US3473924A - Novel photographic products and processes - Google Patents

Novel photographic products and processes Download PDF

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US3473924A
US3473924A US689611A US3473924DA US3473924A US 3473924 A US3473924 A US 3473924A US 689611 A US689611 A US 689611A US 3473924D A US3473924D A US 3473924DA US 3473924 A US3473924 A US 3473924A
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azabenzimidazole
layer
image
dye
silver halide
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Howard G Rogers
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Polaroid Corp
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Polaroid Corp
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D213/00—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members
    • C07D213/02—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members
    • C07D213/04—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom
    • C07D213/60—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom 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 to ring carbon atoms
    • C07D213/72—Nitrogen atoms
    • C07D213/73—Unsubstituted amino or imino radicals
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D471/00—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, at least one ring being a six-membered ring with one nitrogen atom, not provided for by groups C07D451/00 - C07D463/00
    • C07D471/12—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, at least one ring being a six-membered ring with one nitrogen atom, not provided for by groups C07D451/00 - C07D463/00 in which the condensed system contains three hetero rings
    • C07D471/14—Ortho-condensed systems
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03C—PHOTOSENSITIVE MATERIALS FOR PHOTOGRAPHIC PURPOSES; PHOTOGRAPHIC PROCESSES, e.g. CINE, X-RAY, COLOUR, STEREO-PHOTOGRAPHIC PROCESSES; AUXILIARY PROCESSES IN PHOTOGRAPHY
    • G03C1/00—Photosensitive materials
    • G03C1/005—Silver halide emulsions; Preparation thereof; Physical treatment thereof; Incorporation of additives therein
    • G03C1/06—Silver halide emulsions; Preparation thereof; Physical treatment thereof; Incorporation of additives therein with non-macromolecular additives
    • G03C1/34—Fog-inhibitors; Stabilisers; Agents inhibiting latent image regression
    • 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
    • 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
    • G03C8/04—Photosensitive materials characterised by the image-forming section the substances transferred by diffusion consisting of inorganic or organo-metallic compounds derived from photosensitive noble metals
    • G03C8/06—Silver salt diffusion transfer

Definitions

  • the present invention relates to photography and more particularly to photographic products and processes.
  • Chemical fog may be divided into two classes: inherent fog, that is, fog which is emulsion initiated; and induced fog, that is, fog which is initiated during development. Induced fog apears to be due to physical development about extragranular centers and inherent fog is probably due to the presence of grains bearing a catalytic site sensitivity speck which is unavoidably introduced and which is equivalent in its properties to latent image. Induced fog accordingly may be unaffected by the level of inherent fog.
  • an emulsion susceptible to the development of chemical fog requires silver halide grains possessing a catalytic center of sufficient size to be spontaneously developable and/ or grains unprotected from nondiscriminatory development.
  • This invention relates primarily to the latter item above, and more particularly to the use of a specified class of synthetic, organic antifoggants.
  • Another object of the present invention is to provide novel processes and products, particularly adapted for nited States Patent 0 3,473,924 Patented Oct. 21, 1969 'ice obtaining monochromatic and multichromatic images by diffusion transfer, which exhibit decreased fog formation throughout an extended temperature range.
  • a still further object of the present invention is to provide novel photographic elements comprising not less than one silver halide emulsion having associated therewith specified transfer image-forming components which exhibit increased effective processing temperature latitude.
  • the invention accordingly comprises the process involving the several steps and the relation and order of one or more of such steps with respect to each of the others and the product possessing the features, properties and the relation of the elements which are exemplified in the following detailed disclosure and the scope of the application of which will be indicated in the claims.
  • FIGURE 1 is a diagrammatic enlarge cross-sectional view of one embodiment of a film unit for obtaining multicolor images by a diffusion transfer photographic process illustrating the association of elements during one stage of the performance of a diffusion transfer process, the thickness of the various materials being exaggerated;
  • FIG. 2 is a comparative graphical representation of exposure vs. density relationship for hereinafter detailed dif fusion transfer photographic systems employing specified antifoggant compounds, including those of the present invention.
  • an exposed photographic emulsion is developed and, substantially concurrently therewith, an imagewise distribution of transfer image-forming components is provided as a function of the point-to-point degree of development. At least part of that imagewise distribution is transferred by diffusion to a contiguous imagereceiving layer to provide the desired transfer image formation to that layer.
  • an exposed silver halide emulsion 0 is developed and, substantially concurrently therewith, an
  • imagewise distribution of soluble silver complex is obtained by reaction of a silver solvent with silver halide of the emulsion as a function of its point-to-point degree of exposure.
  • the photosensitive silver halide emulsion is developed with a viscous processing composition which is spread between an element comprising the silver halide emulsion and a print receiving element comprising a suitable silver precipitating layer.
  • the processing composition affects development of the emulsion and substantially contemporaneously therewith forms a soluble silver complex, for example, a thiosulfate or thiocyanate, as a function of the point-to-point degree of emulsion exposure.
  • This soluble silver complex is, at least in part, transported in the direction of the print receiving element and the silver thereof is largely precipitated in the silver precipitating layer of said element to form a transfer image therein.
  • U.S. Patents Nos. 2,647,049; 2,661,293; 2,698,798; and 2,802,735 disclose subtractive color diffusion transfer processes wherein color coupling techniques are utilized which comprise, at least in part, reacting one or more developing agents and one or more color formers, as a function of the photoexposure of a photographic emulsion, to provide a color image to a superposed imagereceiving layer.
  • US. Patent No. 3,019,124 discloses the manufacture of photographic color screen elements particularly adapted for employment in multicolor diffusion transfer processes; and U.S. Patents Nos.
