US3628952A - Photographic diffusion transfer materials and processes utilizing balasted hydrazone compounds to release mobile acid dyes for transfer - Google Patents

Photographic diffusion transfer materials and processes utilizing balasted hydrazone compounds to release mobile acid dyes for transfer Download PDF

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US3628952A
US3628952A US41078A US3628952DA US3628952A US 3628952 A US3628952 A US 3628952A US 41078 A US41078 A US 41078A US 3628952D A US3628952D A US 3628952DA US 3628952 A US3628952 A US 3628952A
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dye
alkyl
diffusion
aryl
radical
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Walter Puschel
Justus Danhauser
Karlheinz Kabitzke
Paul Marx
Arnfried Melzer
Karl-Wilhelm Schranz
Hans Vetter
Willibald Pelz
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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
    • C07D277/00—Heterocyclic compounds containing 1,3-thiazole or hydrogenated 1,3-thiazole rings
    • C07D277/60—Heterocyclic compounds containing 1,3-thiazole or hydrogenated 1,3-thiazole rings condensed with carbocyclic rings or ring systems
    • C07D277/62—Benzothiazoles
    • C07D277/68—Benzothiazoles with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached in position 2
    • C07D277/82—Nitrogen atoms
    • 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

  • This invention relates to a photographic dye diffusion transfer process in which at least one silver halide emulsion layer of a photosensitive material is exposed and developed to produce a color image in which process a dye rendered diffusible through development is transferred at least in part to form an image on a receiving layer.
  • the invention also relates to a photosensitive material for carrying out this process.
  • diffusion processes for producing color photographic negative or positive images are already known in which a color-forming coupler or a preformed dye diffuses into an image-receiving layer.
  • the dye formed during chromogenic development is resistant to diffusion
  • the color-fonning coupler from which it is formed and which in principle is capable of diffusion by virtue of its average molecular weight is so incorporated in the photosensitive layer in the form of oil packs," i.e. dissolved in droplets of a high-boiling low molecular weight organic solvent substantially insoluble in water, as to be resistant to diffusion.
  • This process is described, for example, in German Pat. Nos. 1,150,278 and 1,272,716.
  • it is necessary in this process to operate at an extremely high pH value in order to achieve diffusion of the couplers.
  • This process gives azomethine dyes which have their conventional disadvantages, for example limited stability and inadequate resistance to light.
  • dye developers i.e. compounds which contain in the same molecule a dye radical and a group which is capable of developing silver halide.
  • This process is described, for example, in German Pat. No. 1,196,075.
  • extremely complicated materials are required for carrying out this process. 1n addition, it is necessary in this case too to operate at an extremely high pH value due to the nature of the diffusion-promoting hydrophilizing groups, usually phenolic hydroxyl groups.
  • the coupling position of the coupler molecule is the carbon atom in the 4-position, in the case of the phenols and a-naphthols, similarly, the coupling position is the carbon atom in the 4-position and in the case of the openchain ketomethylene couplers the coupling position is the carbon atom of the methylene group in the group -CO-CH CO--.
  • the substituent in the coupling posi tion is split off, resulting in the formation either of a diffusing azomethine dye or even, where the coupler portion is diffusion resistance, of a diffusing dye which may be of another type, depending on the way in which the process is carried out.
  • the diffusible dyes formed diffuse out of the photosensitive layer into an image-receiving layer being in intimate contact with the photosensitive layer whereupon the dyes are anchored in the receiving layer by mordanting.
  • the diffusing dyes are usually azomethine dyes to which reference has already been made, and accordingly show only a moderate stability and fastness to light.
  • other serious disadvantages arise where dyes which can belong to a different class of dyes and which hence can be more resistant to light, are split off from the coupling position of diffusion-resistant couplers in this process.
  • the reaction with oxidized color-forming developer is accompanied in the known manner by the formation of nitrogen which partly escapes from the layer in the form of microscopic bubbles and interrupts the necessary contact between the dye-giving layer and the imagereceiving layer. This is particularly the case where heating is used to accelerate the process.
  • the object of the present invention is to provide both a sim' ple dye-diffusion process and a photographic material suitable for use in this process which does not have any of the disadvantages affecting the processes referred to above.
  • a color photographic diffusion transfer process has now been found in which at least one silver halide emulsion layer of a photosensitive material is exposed and developed to form a color image and in which a dye which has been rendered diffusible through development is transferred imagewise at least in part to a receiving layer, and which is characterized by the fact that a compound of the following formula is incorporated in diffusion-fast form in the silver halide emulsion layer or in a layer adjacent thereto which compound is called dye-giving compound" hereinafter:
  • R represents hydrogen, an alkyl group with up to 20 carbon atoms and preferably with one to five carbon atoms, an aralkyl group for example benzyl, an aryl group, for example pl'ienyl, an amino group substituted by alkyl or aryl, for example phenyl, in which case two alkyl groups on the nitrogen atom can be closed together to form a ring;
  • R represents an alkyl group with up to 20 carbon atoms, an
  • aralkyl group for example benzyl, an aryl group, for example phenyl, an acyl group derived from aliphatic carboxylic acids with up to 20 carbon atoms or aromatic carboxylic acids, for example benzoyl, an amino group substituted by alkyl or aryl, for example phenyl, in which case two alkyl groups on the nitrogen can be closed together to form a ring; or R and R together represent the ring members required to complete a preferably 5- or 6-membered isocyclic or heterocyclic group with an optionally anellated benzene ring; at least one of the radicals R and R contains the group A, X represents a sulfonyl group, a carbonyl group or a single chemical bond; A represents a photographically inert radical rendering the dye-giving compound resistant to diffusion; and B is a dye radical; or A represents a dye radical either on its own or together with R and B represents a photographically inert radical rendering the dye-giving
  • radicals rendering the dye-giving compounds resistant to diffusion include radicals of the kind which enable the compounds according to the invention to be so incorporated in the hydrophilic colloids conventionally used in color photographic materials, as to be resistant to diffusion.
