US3839035A - Photographic processes and recording materials for use therein - Google Patents

Photographic processes and recording materials for use therein Download PDF

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US3839035A
US3839035A US00239598A US23959872A US3839035A US 3839035 A US3839035 A US 3839035A US 00239598 A US00239598 A US 00239598A US 23959872 A US23959872 A US 23959872A US 3839035 A US3839035 A US 3839035A
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developing agent
silver halide
compound
forming
diffusing
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W Janssens
R Lemahieu
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Agfa Gevaert NV
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    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03C—PHOTOSENSITIVE MATERIALS FOR PHOTOGRAPHIC PURPOSES; PHOTOGRAPHIC PROCESSES, e.g. CINE, X-RAY, COLOUR, STEREO-PHOTOGRAPHIC PROCESSES; AUXILIARY PROCESSES IN PHOTOGRAPHY
    • 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
    • G03C8/12—Photosensitive materials characterised by the image-forming section the substances transferred by diffusion consisting of organic compounds of dyes or their precursors characterised by the releasing mechanism

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  • ABSTRACT A process for the formation of transfer images in colour formed by:
  • Useful diffusion-resistant developing agents are of the Useful colourless reagents are selected from the class of a-naphthol, phenol, reactive methylene or N,N-dialkylaniline type coupler compounds capable of oxidatively coupling with a different colourless reagent being a hydrazone compound in order to form dyes containing an azino group.
  • the intramolecularly coupling compounds contain as a first group the reactive part'of one of said coupler compounds chemically liked to a second group containing the hydrazone structure.
  • a photographic silver halide material is used containing a reagent, which is a dye possessing a developing function and which, when oxidized, provides areaction product of lower solubility in a processing liquid than the unreacted reagent. Relying on said property of the dye developer a colour diffusion transfer process was realized, which made possible the production of positive monochromatic or multicolour prints stating from a monolayer or multilayer silver halide material containing the proper dye developer compounds.
  • a multilayer colour photographic material suited for use in said process has silver halide emulsion layers that are spectrally sensitive to blue, green and red light respectively and comprises three alkali-permeable colloid layers each of which is adjacent to a said emulsion layer and contains a different dye developer compound of a colour complementary to that the. adjacent silver halide emulsion layer has been spectrally sensitized to.
  • Such multilayer colour photographic material is not suited for reflex emposure since .each dye developer layer acts as an absorption layer for the reflected light to which the corresponding silver halide emulsion layer is sensitive.
  • a photographic material suitable for use in a process for the production of dye images by image-wise diffusion transfer of compounds soluble in an alkaline aqueous processing liquid, contains photosensitive silver halide grains dispersed in a hydrophilic colloid layer and contains in or in water-permeable relation to such layer at least one colourless reagent, which is capable of forming a dyestuff by an oxidative coupling reaction and of diffusing in aqueous alkaline meduim from said material to a re ceptor material, said photographic material also containing in effective contact with said silver halide grains a developing agent, which is resistant to diffusion in a hydrophilic colloid medium and which when activated in the presence of an alkaline aqueous liquid after the image-wise exposure of said layer reduces the exposed silver halide in said layer and which couples in oxidized state with the colourless reagent to inhibit its diffusion from the exposed portions of the photosensitive material into the receptor material.
  • the process for the formation of transfer colour images according to the present invention comprises the steps of:
  • a photographic material which contains a silver halide emulsion layer having in effective contact with the silver halide grains that are sensitive or have been sensitized to said electromagnetic radiation a developing agent that is resistant to diffusion in a hydrophilic colloid medium and having in effective contact with said developing agent at least one colourless reagent that is capable of diffusing in aqueous alkaline medium from said material to a receptor material and of forming a dyestuff by oxidative intermolecular or intramolecular coupling or coupling with another different colourless rea-- gent being likewise capable of diffusing in aqueous alkaline medium and of forming wiht the oxidation product of said developing agent a compound havpound(s) that posesses(es) a substantially lower diffusion mobility than the unreacted reagents have,
  • the photosensitive layer has associated therewith a pair of different colourless reagents (called A and B respectively) for forming a dye by oxidative coupling and a developing agent for developing that layer and forming an oxidation product that inhibits diffusion of at least one of such reagents.
  • a and B colourless reagents
  • the photosensitive layer has associated therewith a colourless reagent for forming such a dyestuff by oxidative intermolecular or intramolecular coupling, and a developing agent for developing that layer so that an oxidation product forms that inhibits diffusion of said reagent.