  • 2,968,554 and 2,983,606 disclose diffusion transfer processes wherein a color screen element is utilized to provide a multicolor transfer image to a superposed image-receiving layer.
  • U.S. Patents Nos. 2,774,608; 2,983,606; and 3,345,163 disclose diffusion transfer processes wherein complete dyes are utilized to provide a color transfer image to a superposed image-receiving layer.
  • a photosensitive element containing a dye developer and a silver halide emulsion is exposed and wetted by a liquid processing composition, for example, by emersion, coating, spraying, flowing, etc., in the dark, and the exposed photosensitive element is superposed prior to, during or after wetting on a sheet-like support element which may be utilized as an image-receiving element.
  • the liquid processing composition is applied to the photosensitive element in a substantially uniform layer as the photosensitive element is brought into superposed relationship with the imagereceiving layer.
  • the liquid processing composition permeates the emulsion to initiate development.
  • the dye developer is immobilized or precipitated in, for example, exposed areas as a function of the development.
  • Such immobilization is apparently, at least in part, due to a change in the solubility characteristics of the dye developer upon oxidation; particularly with regard to its solubility in alkaline solutions. It may also be due in part to a tanning effect on the emulsion by oxidized developing agent and in part to a localized exhaustion of alkali as a result of development.
  • the dye developer unreacted and diifusible, provides an imagewise distribution of unoxidized dye developer dissolve in a liquid processing composition as a function of the point-to-point degree of exposure of the silver halide emulsion.
  • At least part of this imagewise distribution of unoxidized dye developer is transferred by imbibition to a superposed image-receiving layer or element.
  • the layer of liquid processing composition may be utilized as the image-receiving layer.
  • the image-receiving element receives a depthwise diffusion of dye developer without appreciably disturbing the imagewise distribution thereof to provide the color transfer image.
  • the imagereceiving element may contain agents adapted to mordant or otherwise fix dye developer. If the color of the transferred dye developer is affected by change in the pH of the image-receiving element, this pH may be adjusted to provide a pH affording the desired color.
  • the desired dye image carried by the image-receiving layer may be separated from the photosensitive element by stripping at the end of a suitable imbibition period.
  • Dye developers are compounds which contain in the same molecule both the chromophoric system of a dye and also a silver halide developing function.
  • a silver halide developing function is meant a grouping adapted to develop exposed silver halide.
  • a preferred silver halide developing function is a hydroquinonyl group.
  • Other suitable developing functions include ortho-dihydroxyphenyl and orthoand para-amino substituted hydroxyphenyl groups.
  • the development function includes a benzenoid developing function, that is, an aromatic developing group which forms quinonoid or quinone substances when oxidized.
  • the preferred dye developers comprise monoazo and anthraquinone dyes which possess one or two hydroquinonyl groups attached to the auxochromophoric system of the dye by means of a conjugation-interrupting divalent group such as, for example, in alkylene group.
  • Multicolored images may be obtained using color image-forming components, such as, for example, the previously mentioned dye developers, in diffusion transfer processes, by several techniques.
  • One such technique contemplates the use of a photosensitive silver halide stratum comprising at least two sets of selectively sensitize minute photosensitive elements arrange in the form of a photosensitive screen. Transfer processes of this type are disclose in the previously noted U.S. Patent No. 2,983.- 606.
  • each of the minute photosensitive elements has associated therewith an appropriate dye developer in or behind a silver halide emulsion portion.
  • a suitable photosensitive screen prepared in accordance with the disclosure of said patent comprises minute red sensitized emulsion elements, minute green sensitized emulsion elements and minute blue sensitized emulsion elements arranged in side-by-side relationship in a screen pattern and having assoicated therewith. respectively, a cyan dye developer, a magenta dye developer and a yellow dye developer.
  • Another process for obtaining multicolor transfer images utilizing dye developers employs an integral multilayer photosensitive element such as is disclosed in the aforementioned U.S. Patents Nos. 2,983,606 and 3,345,- 163, wherein at least two selectively sensitized photosensitive strata and associated dye developers are superposed on a single support and are processed simultaneously and without separation with a single common image-receiving layer.
  • a suitable arrangement of this type comprises a support carrying a red-sensitive silver halide emulsion stratum, a green-sensitive silver halide emulsion stratum, and a blue-sensitive silver halide emulsion stratum, said emulsions having assoicated therewith respectively, for example, a cyan dye developer, a magenta dye developer and a yellow dye developer.
  • the dye developer may be utilized in the silver halide emulsion layer, for example, in the form of particles, or it may be employed as a layer behind the appropriate silver halide emulsion stratum, for example, a layer of dye developer applied by the use of a coating solution containing about 0.5 to 8%, by weight, of the respective dye developer.
  • Each set of silver halide emulsion and associated dye developer strata may be separated from other sets by suitable interlayers, for example, gelatin and the synthetic polymeric materials disclosed in copending application of Lloyd D. Taylor, Ser. No. 641,669, filed Feb. 7, 1967, and now abandoned.
  • suitable interlayers for example, gelatin and the synthetic polymeric materials disclosed in copending application of Lloyd D. Taylor, Ser. No. 641,669, filed Feb. 7, 1967, and now abandoned.
  • a yellow dye developer of appropriate spectral characteristics which is present in a state capable of functioning as a yellow filter may be employed. In such instances a separate yellow filter may be omitted.
  • the preceding color image-forming components are preferably selected for their ability to provide colors that are useful in carrying out subtractive color photography, i.e., cyan, magenta and yellow. It should be noted that it is within the scope of this invention to use mixtures of dye developers, for example, to obtain a desired color, e.g., black. Thus it is to be understood that the expression color as used herein is intended to include the use of a plurality of colors to obtain black, as well as the use of a single black dye developer.