  • lt is preferred to use for this purpose organic radicals which may generally contain linear or branched aliphatic groups and optionally also isocyclic or heterocyclic aromatic groups. The aliphatic portion of these radicals generally contains from eight to carbon atoms.
  • These radicals are attached to the remaining portion of the molecule either directly or indirectly, for example, through one of the following groups: CONH-, SO NHl-, -CO-, -SO. NR- in which R represents hydrogen or alkyl, -O or -S-.
  • the radical rendering the dye-giving compounds resistant to diffusion may also contain water-solubilizing groups such as, for example, sulfo groups or carboxyl groups which may also be present in the anionic form. Since the diffusion properties are governed by the molecular size of the overall compound used, it is even sufficient in certain cases.
  • the radicals of dyes of all classes may be used as the dye radicals providing they are sufficiently diffusible after cleavage to be able to diffuse through the layers of the photosensitive material into the image-receiving layer.
  • the dye radicals are preferably pr0- vided with at least one but generally with a plurality of watersolubilizing groups, Suitable water-solubilizing groups include inter alia carboxyl groups, sulfo groups, hydroxyl groups or hydroxy alkyl groups.
  • Suitable water-solubilizing groups include inter alia carboxyl groups, sulfo groups, hydroxyl groups or hydroxy alkyl groups.
  • dyes particularly suitable for use in the process according to the invention azo dyes, anthraquinone dyes, phthalo cyanine dyes, indigo dyes and triphenyl methane dyes.
  • the process according to the invention is distinguished from the processes referred to in the foregoing in regard inter alia to the compounds used which do not contain any of the coupler radicals commonly used in conventional color photography.
  • Another feature which distinguishes the process according to the invention from conventional processes is the relatively wide range of suitable developer substances because the nuance of the dyes transferred is not determined by the chemi cal structure of the developer molecule.
  • the dyes split off from the dye-giving compounds according to the invention during the reaction with developer oxidation products must be sufficiently hydrophilic to enable quick and substantially quantitative diffusion to be obtained.
  • the hydrophilic properties are usually imparted by sulfo groups or carboxyl groups. it is known from coupler chemistry that it is necessary to achieve a balance between the size ofthe radicals rendering the dye-giving compounds resistant to diffusion and the number of solubilizing groups to ensure on the one hand adequate resistance to diffusion and on the other hand adequate solubility in aqueous-alkaline media.
  • the greater the number of solubilizing groups the lower is the re sistance to diffusion.
  • the larger the dye molecular split off the greater the number of solubilizing groups required for diffusion.
  • the dye-giving compounds according to the invention have to be embedded in the photosensitive layer or in a layer adjacent thereto so as to be completely resistant to diffusion, and the dyes liberated during the reaction with the developer oxidation products have to be highly soluble in the reaction media and diffusible.
  • the dye radical of the dye-giving compound is usually very large so that the dye split off should be as hydrophilic as possible, ie should contain as many solubilizing groups as possible, in order to obtain the necessary diffusion rate.
  • the resistance to diffusion of the dye-giving compounds used in accordance with the invention has to meet the same requirements as in conventional chromogenic processes, that is to say these compounds should contain as few solubilizing groups as possible so that they are optimally resistant to diffusion. Accordingly, it is desirable for solubilizing groups which remain connected with the dye molecule and impart to it a certain additional capability of diffusion, to be formed during the cleavage reaction.
  • R, and R are as defined above; at least one of the radicals R, and R contains the group BALL;
  • X represents a sulfonyl group or a carbonyl group
  • BALL represents a ballasting photographically inert radical rendering the dye-giving compound resistant to diffusion
  • DYE is a dye radical.
  • both the dye radical and the radical rendering the dye-giving compound resistant to diffusion contain solubilizing groups, preferably sulfo groups.
  • solubilizing groups preferably sulfo groups.
  • the dye split off is able to diffuse because an additional water-solubilizing group which remains in the dye molecule is formed from the sulfonyl group during cleavage by the developer oxidation product.
  • the starting compounds are highly insoluble in the photosensitive layer and hence resistant to diffusion.
  • R and R together preferably represent the ring members required to complete a heterocyclic group with a 5- or 6 -membered heterocyclic ring, for example with the oxazoline, thiazoline, imidazoline, pyrrolidine, pyrroline, l,2-dihydropyridine, l,4-dihydropyridine, thiadiazoline, pyrazoline or traizoline ring which rings can have benzene rings condensed thereto.
  • the heterocyclic group advantageously contains at least one polar water-solubilizing group, for example a sulfo group or earboxyl group, either directly or by way of a substituent, for example by way of a short-chain alkyl group.