  • the process for forming a dye image by image-wise transfer of colourforming reactant comprises the following steps:
  • the photographic material may comprise a plurality of light-sensitive layers sensitive in different spectral regions and different associated pairs of colour-formers as above referred to so that plural-colour image of a plural-colour original can be produced on the receptor material.
  • a dye image of an individual colour can be formed on a receptor material by means of a photosensitive recording material comprising a sheetlike support and a hydrophilic colloid silver halide emulsion layer containing in effective contact with the silver halide a p-phenylene diamino type developing agent resisting d t usiqntamiamizlure et ye m g QIHEQPEQA and a dye forming compound B, which are both capable of diffusing from their hydrophilic colloid layer by means of an alkaline aqueous liquid.
  • Compound A as well as compound B are incorporated in the same silver halide emulsion layer or one or both of them can be incorporated in a colloid layer subjacent to the silver halide emulsion layer so that the compound(s) which has or have to be immobilized can be intercepted by the oxidized developing agent resisting diffusion.
  • the colourless dye-forming reagents are grouped in three pairs, in which the reagents of each different pair form on the receptor material by oxidatively coupling a dye of a different complementary colour, viz. a yellow, magenta and cyan dye respectively.
  • the photographic material incorporates in the or each light-sensitive layer a diffusion-resistant developing agent, which under the conditions of photographic processing is capable of preferentially reducing exposed silver halide to silver, i.e., of developing a latent image in an exposed silver halide emulsion.
  • halide grains a developing agent that is resistant to diffusion in a hydrophilic colloid medium and in effective contact with said developing agent a colourless reagent that is capable of diffusing in said medium with the aid of an aqueous alkaline liquid, of forming a dyestuff by oxidative intermolecular or intramolecular coupling, and of forming with the oxidation product of said developing agent a compound with a substantially smaller diffusion mobility than said reagent has in unreacted state,
  • intermolecular oxidative coupling is meant that two separate molecules of the colourless dye-forming reagent oxidatively couple with each other to form a dye molecule.
  • intramolecular oxidative coupling is meant that two reactive parts of the same molecule of the colourless dye-forming reagent are oxidatively coupled and form a dye molecule.
  • Compounds for one of these types of coupling will be illustrated further on by a particular example.
  • the colourless colour-forming reagents for intermolecular or intramolecular coupling may be considered as consisting of two chemically linked structural parts C and C forming a compound having the general formula:
  • a silver halide developing agent known from silver halide colour photography being resistant to diffusion and capable of reacting with a phenol type or reactive methylene group type colour coupler.
  • Such developing agent is preferably an aromatic primary amino developing agent that has been made substantially nondiffusing in a hydrophilic colloid medium and in oxidized state forms a non-diffusing coupling product with a colour-forming reagent, which is itself not resistant to diffusion and which contains one or more reactive hydrogen atoms, such reagent on diffusion into the receptor material forming with its colour-forming reaction partner a dye by oxidative coupling.
  • Preferably used developing compounds are of the pphenylene diamine type and correspond to the following general formula:
  • each of R, and R represents an aliphatic residue including a substituted aliphatic residue in which optionally one of these residues is substituted with a polar group, e.g. an acidic group providing, e.g., substantivity to a hydrophilic colloid such as gelatin and/or facilitating the homogeneous distribution of said compounds in a hydrophilic colloid medium, preferred groups being a sulphonic acid, a carboxylic acid group or an alkylsulphonylamino group, or R represents the necessary methylene groups including substituted methylene groups to close a 5- or 6- membered heterocyclic nucleus with the carbon atom in the 6-position of the benzene nucleus, or R represents the necessary methylene groups including substituted groups to close a 5- or 6- membered heterocyclic nucleus with the carbon atom in the 2-position of the benzene nucleus, or R and R together represent the necessary methylene groups including substituted methylene groups to close a S-
  • R represents same or different substituents of the group comprising hydrogen or substitutents that have an influence on properties such as the developing capacity, binding force with the hydrophilic colloid or solubility in water, such as (an) alkyl group(s) e.g. (a) methyl group(s) or an alkoxy group such as methoxy or ethoxy, with the proviso that R in the cases that it does not represent hydrogen is limited to the 3- and/or 5- positions indicated above, and wherein said developing agent contains one or more substituents that provide the desired resistance to diffusion in a hydrophilic colloid medium e.g. at least one of said residues containing more than four carbon atoms in straight line.
  • substituents of the group comprising hydrogen or substitutents that have an influence on properties such as the developing capacity, binding force with the hydrophilic colloid or solubility in water, such as (an) alkyl group(s) e.g. (a) methyl group(s) or an alkoxy group such as methoxy
  • the free amino group in the above p-phenylene diamine type compound may be mono-substituted with an alkyl group including a substituted alkyl group or an alkylene group ring-closed in the indicated 3- position.
