ―SO― (R7 = hydrogène ou alkyle)
p est égal à 0 ou à 1
q est égal à 0 ou à 1 et q = 1 si p = 1
r est égal à 2 ou à 3
s est égal à 0 ou à 1.
EP78100382A 1977-07-22 1978-07-12 Procédé photographique en couleurs par diffusion-transfert Expired EP0000511B1 (fr)

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DE19772733112 DE2733112A1 (de) 1977-07-22 1977-07-22 Fotografisches farbdiffusionsuebertragungsverfahren
DE2733112 1977-07-22

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EP0000511B1 true EP0000511B1 (fr) 1980-07-23

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JPS5945136B2 (ja) * 1979-04-05 1984-11-05 富士写真フイルム株式会社 カラ−拡散転写用写真感光シ−ト
US4435495A (en) 1980-11-17 1984-03-06 Eastman Kodak Company Release of photographic reagents with 3-pyrazolidone developing agents
US4357412A (en) * 1981-07-13 1982-11-02 Eastman Kodak Company Photographic products and processes employing novel nondiffusible bridged azoaminophenol magenta dye-releasing compounds and precursors thereof
US4357411A (en) * 1981-07-13 1982-11-02 Eastman Kodak Company Photographic products and processes employing novel nondiffusible 2-(2-pyridylazo)-4,5-bis(tertiary amino)phenol black dye-releasing compounds and precursors thereof
US4367174A (en) * 1981-07-13 1983-01-04 Eastman Kodak Company Photographic products and processes employing novel nondiffusible pyridylazo(dialkylamino)phenol magenta dye-releasing compounds and precursors thereof
US4357410A (en) * 1981-07-13 1982-11-02 Eastman Kodak Company Photographic products and processes employing novel nondiffusible pyridylazo(dialkylamino) phenol magenta dye-releasing compounds and precursors thereof
FR2589092B1 (fr) * 1985-10-28 1987-11-13 Escofier Tech Sa Procede de formage de filets helicoidaux a flanc d'inclinaison nulle ou negative
WO2025058077A1 (fr) 2023-09-15 2025-03-20 富士フイルム株式会社 Composé, composition, matériau fonctionnel, matériau photographique à halogénure d'argent photosensible et matériau photographique à halogénure d'argent photosensible de type à transfert par diffusion

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US3357969A (en) * 1958-01-15 1967-12-12 Polaroid Corp Monoazo dyes
US4076529A (en) * 1972-08-22 1978-02-28 Eastman Kodak Company Photographic diffusion transfer films, processes and compositions with color moiety releasing compound
DE2339713A1 (de) * 1973-08-06 1975-03-06 Hoechst Ag Basische azofarbstoffe, verfahren zu ihrer herstellung und ihre verwendung
US3923510A (en) * 1973-12-06 1975-12-02 Eastman Kodak Co Process for producing color images by bleaching redox diffusible dye releasers
US3954476A (en) * 1974-02-05 1976-05-04 Eastman Kodak Company Diffusable dye-releasing compounds which are cleavable upon oxidation
AR206142A1 (es) * 1974-03-08 1976-06-30 Ciba Geigy Ag Procedimiento para la obtencion de compuestos azoicos
US4053312A (en) * 1974-09-04 1977-10-11 Eastman Kodak Company O-sulfonamidonaphthol diffusible dye image providing compounds
US4013635A (en) * 1975-02-26 1977-03-22 Eastman Kodak Company Cyan azo dye-providing compounds

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DE2860058D1 (en) 1980-11-13
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JPS5423527A (en) 1979-02-22
US4195992A (en) 1980-04-01

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