  • the polymeric acid layer comprises polymers which contain acid groups, such as carboxylic acid and sulfonic acid groups, which are capable of forming salts with alkali metals, such as sodium, potassium etc., or with organic bases, particularly quaternary ammonium bases, such as tetramethyl ammonium hydroxide, or potentially acidyielding groups, such as anhydrides or lactones, or other groups which are capable of reacting with bases to capture and retain them.
  • the acid-reacting group is, of course, nondirTusible from the acid polymer layer.
  • the acid polymer contains free carboxyl groups and the transfer processing composition employed contains a large concentration of sodium and/ or potassium ions.
  • the acid polymers stated to be most useful are characterized by containing free carboxyl groups, being insoluble in water in the free acid form, and by forming water-soluble sodium and/or potassium salts.
  • polymeric acids are derivatives of cellulose or of vinyl polymers, polymeric acids from other classes of polymers may be used.
  • the acid polymer layer is disclosed to contain at least sufficient acid groups to effect a reduction in the pH of the image layer from a pH of about 12 to l4 to a pH of at least 11 or lower at the end of the imbibition period, and preferably to a pH of about 5 to 8 within a short time after imbibition.
  • the pH of the processing composition employed preferably is of the order of at least 12 to 14.
  • the pH of the image layer is kept at a level of pH 12 to 14 until the positive dye image has been formed after which the pH is reduced very rapidly to at least about pH 11, and preferably about pH 9 to 10, before the positive transfer image is separated and exposed to air.
  • Unoxidized dye developers containing hydroquinonyl developing radicals diffuse from the negative to the positive as the sodium or other alkali salt.
  • the diffusion rate of such dye imageforming components thus is at least partly a function of the alkali concentration, and it is desired that the pH of the image layer remain on the order of 12 to 14 until transfer of the necessary quantity of dye has been accomplished.
  • the subsequent pH reduction in addition to its desirable effect upon image light stability, serves a highly valuable photographic function by substantially terminating further dye transfer.
  • the processing technique thus effectively minimizes changes in color balance as a result of longer imbibition times in multicolor transfer processes using multilayer negatives.
  • the spacer layer of the last-mentioned copending application acts to time control the pH reduction by the polymeric acid layer. This timing is disclosed to be a function of the rate at which the alkali diffuses through the spacer layer. It was stated to have been found that the pH does not drop until the alkali has passed through the spacer layer, i.e., the pH is not reduced to any significant extent by the mere diffusion into the interlayer, but the pH drops quite rapidly once the alkali diffuses through the spacer layer.
  • solution dyeable polymers such as, for example, nylon, N-methoxymethyl polyhexamethylene adipamide; partially hydrolyzed polyvinyl acetate; polyvinyl alcohol with or without plastid cizers; cellulose acetate with fillers, as, for example, onehalf cellulose acetate and one-half oleic acid; gelatin; and other materials of a similar nature.
  • Preferred materials comprise polyvinyl alcohol or gelatin containing a dye mordant such as polyl-vinylpyridine, as disclosed in US. Patent No. 3,148,061.
  • the antifoggant composition is particularly helpful in minimizing or preventing reaction of a dye developer with unexposed silver halide and may be added to the processing composition and/or to one or more processing composition permeable layers of the photosensitive and/or image-receiving elements.
  • the pertinent art has recognized many compounds which have fog inhibiting characteristics, such as sodium and potassium bromide and iodide, 6-nitrobenzimidazole, benzotriazole, chlorobenzotriazole, S-methyl-benzimidazole, Z-aminobenzimidazole, thio acetanilide, etc.
  • R is selected from the group consisting of hydrogen, and lower alkyl groups, i.e., containing less than six carbon atoms;
  • R and R are selected from the group consisting of hydrogen, halogen, lower alkyl, i.e., containing less than six carbon atoms, nitro, amino, hydroxy, lower alkoxy, i.e., containing less than six carbon atoms, aryl, sulfonamido, and carboxamido groups; it being understood that R and R may together constitute the atoms necessary to complete a cyclic structure, for example,
  • R, R and R are specifically intended to encompass equivalents thereof, including R and R taken together to form an annulated hydrocarbon ring system.
  • R and/or R are Weak electron donor moieties.
  • the antifoggant compositions of the present invention may be used alone or in conjunction with other antifoggants.
  • a typical color film processing composition containing a conventional antifoggant such as benzotriazole and the like, generally in the order of about 2%
  • the antifoggants of the present invention may be added to the system with a concomitant reduction in the percentage of or elimination of the benzotriazole.
  • the antifoggants of the present invention are utilized in conjunction with a conventional antifoggant compound, such as benzotriazole, whose effectiveness responds normally to changes in temperature, to provide to the system development and control characteristics satisfactory over a greater temperature range than that achieved by the teachings set forth in the art.
  • a photosensitive element which is specifically adapted to provide for the production of a multicolor dye transfer image and comprises a dimensionally stable support layer carrying at least two selectively sensitized silver halide emulsion strata each having a dye developer material of predetermined color associated therewith which as soluble and dilfusible in alkali at a first pH.
  • the preferred photosensitive image-receiving element comprises an alkaline solution permeable polymeric layer dyeable by the dye developer; a polymeric spacer layer comprising a polymer possessing decreasing alkaline solution permeability with increasing temperature; an alkaline solution permeable polymeric acid layer containing sufficient acidifying groups to effect reduction, subsequent to substantial multicolor transfer dye image formation, of the image-receiving element from the first pH to a second pH, at Which the dye image-providing material is insoluble and nondilfusible; and a dimensionally stable support layer.