  • the free amino group may be blocked in a reversible way, e.g. by substitution with an alkyl group that is further substituted with an anionic group e.g. a sulphonic acid group, a carboxylic acid group, or a hypophosphorous acid group as described, e.g., in the United Kingdom Patent Specifications 691,815 filed Jan. 26, 1951 and 783,887 filed Aug.
  • Trialkyl p-phenylenediamines and their preparation are described in the Belgian Patent Specification 532,736 filed Oct. 22, 1954 by Gevaert Photo- Producten NV.
  • non-diffusing p-phenylene diamine type developing agents correspond to the following general formula:
  • R represents hydrogen, an alkyl group, preferably a C C alkyl group e.g. methyl or ethyl, or an alkoxy group, preferably an alkoxy group containing at most three carbon atoms e.g. methoxy or ethoxy,
  • R represents hydrogen or an alkyl group, preferably a C C alkyl group e.g-. methyl or ethyl,
  • R represents a long chain aliphatic residue preferably a C,,C alkyl group, more preferably dodecyl, heptadecyl or octadecyl;
  • X represents hydrogen, a sulphonic acid group, a car- .boxylic acid group, a hydroxyl group, or a sulphonamido group in which the amido group may be substituted with short chain alkyl e.g. methyl or ethyl, and
  • n 1 to 4.
  • non-diffusing p-phenylene diamine type developing agents also called herein primary developing agents are preferably used in combination with another reducing agent (i.e. an auxiliary developing agent) increasing the development speed.
  • another reducing agent i.e. an auxiliary developing agent
  • pyrazolin-3-one developing compounds may be added to the light-sensitive material and/or to the alkaline activating bath and correspond, e.g., to the following general formula:
  • R represents an aryl group, including a substituted aryl group. e.g. phenyl,
  • R represents hydrogen or an acyl group such as acetyl and each of R R,, R and R (the same or different) represents hydrogen, an alkyl group, including a substituted alkyl group, or an aryl group including a substituted aryl group.
  • reducing agents activating the developing action of the p-phenylene diamine type developing agent are developing compounds used in superadditive development such as described in the United Kingdom Patent Specifications '989,383 filed June 18, 1962 by Gevaert Photo-Producten N.V., 1,191,535 filed May 24, 1967 by Gevaert-Agfa N.V., 1,003,783 filed July 10, 1961 by Gevaert Photo-Producten NV. and 1,154,385 filed Nov. 4, 1966 by Agfa-Gevaert N.V.
  • the auxiliary developing agents When used in the activating bath the auxiliary developing agents are preferably applied therein in an amount of 50 mg to 2 g per litre.
  • One of said reagents called hereinafter compound A is capable of coupling with the non-diffusing oxidation product of the p-phenylene diamine type developing agent so that the coupling product is inhibited from diffusing into a receptor material.
  • Compound A can, e.g., be any compound suitable to act in a dye-forming electrophilic substitution reaction of which diazo coupling is an example.
  • Compound A is preferably'a compound of the type producing a quinone-imine or azomethine dye with an oxidizied N,N-dialkylp-phenylene diamine.
  • Such compounds are sufficiently known to those skilled in the art of colour photography and are described, e.g., by Pierre Glafkides in Photographic Chemistry, Vol. ll Fountain Press London (1960), pages 596-604.
  • Suitable compounds A are, e.g. a-naphthol, phenol, reactive methylene type and reactive methyl couplers, i.e., diazo couplers as described, e.g., in the French Patent Specification l,602,473 filed Dec. 26, 1968 by Gevaert-Agfa N.V. Said compounds must have a chemical structure that allows them to diffuse by means of an alkaline aqueous liguid in a hydrophilic colloid medium e.g. gelatin.
  • the coupler molecules In order to improve the diffusion mobility in an alkaline hydrophilic colloid medium it is desired that the coupler molecules contain a carboxylic acid or sulphonic acid group.
  • each of R and R represents hydrogen, an alkyl group including a substituted alkyl group, an alkoxy group including a substituted alkoxy group, or the group NHR in which R represents a carboxylic acid acyl or sulphonic acid acyl group including said groups in substituted state, e.g. an aliphatic carboxylic acid acyl group, an aromatic carboxylic acid acyl group, an heterocyclic carboxylic acid acyl group e.g.