  • Dye preferably represents a light-resistant dye radical, for example an azo dye radical, an anthraquinone dye radical or a phthalocyanine dye radical.
  • R represents hydrogen, an alkyl group, preferably with one to five carbon atoms, for example methyl, ethyl, or propyl, an aralkyl group, for example benzyl, or an aryl group, for example phenyl;
  • R represents an aryl group, for example a phenyl group which can be part of the chromophoric system of the dye radical;
  • X represents a sulfonyl group, a carbonyl group or a single chemical bond
  • BALL represents a ballasting photographically inert radical rendering the dye-giving compound resistant to diffusion
  • R preferably represents an aryl group, for example a phenyl group, to which a dye radical is attached either directly or indirectly, or which itself represent part of the chromophoric system of such a dye radical.
  • the aryl group can be linked in any position, for example in the 0-, m or p-position, through an azo group to an isocyclic or heterocyclic aromatic group, for example to an aryl group or to a S-pyrazolone group, and together with this group can thus form a dye.
  • the dye-giving compounds originally fixedly incorporated in the layer are split during the reaction with developer oxidation products, as a result of which the dyes are released from their anchorage. Since they generally contain one or even several solubilizing groups, they are able to diffuse into the image-receiving layer which is in intimate contact with the photosensitive layers at least during the development and wherein they are fixed by means of the dye mordant.
  • the radical rendering the dye-giving compound resistant to diffusion remains behind in the emulsion layer.
  • the dye-giving compounds originally fixedly incorporated in the layer are split during the reaction with developer oxidation products, as a result of which the dyes are released from their anchorage. Since they generally contain one or even several solubilizing groups, they are able to diffuse into the image-receiving layer which is in intimate contact with the photosensitive layers at least during the development and wherein they are fixed by means of the dye mordant.
  • the radical rendering the dye-giving compound resistant to diffusion remains behind in the emulsion layer.
  • the dye-giving compounds according to the invention can be prepared by methods known from the literature.
  • the hydrazones of the carbonyl compounds for example benzthiazolone hydrazones or benzaldehyde hydrazones, can be prepared by methods known from the literature.
  • the hydrazones of the carbonyl compounds for example benzthiazolone hydrazones or benzaldehyde hydrazones, can
  • the materials required for carrying out the process according to the invention basically consist of two elements, namely a photosensitive material containing at least one silver halide emulsion layer and at least one of the dye-giving compounds according to the invention, and a nonphotosensitive imagereceiving material which contains a dye mordant and which is intended to absorb the diffusing dye.
  • Conventional silver halide emulsions are suitable for the purposes of the invention. These emulsions may be based on silver halide, silver chloride, silver bromide or mixtures thereof, optionally with a small silver iodide content of up to mol percent.
  • Gelatin is preferably used as a binder for the photographic layers. However, it can be replaced at least in part by other natural or synthetic binders.
  • Suitable natural binders include, for example, alginic acid, and its derivatives such as its salts, esters or amides, cellulose derivatives such as carboxymethyl cellulose, alkyl celluloses such as hydroxy ethyl cellulose, starch or its derivatives such as its ethers or esters or carragenates.
  • Suitable synthetic binders include polyvinyl a1- coho], partially hydrolyzed polyvinyl acetate and polyvinyl pyrrolidone.
  • the emulsions can also be chemically sensitized, for example by the addition during chemical ripening of sulfur-containing compounds such as, for example, allyl isothiocyanate, allyl thiourea and sodium thiosulfate.
  • sulfur-containing compounds such as, for example, allyl isothiocyanate, allyl thiourea and sodium thiosulfate.
  • suitable chemical sensitizers include reducing agents, for example the tin compounds described in Belgian Pat. Nos. 493,464 or 568,687, also polyamines such as diethylenetriarnine, or aminomethane-sulfinic acid derivatives, for example those of the kind described in Belgian Pat. No. 547,323.
  • Suitable chemical sensitizers include noble metals or noble metal compounds such as gold, platinum, palladium, iridium, ruthenium or rhodium. This method of chemical sensitization is described in the article by R. Koslowsky, Z. Wiss. Phot.
  • the emulsions can also be sensitized with polyalkylene oxide derivatives, for example with polyethylene oxide with an average molecular weight of from 1,000 to 20,000, also with 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 and preferably in an excess of 1,000. in order to obtain special effects, these sensitizers can, of course, be used in combination as described in Belgian Pat. No. 537,278 and in British Pat. No. 727,982.
  • the emulsions can also be spectrally sensitized, for example with the usual monomethine or polymethine dyes such as cyanines, hemicyanines, streptocyanines, merocyanines, ox onoles, hemioxonoles, styryl dyes or other methine dyes which also can contain three or more nuclei, for example, rhodacyanines or neocyanines.
  • Sensitizers of this kind are described in the book by F. M. Harmer The Cyanine Dyes and Related Compounds" 1967), lnterscience Publishers, John Wiley and Sons.
  • the emulsions can contain the usual stabilizers, for example homopolar or saltlike compounds of mercury with aromatic or heterocyclic rings, such as mercaptotriazoles, simple mercury salts, sulfonium mercury double salts and other mercury compounds.
  • suitable stabilizers include azaindenes, preferably tetraor penta-azaindenes, especially those that are substituted by hydroxyl or amino groups. Compounds of this kind are described in the article by lBirr, Z. Wiss. Phot. 47, 2-58 (1952).