  • the silver halide emulsions comprising the multicolor photosensitive laminate preferably possess predominant spectral sensitivity to separate regions of the spectrum and each has associated therewith 'a dye, which is a silver halide developing agent and is, most preferably, substantially soluble in the reduced form only at the first pH, possessing a spectral absorption range substantially complementary to the predominant sensitivity range of its associated emulsion.
  • each of the emulsion strata, and its associated dye is separated from the remaining emulsion strata, and their associated dye, by separate alkaline solution permeable polymeric interlayers.
  • the silver halide emulsion comprises photosensitive silver halide dispersed in gelatin and is about 0.6 to 6 microns in thickness; the dye itself is dispersed in a aqueous alkaline solution polymeric binder, preferably gelatin, as a separate layer about 1 to 7 microns in thickness; the alkaline solution permeable polymeric interlayers, preferably gelatin.
  • each of the dimensionally stable support layers are alkaline solution impermeable and about 2 to 6 mils in thickness.
  • the respective silver halide/dye developer units of the photosensitive element will be in the form of a tripack configuration which will ordinarily comprise a cyan dye developer/red-sensitive emulsion unit contiguous the dimensionally stable support layer, the yellow dye developer/blue-sensitive emulsion unit most distant from the support layer and the magenta dye developer/green-sensitive emulsion unit intermediate those units, recognizing that the relative order of such units may be varied in accordance with the desires of the operator.
  • FIGURE 1 of the drawings wherein there is illustrated a preferred film unit of the present invention.
  • film unit 10 comprises a photosensitive laminate 11 including, in order, dimensionally stable support layer 12, preferably a fiexible sheet material; cyan dye developer layer 13; red-sensitive silver halide emulsion layer 14; interlayer 15, magenta dye developer layer 16; green-sensitive silver halide emulsion layer 17; interlayer 18; yellow dye developer layer 19; blue-sensitive sliver halide emulsion layer 20; auxiliary layer 21, which may contain an auxiliary silver halide developing agent; and an image-receiving element 22 including image-receiving layer 23; spacer layer 24; neutralizing layer 25; and dimensionally stable support layer 26, preferably a flexible sheet material.
  • a photosensitive laminate 11 including, in order, dimensionally stable support layer 12, preferably a fiexible sheet material; cyan dye developer layer 13; red-sensitive silver halide emulsion layer 14; interlayer 15, magenta dye developer layer 16; green-sensitive silver halide emulsion layer 17; interlayer 18; yellow dye developer layer 19;
  • the multilayer exposed photosensitive element 11 is shown in processing relationship with an image-receiving element 22 and a layer 27 of processing solution distributed intermediate elements 11 and 22.
  • the unit In the performance of a difiusion transfer multicolor process employing film unit 10, the unit is exposed to radiation, actinic to photosensitive laminate 11.
  • film unit may be processed by being passed through opposed suitably gapped rolls in order to apply compressive pressure to a frangible container in order and to effect rupture of the container and distribution of alkaline processing composition 27, having a pH at which the cyan, magenta and yellow dye developers are soluble and difiusible, intermediate dyeable polymeric layer 23 and auxiliary layer 21.
  • Alkaline processing solution 27 permeates emulsion layers 14, 17 and to initiate development of the latent images contained in the respective emulsions.
  • the cyan, magenta and yellow dye developers, of layers 14, 17 and 20 are immobilized, as a function of the development of their respective associated silver halide emulsions, preferably substantially as a result of their conversion from the reduced form to their relatively insoluble and nondiifusible oxidized forrn, thereby providing imagewise distributions of mobile, soluble and diifusible cyan, magenta and yellow dye developer, as a function of the point-to-point degree of their associated emulsions exposure.
  • At least part of the imagewise distributions of mobile cyan, magenta and yellow dye developer transfers, by diffusion, to aqueous alkaline solution perm able polymeric layer 23 to provide a multicolor dye transfer image to that layer.
  • a sufiicient portion of the ions comprising aqueous alkaline solution 27 transfers, by diffusion, through permeable polymeric layer 23, permeable spacer layer 24 and to permeable polymeric acid layer whereby alkaline solution 27 decreases in pH, as a function of neutralization, to a pH at which the cyan, magenta and yellow dye developers, in the reduced form, are insoluble and nondiffusible, to provide thereby a stable multicolor dye transfer image.
  • print-receiving element 22 may be manually dissociated from the remainder of the film unit, for example, by strip- Y ping.
  • 6-nitro-5-amino-4-azabenzimidazole prepared according to the procedure set forth in Example 1, supra
  • a flask containing 100 ml. of water, 25 ml. of ethanol, 0.8 g. of platinum on carbon catalyst and 0.05 g. of platinum oxide.
  • the reduction was carried out in a hydrogenator under 40 pounds per square inch pressure. When the theoretical amount of hydrogen was taken up the reduction was discontinued, the catalyst filtered from the solution under nitrogen and the solvent evaporated under vacuum. An excess of 97% formic acid was then added to the mixture which was refluxed overnight. The excess formic acid was removed by evaporation under vacuum and the residue was taken up in water and made only slightly acid with 10% sodium hydroxide.
  • the resulting solid was filtered and taken up in hot water and treated with decolorizing charcoal.
  • the resultant 5diimidazo-4-azabenzimidazole is a white solid which separated from the water on cooling. It has a melting point of from 385405 C.
  • the present invention will be illustrated in greater de tail in conjunction with the following specific examples which set out representative photographic products and processes which, however, are also intended to be illustrative and not of limiting effect.