  • a 2-fu'royl group or a 2-thienoyl group an aliphatic sulphonic acid acyl group, an aromatic sulphonic acid acyl group, a sulphonyl thienyl group, an aryloxy-substituted aliphatic carboxylic acid acyl group, a phenylcarbamyl aliphatic carboxylic acid acyl group or a tolyl carboxylic acid acyl group, with the proviso that R and R not represent simultaneously hydrogen and the substituents are not of such type that the diffusion of the phenol compound in an alkaline hydrophilic colloid medium is markedly hindered; a polar substituent such as a carboxylic acid or a sulphonic acid group is preferably present as a substituent to improve the mobility of the phenol couplers in said medium.
  • Couplers are further a-naphthol type couplers 3 :gzrdisg s zlzltlmints; itsmsslzt H l) CON1-IR soar:
  • V R represents an alkyl group including a substituted alkyl group, an aryl group including a substituted 45 5 OH aryl group preferably such groups that are substil tuted with a carboxylic acid or sulphonic acid group.
  • a-naphthol type couplers are prepared, e.g., by
  • R and R each represents an alkyl group including a substituted alkyl group, an aryl group including a substituted aryl group, a N- arylamino group including a substituted N- arylamino group, or an ether group including a substituted ether group, e.g. an alkoxy group,
  • R represents an alkyl group including a substituted alkyl group, or an aryl group including a substituted aryl group,
  • R represents an alkyl group including a substituted alkyl group, an aryl group including a substituted aryl group, carbethoxy, an alkoxy group, cyano, a N-arylamino group including a substituted N- arylamino group, a N-acylamino group including a substituted N-acylamino group or an ureido group including a substituted ureido group.
  • the crude product is purified by crystallization from acetic acid and the crystals washed with chloroform. Purification is continued by recrystallization from nbutanol.
  • N,N-dialkylanilines of the diffusing type containing as a further substituent on one of the alkyl groups, an acid substituent or a substituent containing an acid group, said acid group being present in free acid or salt form, e.g. a sulphonic acid substituent.
  • the N,N-dialkylanilines couple with an oxidized N,N-dialkyl-p-phenylene diamine type developer to form a quino-diimine betaine type salt according to the following reaction scheme:
  • M is hydrogen, a metal cation or cationic group, e.g.,
  • dialkylanilines can be prepared according to known alkylating reactions for anilines.
  • Useful heterocyclic hydrazone compounds are within the scope of the following general formula:
  • R represents a CONH or SO X group in which X represents hydroxyl, an amino group including a substituted amino group, an alkyl group including a substituted alkyl group, an aryl group including a substituted aryl group, and
  • Z represents the necessary atoms to close a 5 or 6- membered heterocyclic nucleus or ring system including such nucleus or ring system in substituted form.
  • Preferred heterocyclic hydrazone compounds correspond to the following formula:
  • R has the same meaning as described under formula R representshydrogen, an aliphatic group including a substituted aliphatic group, e.g an alkyl group including a substituted alkyl group, or an aromatic group including a substituted aromatic group, e.g. an aryl group including a substituted aryl group,
  • L represents a methine group or nitrogen
  • n 1 or 2
  • Z represents the necessary atoms to close a 5--or 6- membered heterocyclic nitrogen-containing nucleus or ring system including such nucleus or ring system in substituted form, e.g. a 2nucleus, nuclues, a 2-indolinylidene nucleus or a 4- quinolinylidene nucleus.
  • said hydrazone compounds contain preferably a carboxylic acid or sulphonic acid group.
  • Developing agents that in oxidized state can couple with said hydrazone compounds and prevent these compounds from diffusing out of a hydrophilic colloid layer to a receptor material are aromatic 1,2-dihydroxy compounds that on coupling with the hydrazones form sufficiently large molecules that are immobilized in the hydrophilic colloid in which they are formed. Examples of such useful 1,2-dihydroxy compounds are listed in the following Table 7.
  • Suitable polar groups for that purpose are, e.g., carboxyl groups and sulphonic acid groups in free acid or salt form.
  • the molecule that has to be resistant to diffusion is large enough, e.g., for it comprises more than one aromatic or heterocyclic nucleus and no polar groups, the introduction of long chain aliphatic residues is not necessary at all or lower alkyl groups (C -C may suffice.
  • oxidatively dyeforming compounds can be applied that are known, e.g., from photographic integral masking techniques according to which a dye image is formed by oxidative coupling in a potassium cyanoferrate(lll) bleaching bath.
  • colourless compounds known from integral masking reference is made, e.g., to 4- aminopyrazolones corresponding to the following general formula:
  • each of R and R represents an alkyl group of at most five carbon atoms
  • R represents an alkyl group of at most five carbon atoms, a phenyl group including a substituted phenyl group.