  • Other suitable stabilizers include inter alia heterocyclic mercapto compounds, for example phenyl mercapto tetrazole, quaternary benzothiazole derivatives and benzotriazole.
  • the emulsions can be hardened in the conventional manner, for example with formaldehyde or with halogen-substituted aldehydes containing a carboxyl group, such as mu cobromid acid, diketones, methane sulfonic acid esters and dialdehydes.
  • formaldehyde or with halogen-substituted aldehydes containing a carboxyl group, such as mu cobromid acid, diketones, methane sulfonic acid esters and dialdehydes.
  • the emulsions may be either conventional negative emulsions or even direct positive emulsions, for example those of the kind which have a high sensitivity inside the silver halide grains, or even emulsions which function in accordance with the principle of solarization.
  • the choice of the emulsions is governed by the purpose for which it is intended to use the end product. If, for example, it is intended to produce a positive image from a positive original, for example from a color transparency, direct positive emulsions would preferably be used. it is, of course, also possible to process a negative emulsion in a reverse development to form a corresponding positive image.
  • the photosensitive material contains only one photosensitive layer and, for example, only one of the dye-giving compounds according to the invention.
  • a photosensitive color photographic multilayer material with at least three separate silver halide emulsion layers of which, for example, one is sensitive to red light, another to green light and a third to blue light, will be used for the production of multicolor images.
  • Each of the aforementioned photosensitive layers is in intimate contact with one of the dye-giving compounds according to the invention.
  • the intimate contact between the dye-giving compound and the silver halide required to obtain the desired effect can be established by introducing the dye-giving compounds from aqueous-alkaline solutions into the silver halide emulsion layers utilizing the water-solubilizing groups present.
  • the diffusion-resistant compounds can also be introduced into the layers by any one of the conventional emu'
  • the dye-giving compounds together with silver ha lide and optionally developer substances in the layer in the form of so-called microcapsules, in which case two or more differently sensitized photosensitive silver halide emulsions and the corresponding diffusion-resistant compounds can also be combined in a single layer on the lines of so-called mixed grain emulsions as described, for example, in U.S. Pat. No. 2,698,794.
  • the diffusion-resistant dyes can be incorporated either in a photosensitive layer itself or in an adjacent layer.
  • the red-sensitive layer is associated with a cyan dye
  • the green-sensitive layer with a magenta dye
  • the bluesensitive layer with a yellow dye for example, to incorporate the red-sensitive layer together with silver ha lide and optionally developer substances in the layer in the form of so-called microcapsules, in which case two or more differently sensitized photosensitive silver halide emulsions and the corresponding diffusion-resistant compounds can also be combined in a single layer on the lines of so-called mixed grain e
  • the multilayer material can contain intermediate layers in which there are in corporated other substances such as, for example, filter dyes, white couplers or antioxidants in order to limit the activity of the developer oxidation products in each case to the photosensitive layer, wherein they are formed and the layers wherein the oxidation products are desired to become active.
  • the layers of the photosensitive material can also contain as a further additive developer substances, for example conventional color-forming developers of the pphenylene diamine type, and also other developers, for example hydroquinone catechol, N-methyl aminophenol or phenidone.
  • the developers may be embedded in the layer in the form of their free molecules or in the form of their salts.
  • the developers may be introduced into the layer, for example, again in the form of the aforementioned packs.
  • developing agent precursors or so-called masked developers i.e. developer derivatives which do not act independently as developers but liberate the actual developers, for example after a cleavage or a dissociation reaction initiated by heat or by alkali.
  • Masked developers of this kind and their use in photographic layers are described, for example, in German Pat. No. 1,246,406, in German Auslegeschrift 1,019,560, in British Pat. Nos. 632,836; 691,815; 783,887; 1,069,061 and 1,114,227 and in US. Pat. Nos. 3,243,294 and 3,342,599.
  • the nonphotosensitive image-receiving material usually consists of an arbitrary layer support, for example a transparent film or a suitable paper, for example a plastics-coated paper and a layer of binder which represents the image-receiving layer and which contains a dye mordant in order to fix the diffusing dyes.
  • Preferred mordants for acid dyes include long-chain quaternary ammonium or phosphonium compounds or ternary sulfonium compounds, for example of the kind described in U.S. Pat. Nos. 3,27l,l47 and 3,271,]48, also certain metal salts and their hydroxides which form substantially insoluble compounds with the acid dyes.
  • the dye mordants are dispersed in the receiving layer in one of the usual hydrophilic binders, for example in gelatin,
  • binders can, of course, also function as mordants, especially those of the kind which represents polymers of nitrogen-containing quaternary bases, for example polymers of N-methyl-Z-vinyl pyridine of the kind described, for example, in U.S. Pat. No. 2,484,430, or polymers of aminoquanidine derivatives of alkyl vinyl ketones of the kind described, for example, in U.S. Pat. No. 2,882,l 56.
  • other binders for example gelatines, will usually he added to the last of these mordant binders.
  • thephotosensitive material is initially immersed briefly in a developer solution following exposure behind a colored original, and then brought into effective contact with the nonphotoscnsitive receiving material which has also been impregnated with a developer solution. Silver halide is reduced at the exposed areas.