  • the examples clearly show not only the excellent antifoggant properties of the compounds of the present invention, particularly at low 14 temperatures, but also illustrate the speed stability of photographic systems employing the compounds.
  • EXAMPLE 12 An image-receiving element was prepared by coating a cellulose nitrate subcoated baryta paper with the partial butyl ester of polyethylene/maleic anhydride copolymer prepared by refluxing, for 14 hours, 300 gms. of DX- 84031 resin [trade name of Monsanto Chemical Co., St. Louis, Mo., for high viscosity poly(ethylene/maleic anhydride)], 140 grns. of n-butyl alcohol and 1 cc. of phosphoric acid to provide a polymeric acid layer approximately 0.3 mil thick.
  • the external surface of the acid layer was coated with a 4% solution of partial acetaldehyde acetal of polyvinyl alcohol in water-methanol-isopropanol to provide a polymeric spacer layer approximately 0.15 mil thick.
  • the external surface of the spacer layer was then coated with a 2:1 mixture, by weight, of polyvinyl alcohol and poly-4-vinylpyridine, at a coverage of approximately 600 mgs. per square foot, to provide a polymeric image-receiving layer approximately 0.40 mil thick.
  • the thus-prepared image-receiving element was then baked at 180 F. for 30 minutes and then allowed to cool.
  • a multicolor, multilayer photosensitive element was prepared in a manner similar to that disclosed in the aforementioned U.S. Patent No. 3,345,163 and detailed hereinbefore.
  • the photosensitive elements comprised a support carrying a red-sensitive silver halide emulsion stratum, a green-sensitive silver halide emulsion stratum and a blue-sensitive silver halide emulsion stratum.
  • the emulsions had dispersed behind them in water-immiscible organic solvents and contained in separate gelatin polymeric layers, respectively, a cyan dye developer, a magenta dye developer and a yellow dye developer.
  • a gelatin interlayer was positioned between the yellow dye developer layer and the green-sensitive emulsion stratum, and also between the magenta dye developer layer and the red-sensitive emulsion stratum.
  • the particular dye developers employed in the photosensitive elements were 1,4-bis (a-methyl- ⁇ i-hydroquinonyl-ethylamino) 5,8 dihydroxyanthraquinone (a cyan dye developer) 2-(p-[2,5'-dihydroxyphenethyl] -phenylazo)-4- isopropoxy-l-naphthol (a magenta dye developer); and 1 phenyl 3 n hexyl carbamyl 4 (p-[hydroquinonylethyl]-phenylazo)-5-pyrazolone (a yellow dye developer).
  • the last-mentioned yellow and magenta dye developers are disclosed in U.S. Patent- No. 3,134,764 and the cyan dye developer is disclosed in U.S. Patent No. 3,13
  • the photosensitive element was then exposed through a step wedge to selectively filtered radiation and processed by spreading an aqueous liquid control processing composition comprising:
  • a second control was formulated as above with the addition of 3.5 grns. of benzotriazole antifoggant to the processing composition.
  • Example 15 The procedure of Example 13 was again carried out utilizing as an antifoggant 6-methyl-4-azabenzimidazole.
  • Example 13 The procedure of Example 12 was followed utilizing a primary control processing composition comprising:
  • the fog buildup at 5, 10 and 60 seconds processing time, comprised 0.15, 0.18, 0.23; 0.3, 0.5, 0.8; and 0.00, 0.00, 0.05, respectively.
  • the following tabulation depicts the antifoggant prop-
  • the primary control processing composition comprised:
  • a processing composition containing 0.783% G-methyl- 4-azabenzimidazole was compared with the primary control processing composition and a secondary control processing composition containing an equimolar amount (0.7%) of benzotriazole.
  • the fog buildup, at 5, l0 and 60 seconds processing time, comprised 0.15, 0.20 and 0.20 for the primary control; 0.02, 0.05 and 0.05 for the secondary control; and 0.00, 0.00 and 0.05 for the test composition.
  • test compound 6-methyl-4-azabenzimidazole
  • EXAMPLE 16 In order to demonstrate the unusual low temperature antifogging effect of the compounds utilized in the instant invention, photosensitive sheet material of Example 12 was selectively exposed to blue light and processed according to the procedure of that example employing processing compositions containing illustrative antifoggant compositions of the present invention. The following formulation was utilized as a control processing composition:
  • the lower stain points and speed stability may be eascompositions containing the antifoggants of the present ily appreciated by referring to FIG. 2 of the drawings, invention were modified slightly in the following manwhich depicts log exposure vs. density for the blue curve, ner: In lieu of 0.5 gm. of potassium thiosulfate, 0.45 gm. i.e., yellow dye density, for diffusion transfer processof potassium thiosulfate was utilized; and in lieu of the ing at 50 F. utilizing the specified antifoggants of the 3.5 gms. of benzotriazole, 1.5 gms. of benzotriazole was present invention, as compared with difiusion transfer utilized.
  • aqueous potassium iodide solution 5 grns. was utilized.
  • the optimum concentration of the agents The antifoggant-containing processing compositions to be employed should be determined empirically for of the instant invention contained the following amounts each specific photographic system. In general, such conof antifoggant, respectively centration range is between 0.005 to 5.0 mgs.
  • Test 1 0.1% 4-azabenzimidazole
  • Test 2 0.173% 5- mole of silver halide present in the silver halide emulamino 4 azabenzimidazole hydrochloride
  • Test 3 sion of concern, depending on the fogging characteris- 0.111% 5 methyl 4 azabenzimidazole
  • Test 4 tics of the silver halide emulsion.