  • Suitable oxidatively coupling dye-forming compounds are p-phenylene diamines with sterically hindered amino group and sterically hindered phenols as described, e.g., in the United Kingdom Patent Specification 1,153,561 filed Jan. 18, 1966 by Agfa-Gevaert N.V. and 975,940 filed Nov. 30, 1959 by Gevaert Photo-Producten N.V. respectively.
  • a blue-sensitive silver halide emulsion layer containing a non-diffusing silver halide developing agent and in effective contact with said developing agent a pair of colourless reagents that are capable of diffusing in said medium when wetted with an aqueous alkaline liquid and of forming a yellow dyestuff by oxidative coupling with each other, at least one of said reagents being capable of forming with the oxidation product of the developing agent a compound with a substantially smaller diffusion mobility than said reagent has in unreacted state,
  • a green-sensitive silver halide emulsion layer containing a non-diffusing silver halide developing agent and in effective contact with said developing agent a pair of colourless reagents, that are capable of diffusing in said medium when wetted with an aqueous alkaline liquid and of forming a magenta dyestuff by oxidative coupling with each other, at least one of said reagents being capable of forming with the oxidation product of the developing agent a compound with a substantially smaller diffusion mobility than said reagent has in unreacted state,
  • a red-sensitive silver halide emulsion layer containing a non-diffusing silver halide developing agent and in effective contact with said developing agent a pair of colourless reagents that are capable of diffusing in said medium when wetted with an alkaline aqueous liquid and of forming a cyan dyestuff by oxidative coupling with each other, at least one of said reagents being capable of forming with the oxidation product of the developing agent a compound with a substantially smaller diffusion mobility than such reagent has in unreacted state; and any said reagent, which does not form a compound photographic material one of the reaction partners of each pair of partners has to be common to all of the pairs and those partners that are not common are to be immobilized by reaction with one or more oxidation products of a developing agent or agents.
  • the partner that is common to all of the pairs may be applied in hydrophilic colloid layers that are adjacent to the silver halide emulsion layers.
  • Each silver halide emulsion layer may be separated from an other silver halide emulsion layer by a suitable spacer stratum, e.g., by a layer of gelatin or polyvinyl alcohol.
  • the spacer stratum may act as a kind of a permeable barrier layer controlling the diffusion of the dye-forming compound(s), e.g., is a layer of slowly permeable material, such as a layer of cellulose acetate-hydrogen phthalate occasionally in combination with a more water-permeable spacer layer, e.g., gelatin layer.
  • three different compounds C,C are used in which one group either C or C has the same structure in these three compounds or is of the same chemical type, i.e., operates along the same chemical reaction mechanism (e.g. electrophilic or nucleophilic substitution) preferably with substantially the same reaction speed.
  • chemical reaction mechanism e.g. electrophilic or nucleophilic substitution
  • Useful sets of colour-forming reagents C -C for three colour materials with true colour reproduction possibilities in multicolour photography contain a same structural colour-forming part and may be represented, e.g., by the following sets of chemically linked reactive molecule parts A, B, C, X, Y and Z:
  • the part C is a group containing the structure of an a-naphthol coupler and corresponds to the formula:
  • R represents an alkyl group including a substituted alkyl group or an aryl group including a substituted aryl group, an alkoxy group or a substituted amino group, e.g. an alkyl or aryl substituted amino group, and
  • R represents an alkyl group including a substituted alkyl group, an aryl group including a substituted aryl group, cyano, an alkoxy group, a carbonylalkoxy group, a N-arylamino group including a substituted N-arylamino group, a N-acylamino group in- 1 in which Z represents the necessary atoms to close a 5- or 6-membered heterocyclic nucleus or ring system including such nucleus or ring system in substituted form.
  • Particularly suitable C,C compounds contain a group C corresponding to the following general formula:
  • R represents hydrogen, an aliphatic group including a substituted aliphatic group or an aromatic group including a substituted aromatic group
  • L represents methine or nitrogen
  • n is 1 or 2
  • nucleus or ring system represents the necessary atoms to close a 5- or 6- membered heterocyclic nucleus or ring system, said nucleus or ring system being either or not in substituted form.
  • Compound 1 is prepared from compound 6 by saponification of the fluorosulphonyl group with sodium hydroxide.
  • 210C has been prepared by a technique known for preparing a-hydroxy-B-naphthoic acid anilides starting from p-fluorosulphonylaniline and the phenyl ester of a-hydroxy-B-naphthoic acid.