  • the developer oxidation product formed splits the dye-giving compounds according to the invention and the dyes which have thus been rendered diffusible diffuse imagewise into the receiving layer where they are anchored by the mordant.
  • effective contact means that the dye split off is able to diffuse between the photosensitive material and the image-receiving material.
  • This does not necessarily mean that the layers of the photosensitive material containing the dye-giving compounds according to the invention and the image-receiving layer cannot be separated from one another by further colloid layers providing this does not prevent the dyes split off from diffusing.
  • the two elements may be arranged one above the other on the same layer sup port.
  • the layer support initially carries the imagerecciving layer containing a dye mordant and a binder, and above the image-receiving layer the various layers of the photosensitive material.
  • the photosensitive layers are washed off following exposure and development and after the dyes which have been liberated imagewise by development have diffused into the lowermost image-receiving layer.
  • readily soluble emulsions for example of the kind based on polyvinyl alcohol or alkali-soluble cellulose ether phthalate, are generally used.
  • liquid or pasty mixtures required to initiate the development process can, of course, also be accommodated in breakable containers or in rupturable pods that are split open under moderate mechanical pressure, and can be arranged, for example, between the photosensitive material and the nonphotosensitive image-receiving layer as described, for example, in U.S. Pat. Nos. 2,698,244; 2,559,643; 2,647,049;
  • a composite material of p-phenylene-diamine type Suitable color-forming developers are for example N,N-dimethyl-p-phenylenediamine, N,N- diethyl-p-phenylenediamine, monomethyl-p-phenylenediamine 2-amino-5-diethyl-aminotoluene, N-hutyl-N-wsulfobutyl-p-phenylenediamine, Z-amino-S-(N-ethyl-N-fimethanesulfonamidoethylamino)-toluene, Methyl-N43- hydroxyethyl-p-phenylene-diamine, N,N-bis-(B-hydroxyethyl)-p-phenylenediamine or Z-amino-S-(N-ethyl-N-[ihydroxyethylamino)
  • color-forming developers are described, for example, in .I. Am. Chem. Soc. 73, 3,000 I I
  • black-and-white developers such as, for example, 4- aminophenol, 4-methyl aminophenol, Lmethylaminophenol or 3-methyl-4-aminophenol, can also be used for development.
  • eatechol and derivatives thereof can be used as developing substances, for example, eatechol, 4-cyclohexylcatechol, 3- methoxycatechol, 4-(N-octadecoylamino)-catechol or 5- dodecoylamino-benzodioxolone-(2).
  • the baths normally used in conventional development processes, for example in color photography, can be used as developing baths in the process according to the invention. It is also possible however, to establish the prerequisites for optimum diffusion by varying the mineral salt content of the baths, the pH value, the viscosity and by adding organic solvents. As a rule, any competent expert need only conduct a few routine preliminary tests for this purpose.
  • a red-sensitive layer which, for 500 g. of an iodide-containing silver bromide emulsion (50 g. of silver per kg. of emulsion of which 4 mol percent are in the iodide form), contains 12 mg. ofa red-sensitizer of the formula:
  • sensitizer has been mentioned in example ll of the German Auslegeschrift 1,213,240, 0.4 g. of saponin, 0.25 g. of N, N, N-tris-acryloyl hexahydro-l,3,5-triazine as hardener and 5 g. of compound 2.
  • Silver coating approximately 0.9 g./m.
  • a green-sensitive layer which, for 500 g. of the iodidecontaining silver bromide emulsion described in l, contains l5 mg. of a green-sensitizer of the formula which sensitizer has been described as dye No. 9 in Germ an Auslegeschrift 1,177,481, 0.53 g. of saponin as wetting agent, 0.25 g. of N, N, N"-tris-acryloyl hexahydrol ,3,5- triazine and 6 g. of compound 1 1. Silver coating approximately 1 g./m.
  • An unsensitized blue-sensitive emulsion layer which, for 500 g. of the iodide-containing silver bromide: emulsion, described in 1, contains 0.3 g. ofsaponin, 0.25 g. ofN, N, N"-tris-acryloyl hexahydro-l ,3,5-triazine and 6 g. of compound 32. Silver coating approximately 0.9 g./m.”
  • the photographic material is exposed behind colored originals and then processed as follows:
  • the material is immersed for 45 seconds in a developer of the following composition:
  • the photographic material is then brought into contact with an image-receiving layer which has also been immersed in the developer for 45 seconds.
  • the image-receiving layer consists of a pigmented cellulose triacetate support, onto which the following layer is cast in a thickness of from 5 to 8a: a gelatin layer containing 20 g. of polyvinyl pyridine per kg. of percent aqueous gelatin solution.
  • catechol 3 g. of catechol 0.3 g. of potassium bromide 25 g. of potassium carbonate 0.5 g. of anhydrous sodium sulfite 1 g. of ascorbic acid water up to 1,000 ml. pl-l adjusted to 12.
  • catechol is replaced by 3 g. of 4- cyclohexylcatechol.
  • a gelatin layer which. per kg. of 5 percent aqueous gelatin solution contains 30 g. of trimethyl octadecyl ammonium sulfate, 0.4 g. of saponin and 0.3 g. of N,N.N"- tris-acryloyl hexahydro-l,3,5-triazinc as hardener. This layer is cast in a thickness of 8a.
  • a sodium alginate layer approximately 1.0;; thick.