  • concentrations below that of the designated Stain point as applied to the instant invention is synrange merely decrease fog control below the effective onymous with D of the receiving sheet after process levels generally sought, but do not negate the achieveing, which is a measure of the dye density in the receivment of some beneficial fog control.
  • one or more processing composition permeable layers of Stain may be characterized as the film units photosensitive and/or image-receiving elethe level of transfer image dye density achieved, at total ments, for example, at any stage during its manufacture,
  • the liquid processing composition referred to for efwith a control processing composition, as described fectmg monochromatic and multicolor transfer processes above, at 50 F. comprises at least an aqueous solution of an alkaline Yellow 0.3 Test Stain Blue No. Processing Composition Point Speed Primary controL.. 0.26 0.25 1 Composition containing .1% 4-azabenzim1dazole 0.20 0.
  • the following tabulation compares the antifoggant compound, for example, diethylamine, sodium hydroxproperties of the compounds of the instant invention ide or sodium carbnoate and possesses a pH in excess of with a control processing composition, as described 50 12 preferably. If the liquid processing composition is to above, at F. be applied to the emulsion by being spread thereon, pref- Yellow 0.3 Test Stain Blue No. Processing Composition Point Speed Primarycontrol. 0.16 0.82 1 Composition containing 0.1% 4-azabenzimidazole- 0 12 0. 2. Composition containing 173% fi-amino-azabenz' 0.14 0. 82 3. Composition containing .111% 5-methyl-4azabenzirnidazole- 0. 12 0.85 4.
  • the following tabulation compares the antifoggant erably in a relatively thin uniform layer, it includes a activities of the compounds of the present invention with a viscosity-increasing compound constituting a film-formprocessing composition control, as described above, at 65 ing material of the type which, when said composition 100 F. 1s spread and dried, forms a relatively firm and relatively Yellow 0.3 Test Stain Blue No. Processing Composition Point Speed Primary control- 0.13 96 1 Composition containing 0.1% i-azabenzim dazole 0. 11 0. 99 2. Composition containing 0.173% of 5-amino-4-azabenzimidazole dihydrochloride 0. 12 95 3 Composition containing 0.111% 5-methyl-4azabenzimidazole 0.12 97 4.
  • a preferred film-forming material is a high molecular weight polymer such as a polymeric, watersoluble ether which is inert to an alkaline solution such as, for example, a hydroxyethyl cellulose or sodium carboxymethyl cellulose.
  • a high molecular weight polymer such as a polymeric, watersoluble ether which is inert to an alkaline solution such as, for example, a hydroxyethyl cellulose or sodium carboxymethyl cellulose.
  • Other film-forming materials or thickening agents whose ability to increase viscosity is substantially unafiected if left in solution for a long period of time may also be used.
  • the film-forming material is preferably contained in the processing composition in suitable quantities to impart to said composition a viscosity in excess of 1,000 centipoises at a temperature of approximately 24 C. and preferably of the order of 1,000 to 200,000 centipoises at said temperature.
  • suitable liquid processing compositions may be found in the several patents and copending applications herein mentioned and also in examples herein given. Under certain circumstances, it may be desirable to apply a liquid processing composition to the photosensitive element prior to exposure, in accordance with the technique described in U.S. Patent No. 3,087,816, issued Apr. 30, 1963.
  • liquid processing composition employed may contain an auxiliary or accelerating developing agent, such as p-methylaminophenol, 2,4-diaminophenol, p-benzylaminophenol, hydroquinone, toluhydroquinone, phenylhydroquinone, 4-methylphenylhydroquinone, etc. It is also contemplated to employ a plurality of auxiliary or accelerating developing agents, such as a 3-pyrazolidone developing agent and a benzenoid developing agent, as disclosed in U.S. Patent No. 3,039,- 869, issued June 19, 1962.
  • auxiliary developing agents As examples of suitable combinations of auxiliary developing agents, mention may be made of 1-phenyl-3-pyrazolidone in combination with p-benzylaminophenol and l-phenyl 3 pyrazolidone in combination with 2,5 bis-ethyleneimino hydroquinone.
  • auxiliary developing agents may be employed in the liquid processing composition or they may be initially incorporated, at least in part, in one or more permeable strata of the film unit. It may be noted that at least a portion of the dye developer oxidized during development may be oxidized and immobilized as a result of a reaction, e.g., an energy-transfer reaction, with the oxidation product of an oxidized auxiliary developing agent, the latter developing agent being oxidized by the development of exposed silver halide. Such a reaction of oxidized developing agent with unoxidized dye developer would regenerate the auxiliary developing agent for further reaction with the exposed silver halide.
  • development may be desirably effected in the presence of an onium compound, particularly a quaternary ammonium compound, in accordance with the processes disclosed in U.S. Patent No. 3,173,786.
  • the support layers referred to may comprise any of the various types of conventional rigid or flexible supports, for example, glass, paper, metal, and polymeric films of both synthetic types and those derived from naturally occurring products.
  • Suitable materials include paper; aluminum; polymethacrylic acid, methyl and ethylesters; vinyl chloride polymers; polyvinyl acetal; polyamides such as nylon; polyesters such as polymeric films derived from ethylene glycol terephthalic acid and cellulose derivatives such as cellulose acetate, triacetate, nitrate, propionate, butyrate, acetate-propionate, or acetatebutyrate.
  • silver halides of varying halide concentrations may be advantageously employed and that the silver halide emulsions employed may be sensitized chemically and optically by any of the accepted procedures.
  • a rupturable container provides a convenient means for spreading a liquid processing composition between layers of a film unit whereby to permit the processing to be carried out within a camera apparatus
  • the practices of this invention may be otherwise effected.