  • This sulphonylhydrazinde (IV) was used in the preparation of the compounds 1 to 6 and 8 to 13.
  • Reaction Scheme B 111) -oocmooootm Reaction scheme C NaOH acetone/ H 20 20 g of the sulphofluoride (V), 33 ml of sodium hydroxide (30 percent by weight in water) and 200 ml of acetone are refluxed for 30 min. with stirring.
  • a particular advantage of the intramolecularly reactive compounds C C resided in the fact that the reactive parts C and C reach the receiving material in perfect stoechiometric amounts so that practically no undesired colour fog is produced in the diffusion transfer picture and very clear whites are obtained.
  • a photosensitive recording material comprising a sheetlike support and a hydrophilic colloid silver halide emulsion layer containing in effective contact with the silver halide a non-diffusing p-phenylenediamino type developing agent and said compound C -C which is capable to diffuse out of the hydrophilic colloid layer by means of an alkaline aqueous liquid.
  • Compound C C is incorporated into the same silver halide emulsion layer or into a colloid layer subjacent to the silver halide emulsion layer so that the compound that has to be immobilized can be intercepted by the oxidized non-diffusing developing agent.
  • the silver halide emulsion layer composition may contain spectral sensitizing agents.
  • Useful spectral sensitizing agents are in the class of the methine dyes, e.g., the cyanine dyes, hemicyanine, merocyanine, oxonol, hemi-oxonol and styryl dyes and polynucleic methine dyes such as rhodacyanine dyes and neocyanine dyes.
  • the methine dyes e.g., the cyanine dyes, hemicyanine, merocyanine, oxonol, hemi-oxonol and styryl dyes and polynucleic methine dyes such as rhodacyanine dyes and neocyanine dyes.
  • Such sensitizing agents are described by F. M. Hamer in his book The Cyanine Dyes and Related Compounds (1964).
  • Preferably used cyanine dyes have a betaine-like structure owing to the presence on the nitrogen atom of at least one'of the heterocyclic nuclei of an alkyl group wherein each of R and R is hydrogen or a hydrocarbon radical, at least one of them being hydrogen.
  • Suitable spectral sensitizing dyes of that type are described, e.g. in the United Kingdom Patent Application 16,998/70 filed Apr. 9, 1970 by Agfa-Gevaert NV. and in the published Dutch Patent Application 7004174 filed Mar. 24, 1970 by Agfa-Gevaert N.V.
  • Preferably used merocyanine dyes are the so-called zeromethine and dimethine merocyanine dyes containing a barbituric acid or thiobarbituric acid nucleus, e.g. as described in the US. Pat. No. 2,170,807 of Leslie 6. S. Brooker, issued Aug. 20, 1939 and the German Democratic Republic Patent Specification 12,477 filed Sept. 20, 1954 by G. Back and J. Brunken.
  • the silver halide emulsion layer(s) may further contain the usual additives such as e.g., antifogging agents, chemical sensitizing agents, stabilizing agents, development accelerators, plasticizers, hardening agents and wetting agents.
  • additives such as e.g., antifogging agents, chemical sensitizing agents, stabilizing agents, development accelerators, plasticizers, hardening agents and wetting agents.
  • the photosensitive material may contain any type of support known for silver halide photographic materials but comprises preferably a flexible support, e.g., a
  • paper or plastic film base in sheet, web or ribbon form.
  • a photographic material with a transparent or semi-transparent (at least 50 percent light transmission) support is used.
  • the imagereceiving material is a flexible plastic film or a paper sheet coated with a hydrophilic colloid layer containing an oxidizing agent that is capable of effecting the oxidative coupling of the couplers as defined above and which has a structure that makes it difficult or impossible to leave said hydrophilic colloid layer by diffusion in an aqueous alkaline liquid.
  • Suitable oxidizing compounds are nondiffusing organic peroxides, long chain (C -C20) aliphatic onium salts of peracids and compounds that easily split off halogen in aqueous medium such as halogen amides and imides, examples of which are bromosuccinimide and non-diffusing chloramine T and dichloramine T type compounds.
  • Useful receiving materials contain in a hydrophilic colloid layer, e.g., incorporated in gelatin an amount of 0.01-0.05 mole of dibenzoyl peroxide per sq.m.
  • the image-receiving element may contain agents adapted to mordant or otherwise fix the dyes, e.g. azine dyes, formed by oxidative coupling.
  • the image-receiving element contains a polymer, preferably a cationic polymer that acts as a mordant for anionic dyes as described e.g. in the United Kingdom Patent Specification 1,221,195 filed Mar. 26, 1968 by Gevaert-Agfa NV.