  • the color photographic material is exposed behind a mul ticolored original and processed as follows:
  • the material is immersed for 30 seconds in a developer of the following composition:
  • the material is then removed from the developer. After a contact time of 2 minutes, the developer and the emulsion layers are removed with concentrated jet of water. A full colored negative of the original with brilliant colors and deep blacks is obtained after drying.
  • EXAMPLE 4 A green-sensitized silver bromoiodide emulsion which contains per kg. 48 g. of silver and thereof 4 mol percent in the iodide form and to which have been added per kg. 15 g. of dye-giving compound 17, and 8 g. of 4-(N-octadecoylaminolcatechol is coated on to a layer support ol'cellulose triacetate. Silver coating 1,3 g. per m.
  • an imagereceiving material which consists of a layer support of cellulose triacctate on to which has been coated a 10 percent aqueous gelatin solution containing per kg. 35 kg. of trimethyl octadecyl ammonium sulfate; layer thickness 411..
  • a negative wedge is obtained in the image-receiving layer having a maximum density of 1.55 and a minimum density of 0. l 3.
  • a solution of the following composition is used as activator: 0.8 g. of anhydrous sodium sulfite 0.5 g. of potassium bromide 0.03 g. of l-phenyl-3-pyrazolidone 25 g. of potassium carbonate water up to l,000 ml. pH adjusted to 12. After processing a magenta wedge is obtained having a maximum density of 1.2 and a minimum density of0.2.
  • EXAMPLE 6 A 10 percent aqueous gelation solution which contains per kg. 20 g. of dye-giving compound 34 and mg. of silver sulfide is coated onto a'layer support of cellulose triacetate; layer thickness l.8p.. As a second layer is coated thereon a greensensitive silver bromoiodide emulsion, which contains per kg. 64 g. of silver and 4 mol percent thereof in the form of iodide; silver coating 1.6 g. per m.
  • the material After exposing behind a green step wedge, the material s dipped for 30 seconds into a developing mixture of the following composition:
  • the material is brought into contact for 3 minutes with a image-receiving material as described in example 4. After separation of the two materials a positive magenta wedge is obtained in the image-receiving material having a maximum density of 1.38 and a minimum density of 0.23.
  • a color photographic diffusion transfer process for the production of color images which comprises forming a pattern of developable silver halide in a light-sensitive photographic material comprising at least one silver halide emulsion layer and having distributed therein or in an adjacent layer a dye-giving compound being resistant to diffusion during development in the presence of an alkaline developing solution, capable of forming a diffusible acid dye on reaction with developer oxidation products and having the formula:
  • R represents hydrogen, alkyl with up to 20 carbon atoms, aryl or amino substituted by alkyl or aryl, in which case two alkyl groups on the nitrogen can be closed together to form a ring
  • R represents alkyl with up to 20 carbon atoms, aryl, acyl derived from an aliphatic carboxylic acid with up to 20 carbon atoms or an aromatic carboxylic acid, or amino substituted by alkyl or aryl, in which case two alkyl groups on the nitrogen can be closed together to form a ring
  • R, and R together represent the ring members required to complete an isocyclic or heterocyclic group; at least one of the radicals R, and R., carries the group A;
  • X represents a sulfonyl group, a carbonyl group or a single chemical bond;
  • A represents a photographically inert radical rendering the dye-giving compound resistant to diffusion; and B represents a dye radical; or A represents a dye radical either on its own or
  • R represents hydrogen, alkyl with up to 20 carbon atoms. aryl or amino substituted by alkyl or aryl, in which case two alkyl groups on the nitrogen can be closed together to form a ring;
  • R represents alkyl with up to 20 carbon atoms, aryl, acyl derived from aliphatic carboxylic acids with up to 20 carbon atoms or aromatic carboxylic acids, or amino substituted by alkyl or aryl, in which case two alkyl groups on' the nitrogen can be closed together to form a ring; or
  • R, and R together represent the ring members required to complete an isocyclic or heterocylic ring; at least one of the radicals R, and R carries the group BALL;
  • X represents a sulfonyl group or a carbonyl group
  • BALL represents a ballasting photographically inert radical rendering the dye-giving compound resistant to diffusion
  • DYE represents a dye radical
  • R represents hydrogen, alkyl or aryl.
  • R represents an aryl group which can be part of th chromophoric system of the dye radical
  • X represents a sulfonyl group, a carbonyl group or a single chemical bond
  • BALL represents a ballasting photographically inert radical rendering the dye-giving compound resistant to diffusion
  • DYE represents a dye radical either on its own or together with R,.