  • a photosensitive element after exposure in suitable apparatus and while preventing further exposure thereafter to actinic light, may be removed from such apparatus and permeated with the liquid processing composition, as by coating the composition on said photosensitive element or otherwise wetting said element with the composition, following which the permeated, exposed photosensitive element, still, without additional exposure to actinic light, is brought into contact with the imagereceiving element for image formation in the manner heretofore described.
  • the expression positive image has been used. This expression should not be interpreted in a restrictive sense since it is used primarily for purposes of illustration, in that it defines the image produced on the image-carrying layer as being reversed, in the positive-negative sense, with respect to the image in the photosensitive element.
  • positive image assume that the photosensitive element is exposed to actinic light through a negative transparency. In this case, the latent image in the photosensitive element Wlll be a positive and the image produced on the image-carrying layer will be a negative.
  • the expression positive image is intended to cover such an image produced on the image-carrying layer.
  • a process for forming a photographic silver image which comprises the step of developing an ex posed photosensitive element containing a silver halide emulsion with an aqueous processing composition, the improvement which comprises conducting said process in the presence of an effective amount of an antifoggant of the formula:
  • R and R are each a hydrogen, halogen, lower alkyl.
  • R is a hydrogen or lower alkyl group.
  • said antifoggant is selected from the group consisting of S-methyi- 6-bromo-4-azabenzimidazole, 6 chloro-4-azabenzimida- 21 zole, -methyl-4-azabenzimidazole, 6-bromo-4-azabenzimidazole and 6-methyl-4-azabenzimidazole.
  • a process as defined in claim 1 which includes the steps of developing said exposed photosensitive element with an aqueous alkaline difiusion transfer processing composition; forming thereby an imagewise distribution of image-forming components in said photosensitive element, as a function of the point-to-point degree of exposure thereof; and transferring at least part of said imagewise distribution, by diffusion, to a contiguous imagereceiving layer to provide thereto a photographic diffusion transfer image.
  • said antifoggant is selected from the group consisting of 5-methyl- 6-bromo-4-azabenzimidazole, 6 chloro-4-azabenzimidazole, 5-methyl-4-azabenzimidazole, 6-bromo-4-azabenzimidazole and 6-methyl-4-azabenzimidazole.
  • said color image-forming components comprise a dye which is a silver halide developing agent.
  • a process for forming transfer images in color which includes, in combination, the steps of exposing a photosensitive element which comprises at least two selectively sensitized silver halide emulsion layers each having a dye of predetermined color associated therewith, which dye is a silver halide developing agent and is soluble and diifusible in alkali; contacting said exposed photosensitive element with an aqueous alkaline processing composition; effecting thereby development of the latent images contained in each of said silver halide emulsions; immobilizing the dye associated with each of said emulsions as a result of development; forming thereby an imagewise distribution of mobile dye, as a function of the point-to-point degree of exposure thereof; and transferring, by imbibition, at least a portion of each of said imagewise distributions of mobile dye to a superposed image-receiving element to provide thereto a multicolor dye transfer image.
  • a process of forming transfer images in color which includes, in combination, the steps of exposing a photosensitive element comprising blue-sensitive, green-sensitive and red-sensitive gelatino silver halide emulsion layers mounted on a common support, said blue-sensitive, green-sensitive and red-sensitive silver halide emulsion layer having associated therewith, respectively, yellow, magenta and cyan dyes, each of said dyes being a silver halide developing agent soluble and diifusible in alkali; contacting said exposed photosensitive element with an aqueous alkaline processing composition; effecting thereby development of the latent image contained in each silver halide emulsion; immobilizing said yellow, magenta, and cyan dye, as a function of development of their respective associated silver halide emulsion; forming thereby an imagewise distribution of mobile yellow, magenta and cyan dye; and transferring, by imbibition, at least a portion of each of said imagewise distributions of mobile dye to a superposed image
  • said antifoggant is selected from the group consisting of S-methyl- 6-bromo-4-azabenzimidazole, 6 chloro-4-azabenzimidazole, 5-methyl-4-azabenzimidazole, 6-bromo-4-azabenzimidazole and 6-methyl-4-azabenzimidazole.
  • a photosensitive element which comprises a support layer carrying a photosensitive silver halide emulsion having associated therewith an antifoggant of the formula:
  • R is a hydrogen or lower alkyl group.
  • a photosensitive element as defined in claim 13 wherein said antifoggant is selected from the group consisting of S-methyl-6-bromo-4-azabenzimidazole, 6 chloro-4-azabenzimidazole, 5-methyl-4-azabenzimidazole, 6-bromo-4azabenzimidazole and 6-methyl-4- azabenzimidazole.
  • a photosensitive element as defined in claim 13 wherein said support layer carries on one surface at least two selectively sensitized silver halide emulsion layers each having a dye, which dye is a silver halide developing agent, of predetermined color associated therewith.
  • each of said selectively sensitized photosensitive emulsion layers has predominant spectral sensitivity to separate regions of the spectrum and the dye associated with each of said emulsion layers possesses a spectral absorption range substantially complementary to the predominant sensitivity range of its associated emulsion layer.
  • a photographic film unit as defined in claim 13 including a diffusion transfer image-receiving element affixed at least one edge of said photosensitive element.
  • a photographic film unit as defined in claim 20 including a rupturable container retaining an aqueous alkaline processing composition affixed one edge of one of said photosensitive and said image-receiving elements and adapted upon rupture to distribute its contents intermediate said photosensitive element and said image-receiving element upon super-positioning of said elements.