  • the mordanting agent may be applied in admixture with the oxidizing agent or in a layer adjacent to the layer containing the oxidizing agent.
  • the aqueous alkaline activating liquid has preferably a pH between 8 and 13 and contains, e.g., from to 50 g of sodium carbonate-per litre. It may contain development accelerating compounds, viscositycontrolling agents, e.g. hydroxyethylcellulose, wetting agents and water-miscible organic liquids for the purpose of improving the density of the dye image on the receptor material.
  • the activating liquid may be applied to the photosensitive material after its exposure by any technique known in the art of applying liquids to sheet materials, e.g., by spreading, imbibition, liquid film coating practices or spraying and may be similarly applied to the image-receiving element before the latter and the photosensitive material are brought into superposed relation or contact for carrying out the diffusion transfer of oxidatively coupling compounds from the undeveloped portions.
  • the alkaline agent may also be applied in pods or pressure-rupturable micro-containers, e.g., microcapsules, and squeezed into contact with the receptor material.
  • multilayer photosensitive materials are used as illustrated in the accompanying FIGS. 1 and 2.
  • a multilayer photosensitive element comprises a blue-sensitive silver halide emulsion layer 1 containing a non-diffusing silver halide developing agent the oxidation products of which in alkaline medium couple with an alkali-soluble coupler A that in its turn in the presence of a stronger oxidant than exposed silver halide oxidatively couples with an alkalisoluble reagent B and forms a yellow dye after diffusion onto a receptor material containing the stronger oxidant.
  • Element 2 is a hydrophilic colloid spacer layer, eg a gelatin layer.
  • Element 3 is a green-sensitive silver halide emulsion layer that is substantially insensitive to blue and red light and contains a non-diffusing silver halide developing agent the oxidation products of which in alkaline medium couple with an alkali-soluble coupler A ma in its turn in the presence of a stronger oxidant than exposed silver halide oxidatively couples with a same alkali-soluble reagent B and forms a magenta dye after diffusion onto the receptor material containing the stronger oxidant.
  • Element 4 is a hydrophilic colloid spacer layer, e.g., a gelatin layer.
  • Element 5 is a red-sensitive silver halide emulsion layer that is substantially insensitive to blueand green light and contains a non-diffusing silver halide developing agent the oxidation products of which in alkaline medium couple with an alkali-soluble coupler A that in its turn in the presence of a stronger oxidant than exposed silver halide oxidatively couples with a same alkali-soluble reagent B and forms a cyan dye after diffusion onto the receptor material containing the stronger oxidant.
  • Element 6 is a subbing layer for a gelatino silver halide colloid layer and a support 7, which is, e.g., a film support or semi-transparent paper base.
  • a multilayer photosensitive element according to FIG. 2 contains a blue-sensitive silver halide emulsion layer 1 containing a non-diffusing silver halide developing agent and an alkali-soluble coupler B that in alkaline medium by means of a stronger oxidant than exposed silver halide couples to form a yellow dye with an alkalisoluble coupler A, that is present in the hydrophilic water-permeable colloid layer 2.
  • the coupler A diffusing out of the colloid layer 2 and penetrating into the exposed emulsion layer 1 reacts therein with the non-diffusing developer oxidation products and is inhibited thereby from further migration.
  • Element 3 is a hydrophilic colloid spacer layer, e.g., a gelatin layer.
  • Element 4 is a green-sensitive silver halide emulsion layer that is substantially insensitive to blue and red light and contains a non-diffusing silver halide developing agent and a same alkali-soluble coupler B that in alkaline medium by means of a stronger oxidant than exposed silver halide couples to form a magenta dye with an alkali-soluble coupler A that is present in a hydrophilic water-permeable colloid layer 5.
  • Element 6 is a hydrophilic colloid spacer layer, e.g., a gelatin layer.
  • Element 7 is a red-sensitive silver halide emulsion layer that is substantially insensitive to blue and green light and contains a non-diffusing silver halide developing agent and a same alkali-soluble coupler B that in alkaline medium by means of a stronger oxidant than exposed silver halide couples to form a cyan dye with an alkali-soluble coupler A that is present in a hydrophilic water-permeable colloid layer 8.
  • Element 9 is a subbing layer, e.g., a gelatin layer and element 10 is a support, e.g., a paper support.
  • reaction partners A and B capable of diffusing in alkaline medium through a hydrophilic colloid mass are mentioned as examples of practice.