  • a color photographic diffusion transfer process for the production of color images which comprises exposing to a visible subject a light-sensitive photographic material comprising superposed red, green, and blue light-sensitive silver halide emulsion layers and having distributed therein or in layers adjacent thereto dye-giving compounds being resistant to diffusion during the development in the presence of an alkaline developing solution, capable of forming a cyan, magenta, and yellow diffusible acid dye on reaction with developer oxidation products and having the formula:
  • R represents hydrogen, alkyl with up to carbon atoms, aryl or amino substituted by alkyl or aryl, in which case two alkyl groups on the nitrogen can be closed together to form a ring;
  • R represents alkyl with up to 20 carbon atoms, aryl, acyl derived from an aliphatic carboxylic acid with up to 20 carbon atoms or an aromatic carboxylic acid, or amino substituted by alkyl or aryl, in which case two alkyl groups on the nitrogen can be closed together to form a ring; or
  • R, and R together represent the ring members required to complete an isocyclic or heterocylic group; at least one of the radicals R, and R, carries the group .A;
  • X represents a sulfonyl group, a carbonyl group or a single chemical bond
  • A represents a photographically inert radical rendering the dye-giving compound resistant to diffusion
  • B represents a dye radical
  • A represents a dye radical either on its own or in conjunction with R and B represents a photographically inert radical rendering the dye-giving compound resistant to diffusion;
  • said dye-giving compounds reacting with the oxidation product of the developing agent during the development and thereby releasing each a cyan, magenta and yellow diffusible acid dye image in the areas of development, during the course of said development said dye images being transferred by diffusion wholly or in part imagewise in register to an image-receiving layer containing a basic mordant for acid dyes.
  • R represents hydrogen, alkyl with up to 20 carbon atoms, aryl or amino substituted by alkyl or aryl, in which case two alkyl groups on the nitrogen can be closed together to form a ring;
  • R represents alkyl with up to 20 carbon atoms, aryl, acyl derived from an aliphatic carboxylic acid with up to 20 carbon atoms or an aromatic carboxylic acid, or amino substituted by alkyl or aryl, in which case two alkyl groups on the nitrogen can be closed together to form a ring; or
  • R and R together represent the ring members required to complete an isocyclic or heterocyclic group; at least one of the radicals R and R, carries the group A;
  • X represents a sulfonyl group, a carbonyl group or a single chemical bond
  • A represents a photographically inert radical rendering the dye-giving compound resistant to diffusion
  • B represents a dye radical
  • A represents a dye radical either on its own or in conjunction with R,
  • B represents a photographically inert radical rendering the dye-giving compound resistant to diffusion
  • a color photographic material is claimed in claim 9 which contains as dye-giving compound a compound of the following general formula:
  • R represents hydrogen, alkyl with up to 20 carbon atoms, aryl or amino substituted by alkyl or aryl, in which case two alkyl groups on the nitrogen can be closed together to form a ring;
  • R represents alkyl with up to 20 carbon atoms, aryl, acyl derived from aliphatic carboxylic acids with up to 20 carbon atoms or aromatic carboxylic acids, or amino substituted by alkyl or aryl, in which case two alkyl groups on the nitrogen can be closed together to form a ring; or
  • R and R together represent the ring members required to complete an isocyclic or heterocyclic group; at least one of the radicals R, and R contains the group BALL;
  • X represents a sulfonyl group or carbonyl group
  • BALL represents a ballasting photographically inert radical rendering the dye-giving compound resistant to diffusion
  • DYE represents a dye radical
  • R represents hydrogen, alkyl or aryl
  • R represents an aryl group which can be part of the chromophoric system of the dye radical
  • X represents a sulfonyl group, a carbonyl group or a single chemical bond
  • BALL represents a ballasting photographically incrt radical rendering the dye-giving compound resistant to diffusion
  • DYE represents a dye radical either on its own or together with R ggg UNITED STATES PATENT OFFICE CETIFICATE 0F CORECTWN Patent, 3, ,952 Dated December 21, 1971 Walter Puschel et al Inventor(s) It is certified that error appears in the above-identified patent and that said Letters Patent are hereby corrected as shown below:

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  • Organic Chemistry (AREA)
  • Physics & Mathematics (AREA)
  • General Physics & Mathematics (AREA)
  • Silver Salt Photography Or Processing Solution Therefor (AREA)
  • Plural Heterocyclic Compounds (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
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Cited By (18)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3839035A (en) * 1971-03-31 1974-10-01 Agfa Gevaert Nv Photographic processes and recording materials for use therein
US3844785A (en) * 1972-06-10 1974-10-29 Agfa Gevaert Ag Color photographic diffusion transfer process and photographic material for use in this process
US3925075A (en) * 1973-06-01 1975-12-09 Agfa Gevaert Ag Photographic dye diffusion transfer process using silver salt transfer for reversal
US3929760A (en) * 1973-02-12 1975-12-30 Eastman Kodak Co Cyan image-providing phenylazonaphthyl dyes
US3931144A (en) * 1973-02-12 1976-01-06 Eastman Kodak Company Magenta image-providing phenylazonaphthyl dyes
US3932381A (en) * 1973-02-12 1976-01-13 Eastman Kodak Company Magenta image-providing phenylazo-naphthyl dyes
US3932380A (en) * 1974-02-05 1976-01-13 Eastman Kodak Company Magenta image-providing phenylazo-naphthyl dyes
US3933493A (en) * 1971-07-02 1976-01-20 Mitsubishi Paper Mills, Ltd. Amidrazones as dye components and developer scavengers in diffusion transfer materials and processes
US3998637A (en) * 1974-07-10 1976-12-21 Eastman Kodak Company Process for producing positive color diffusion transfer images using redox dye releasers
US4029503A (en) * 1973-03-28 1977-06-14 Konishiroku Photo Industry Co., Ltd. Diffusible-dye releasing type dyes which couple to form colorless products
US4386149A (en) * 1978-02-28 1983-05-31 Ciba-Geigy Ag Process for the production of photographic images by dye diffusion transfer and photographic material suitable in this process
US4386150A (en) * 1981-12-18 1983-05-31 Polaroid Corporation Novel image dye-providing materials and photographic products and processes
US4420627A (en) * 1981-12-18 1983-12-13 Polaroid Corporation Hydrazine dyes
US4548888A (en) * 1983-12-20 1985-10-22 Eastman Kodak Company Photographic products employing novel nondiffusible hydrazone dye-releasing compounds
US4598158A (en) * 1981-12-18 1986-07-01 Polaroid Corporation, Patent Dept. Novel image dye-providing materials and photographic products and processes
US4663273A (en) * 1984-01-12 1987-05-05 Agfa-Gevaert, N.V. Non-diffusing compounds capable of releasing a diffusible dye or dye precursor compound with multiple dye units
US4684604A (en) * 1986-04-24 1987-08-04 Eastman Kodak Company Oxidative release of photographically useful groups from hydrazide compounds
US5134055A (en) * 1989-04-21 1992-07-28 Fuji Photo Film Co., Ltd. Silver halide photographic materials

Families Citing this family (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE3778363D1 (de) 1987-09-11 1992-05-21 Agfa Gevaert Nv Polymerisches phosphoniumbeizmittel und photographisches element, das dieses enthaelt.