  • a photographic film unit as defined in claim 19 including a diffusion transfer image-receiving element afiixed one edge of said photosensitive element and a rupturable container retaining an aqueous alkaline processing composition containing said antifoggant af- 23 fixed one edge of one of said photosensitive and said image-receiving elements and adapted upon rupture to distribute its contents intermediate said photosensitive element and said receiving element upon super-positioning of said elements.
  • a photographic film unit as defined in claim 23, wherein said antifoggant is selected from the group consisting of 5-methyl-6-brom0-4-azabenzimidazole, 6 chloro-4-azabenzimidazole, 5-methyl-4-azabenzimidazole, 6-bromo-4-azabenzimidazole and 6-methyl-4- azabenzimidazole.

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Cited By (7)

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DE2118943A1 (de) * 1971-04-19 1972-10-26 Polaroid Corp., Cambridge, Mass. (V.St.A.) Photographisches Aufzeichnungsmaterial mit einem Antischleiermittel und dessen Anwendung
US3833370A (en) * 1973-01-05 1974-09-03 Polaroid Corp Color diffusion transfer with development controlling polymeric salt
US3899331A (en) * 1973-11-14 1975-08-12 Polaroid Corp Multicolor dye developer diffusion transfer processes with pyrazolo-{8 3,4d{9 {0 pyrimidines
DE2631878A1 (de) * 1975-07-16 1977-02-03 Polaroid Corp Farbdiffusionsuebertragungsverfahren
JPS549058B1 (enrdf_load_stackoverflow) * 1971-04-19 1979-04-20
JPS5434335B1 (enrdf_load_stackoverflow) * 1970-10-15 1979-10-26
EP0034038B1 (en) * 1980-02-06 1984-05-30 E.I. Du Pont De Nemours And Company Use of silver halide development accelerators, photographic films and processes for developing lithografic film

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Publication number Priority date Publication date Assignee Title
GB2571924B (en) * 2018-03-07 2020-10-14 Subsea 7 Ltd Electrofusion fittings for lined pipes

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US2324123A (en) * 1941-07-08 1943-07-13 Eastman Kodak Co Fog inhibitor for photographic developers
US2353754A (en) * 1942-11-07 1944-07-18 Eastman Kodak Co Color photography using metallic salt coupler compounds
US2860976A (en) * 1956-08-03 1958-11-18 Eastman Kodak Co Antifoggants for photographic developers
US3173786A (en) * 1960-08-22 1965-03-16 Polaroid Corp Color diffusion transfer process, element and composition therefor
US3212893A (en) * 1961-03-27 1965-10-19 Eastman Kodak Co Photographic multicolor diffusion transfer process using dye developers
US3265498A (en) * 1960-08-22 1966-08-09 Polaroid Corp Diffusion transfer photographic process utilizing development restrainers
US3271154A (en) * 1961-11-30 1966-09-06 Gen Aniline & Film Corp Antifogging and stabilizing agents for photography
US3307947A (en) * 1964-12-16 1967-03-07 Polaroid Corp Photographic products and processes

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2324123A (en) * 1941-07-08 1943-07-13 Eastman Kodak Co Fog inhibitor for photographic developers
US2353754A (en) * 1942-11-07 1944-07-18 Eastman Kodak Co Color photography using metallic salt coupler compounds
US2860976A (en) * 1956-08-03 1958-11-18 Eastman Kodak Co Antifoggants for photographic developers
US3173786A (en) * 1960-08-22 1965-03-16 Polaroid Corp Color diffusion transfer process, element and composition therefor
US3265498A (en) * 1960-08-22 1966-08-09 Polaroid Corp Diffusion transfer photographic process utilizing development restrainers
US3212893A (en) * 1961-03-27 1965-10-19 Eastman Kodak Co Photographic multicolor diffusion transfer process using dye developers
US3271154A (en) * 1961-11-30 1966-09-06 Gen Aniline & Film Corp Antifogging and stabilizing agents for photography
US3307947A (en) * 1964-12-16 1967-03-07 Polaroid Corp Photographic products and processes

Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS5434335B1 (enrdf_load_stackoverflow) * 1970-10-15 1979-10-26
DE2118943A1 (de) * 1971-04-19 1972-10-26 Polaroid Corp., Cambridge, Mass. (V.St.A.) Photographisches Aufzeichnungsmaterial mit einem Antischleiermittel und dessen Anwendung
JPS549058B1 (enrdf_load_stackoverflow) * 1971-04-19 1979-04-20
US3833370A (en) * 1973-01-05 1974-09-03 Polaroid Corp Color diffusion transfer with development controlling polymeric salt
US3899331A (en) * 1973-11-14 1975-08-12 Polaroid Corp Multicolor dye developer diffusion transfer processes with pyrazolo-{8 3,4d{9 {0 pyrimidines
DE2631878A1 (de) * 1975-07-16 1977-02-03 Polaroid Corp Farbdiffusionsuebertragungsverfahren
JPS5215324A (en) * 1975-07-16 1977-02-04 Polaroid Corp Color diffusion transfer process
EP0034038B1 (en) * 1980-02-06 1984-05-30 E.I. Du Pont De Nemours And Company Use of silver halide development accelerators, photographic films and processes for developing lithografic film

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DE1814020B2 (de) 1977-03-03
DE1814020A1 (de) 1969-12-11
BE725273A (enrdf_load_stackoverflow) 1969-06-11
NL159790B (nl) 1979-03-15
NL6817754A (enrdf_load_stackoverflow) 1969-06-13
FR1594983A (enrdf_load_stackoverflow) 1970-06-08
GB1235747A (en) 1971-06-16

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