  • A's common mobile reaction partner B a hydrazone compound having the following structural formula may be used:
  • nd Q-ooomoormQooon 'fifil'loivf'hiine dye formed with compouF(A )fi and the hydrazone B has the following structure:
  • magenta azine dye formed with compound (A' and the hydrazone B has the following structure:
  • the cyan azinc dye formed with compound (A' and 5 the hydrazone B has the following structure: 5
  • N,N-dialkylanilino coupler e.g. as exemplified in the following N,N-dialkylanilino coupler:
  • the introduced reactive methylene group does not influence the absorption of the finally formed azine dye in the visible spectrum since the chromophoric system formed with the aid of that methylene group will only cause absorption in the non-visible short wave ultraviolet range.
  • a p-phenylenediamine type developing agent that is resistant to diffusion in an alkaline hydrophilic colloid medium and is particularly useful for application according to the present invention has the following formula:
  • a multilayer photographic material suited for use according to the second embodiment of the present invention in the formation of multicolour images by imagewise diffusion transfer of intramolecularly or intermolecularly dye-forming reactants from a photographic material into a receptor material comprises preferably:
  • a blue-sensitive silver halide emulsion layer containing a non-diffusing silver halide developing agent and in effective contact therewith a colourless reagent A-X that is capable of diffusing in said medium with the aid of an alkaline aqueous liquid, of forming a yellow dyestuff by oxidative intramolecular or intermolecular coupling, and of forming with the oxidation product of the developing agent a compound with a substantially smaller diffusion mobility than it has in unreacted state,
  • a green-sensitive silver halide emulsion layer containing a non-diffusing silver halide developing agent and in effective contact therewith a colourless reagent A-Y or B-X that is capable of diffusing in said medium with the aid of an alkaline aqueous liquid, of forming a magenta dyestuff by oxidative intramolecular or intermolecular coupling and of forming with the oxidation product of the developing agent a compound with a substantially smaller diffusion mobility than it has in unreacted state,
  • a red-sensitive silver halide emulsion layer containing a non-diffusing silver halide developing agent and in effective contact with said developing agent a colourless reagent A-Z or C-X that is capable of diffusing in said medium with the aid of an alkaline aqueous liquid, of forming a cyan dyestuff by oxidative intramolecular or intermolecular coupling and of forming with the oxidation product of the developing agent a compound with a substantially smaller diffusion mobility than it has in unreacted state.
  • Each silver halide emulsion layer may be separated from another silver halide emulsion layer by a suitable

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  • Physics & Mathematics (AREA)
  • General Physics & Mathematics (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Silver Salt Photography Or Processing Solution Therefor (AREA)
US00239598A 1971-03-31 1972-03-30 Photographic processes and recording materials for use therein Expired - Lifetime US3839035A (en)

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GB833871A GB1392433A (en) 1971-03-31 1971-03-31 Photographic diffusion transfer methods and recording materials therefor
GB4788371A GB1321348A (en) 1971-08-16 1971-10-14 Roller for roller conveyors

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4066457A (en) * 1974-12-10 1978-01-03 Gaf Corporation Color developer for diffusion transfer
US5468258A (en) * 1993-01-20 1995-11-21 Agfa-Gevaert N.V. Thermal dye transfer methods utilizing heterocyclic hydrazono dyes

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2983606A (en) * 1958-07-14 1961-05-09 Polaroid Corp Processes and products for forming photographic images in color
US3384484A (en) * 1963-04-11 1968-05-21 Agfa Ag Silver halide photographic materials containing organic hydrazone compounds
US3628952A (en) * 1969-06-13 1971-12-21 Agfa Gevaert Ag Photographic diffusion transfer materials and processes utilizing balasted hydrazone compounds to release mobile acid dyes for transfer

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2983606A (en) * 1958-07-14 1961-05-09 Polaroid Corp Processes and products for forming photographic images in color
US3384484A (en) * 1963-04-11 1968-05-21 Agfa Ag Silver halide photographic materials containing organic hydrazone compounds
US3628952A (en) * 1969-06-13 1971-12-21 Agfa Gevaert Ag Photographic diffusion transfer materials and processes utilizing balasted hydrazone compounds to release mobile acid dyes for transfer

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4066457A (en) * 1974-12-10 1978-01-03 Gaf Corporation Color developer for diffusion transfer
US5468258A (en) * 1993-01-20 1995-11-21 Agfa-Gevaert N.V. Thermal dye transfer methods utilizing heterocyclic hydrazono dyes

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FR2132014A1 (enExample) 1972-11-17
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CA998277A (en) 1976-10-12
GB1392433A (en) 1975-04-30

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