JP2597908B2 (ja) 1989-04-25 1997-04-09 富士写真フイルム株式会社 ハロゲン化銀カラー写真感光材料
EP0502508B1 (de) 1991-03-05 1999-07-07 Fuji Photo Film Co., Ltd. Farbphotographisches Diffusionsübertragungsmaterial und farbphotographisches hitzeentwickelbares Material
JP4022271B2 (ja) 1995-10-31 2007-12-12 富士フイルム株式会社 ピラゾリルアゾフエノール色素
ATE462578T1 (de) 2006-12-07 2010-04-15 Agfa Gevaert Informationsträgervorläufer und damit hergestellter informationsträger

Citations (1)

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Publication number Priority date Publication date Assignee Title
US3443940A (en) * 1967-07-24 1969-05-13 Polaroid Corp Diffusion transfer employing ringclosure to release color-providing material for transfer

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3443940A (en) * 1967-07-24 1969-05-13 Polaroid Corp Diffusion transfer employing ringclosure to release color-providing material for transfer

Cited By (18)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3839035A (en) * 1971-03-31 1974-10-01 Agfa Gevaert Nv Photographic processes and recording materials for use therein
US3933493A (en) * 1971-07-02 1976-01-20 Mitsubishi Paper Mills, Ltd. Amidrazones as dye components and developer scavengers in diffusion transfer materials and processes
US3844785A (en) * 1972-06-10 1974-10-29 Agfa Gevaert Ag Color photographic diffusion transfer process and photographic material for use in this process
US3929760A (en) * 1973-02-12 1975-12-30 Eastman Kodak Co Cyan image-providing phenylazonaphthyl dyes
US3931144A (en) * 1973-02-12 1976-01-06 Eastman Kodak Company Magenta image-providing phenylazonaphthyl dyes
US3932381A (en) * 1973-02-12 1976-01-13 Eastman Kodak Company Magenta image-providing phenylazo-naphthyl dyes
US4029503A (en) * 1973-03-28 1977-06-14 Konishiroku Photo Industry Co., Ltd. Diffusible-dye releasing type dyes which couple to form colorless products
US3925075A (en) * 1973-06-01 1975-12-09 Agfa Gevaert Ag Photographic dye diffusion transfer process using silver salt transfer for reversal
US3932380A (en) * 1974-02-05 1976-01-13 Eastman Kodak Company Magenta image-providing phenylazo-naphthyl dyes
US3998637A (en) * 1974-07-10 1976-12-21 Eastman Kodak Company Process for producing positive color diffusion transfer images using redox dye releasers
US4386149A (en) * 1978-02-28 1983-05-31 Ciba-Geigy Ag Process for the production of photographic images by dye diffusion transfer and photographic material suitable in this process
US4386150A (en) * 1981-12-18 1983-05-31 Polaroid Corporation Novel image dye-providing materials and photographic products and processes
US4420627A (en) * 1981-12-18 1983-12-13 Polaroid Corporation Hydrazine dyes
US4598158A (en) * 1981-12-18 1986-07-01 Polaroid Corporation, Patent Dept. Novel image dye-providing materials and photographic products and processes
US4548888A (en) * 1983-12-20 1985-10-22 Eastman Kodak Company Photographic products employing novel nondiffusible hydrazone dye-releasing compounds
US4663273A (en) * 1984-01-12 1987-05-05 Agfa-Gevaert, N.V. Non-diffusing compounds capable of releasing a diffusible dye or dye precursor compound with multiple dye units
US4684604A (en) * 1986-04-24 1987-08-04 Eastman Kodak Company Oxidative release of photographically useful groups from hydrazide compounds
US5134055A (en) * 1989-04-21 1992-07-28 Fuji Photo Film Co., Ltd. Silver halide photographic materials

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FR2052521A5 (de) 1971-04-09
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CA942564A (en) 1974-02-26
GB1321046A (en) 1973-06-20
DE1930215B2 (de) 1974-04-04
BE751723A (nl) 1970-12-10
NL7008600A (de) 1970-11-25
CH532269A (de) 1972-12-31
JPS4839165B1 (de) 1973-11-22

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