US3649266A - Magenta dye developer and transfer system employing same - Google Patents

Magenta dye developer and transfer system employing same Download PDF

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US3649266A
US3649266A US38510A US3649266DA US3649266A US 3649266 A US3649266 A US 3649266A US 38510 A US38510 A US 38510A US 3649266D A US3649266D A US 3649266DA US 3649266 A US3649266 A US 3649266A
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layer
silver halide
halide emulsion
photosensitive element
dye
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Derek D Chapman
Leslie G S Brooker
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Eastman Kodak Co
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Eastman Kodak Co
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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
    • C09B23/00—Methine or polymethine dyes, e.g. cyanine dyes
    • C09B23/02—Methine or polymethine dyes, e.g. cyanine dyes the polymethine chain containing an odd number of >CH- or >C[alkyl]- groups
    • C09B23/06—Methine or polymethine dyes, e.g. cyanine dyes the polymethine chain containing an odd number of >CH- or >C[alkyl]- groups three >CH- groups, e.g. carbocyanines
    • 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
    • G03C8/14—Oxidation of the chromogenic substances
    • G03C8/16—Oxidation of the chromogenic substances initially diffusible in alkaline environment
    • G03C8/18—Dye developers

Definitions

  • Diffusion transfer color processes have been described in a number of patents, including US. Pat. No. 2,983,606, wherein photographic elements containing silver halide emulsion layers and layers containing diffusible dye developers (dyes having a silver halide developing function) are exposed to record the latent image in the silver halide and then treated with an alkaline processing composition which permeates the emulsion layers and layers containing the dye developers which then develop the latent images to silver images. At the same time, oxidation products of the dye developers are formed in situ with the silver images and which are relatively nondiffusing in the colloid vehicle of the layers.
  • diffusible dye developers dye having a silver halide developing function
  • the nondiffusing character of the oxidized dye developers is apparently due, at least in part, to a decrease in solubility in the alkaline processing liquid, and may also be due to a hardening effect of the oxidized developer upon the colloid vehicles of the layers which retards the diffusion of the oxidized dye developers.
  • the residual unoxidized dye developers remaining in the layers in imagewise distribution are transferred by diffusion to a superposed reception element substantially to the exclusion of the silver image and oxidized dye developer to provide a positive dye image.
  • the dye developers are oxidized and rendered nondiffusing in the developed regions of the layers upon treatment with the processing liquid.
  • the residual dye developer images in the positive regions are transferred by diffusion and in register to the reception element to provide a multicolor reproduction.
  • each silver halide emulsion layer has associated therewith a dye developer possessing a spectral absorption range substantially complementary to the predominant sensitivity range of its associated emulsion, i.e., the blue-sensitive silver halide emulsion layer will have a yellow dye developer associated therewith, the green-sensitive silver halide emulsion layer will have a magenta dye developer associated therewith, and the red-sensitive silver halide emulsion layer will have a cyan dye developer associated therewith.
  • the dye developer associated with each silver halide emulsion layer is contained either in a silver halide emulsion layer itself or in a layer contiguous to the silver halide emulsion layer, typically under the silver halide layer with respect to the exposure direction.
  • magenta dye developer would be normally associated with a green-sensitive silver halide emulsion for use in a three-color system, although it could actually be associated with any light-sensitive silver halide emulsion to obtain e.g., monochrome images, false color" images etc.
  • the spectral absorption range for a magenta dye developer should be high in the green region of the spectrum and low in the red and blue regions in order to have as little color contamination as possible in the resulting prints. It would be highly desirable to provide a magenta dye developer that is capable of yielding increased absorption in the green region, while at the same time providing less absorption in the red and blue regions as compared with dye developers previously employed.
  • a further object of the present invention is to provide a novel color diffusion transfer system wherein transfer images have increased absorption in the green region of the spectrum and much less absorption in the red and blue regions when compared to images obtained with prior art magenta dye developers.
  • magenta photographic dye developers 1-(dihydroxybenzyl)indocarbocyanine dye developers. It has been found that the dye developers of the present invention possess a spectral absorption range having high absorption in the green region of the spectrum, while at the same time providing very little absorption in the red and blue regions as compared with magenta dye developers of the prior art. Thus, as will be hereinafter illustrated, much less color contamination results if the dye developers of the present invention are employed in a diffusion transfer system than is the case when such known magenta dye developers as 4-isopropoxy-2-[p-B-hydroquinonylethyl)-phenylazo]-1- naphthol described in U.S. Pat. Nos. 3,362,819 and 3,415,644, are employed.
  • R represents a hydrogen atom, an alkyl group, or an aryl group
  • R and R represent alkyl groups or when taken together constitute the number of carbon atoms necessary to form a carbocyclic ring having five, six or seven members
  • X represents an acid anion
  • R groups include an alkyl group, preferably a lower alkyl group, i.e., having from one to four carbon atoms in the chain, particularly methyl and ethyl; and an aryl group, e.g., phenyl, etc.
  • substituted alkyl groups are intended to come within the meaning of alkyl.38
  • the substituted alkyl groups are substituted lower alkyl groups containing from one to four carbon atoms in the chain, such as an aralkyl group, e.g., benzyl, phenethyl, etc., a hydroxyalkyl group, e.g., B-methoxyethyl, etc., a carboxyalkyl group, e.g., B-carboxyethyl, etc., a sulfoalkyl group, e.g., w-sulfobutyl, etc.
  • an aralkyl group e.g., benzyl, phenethyl, etc.
  • a hydroxyalkyl group e.g., B-methoxyethyl, etc.
  • a carboxyalkyl group e.g., B-carboxyethyl, etc.
  • substituted aralkyl groups are intended to come within the meaning of the term alkyl.”
  • a preferred substituted aralkyl group is a 2,5-dihydroxy benzyl group.
  • R represents a methyl group or a 2,5-dihydroxyl group.
  • R represents a methyl group or 2 2,5- dihydroxyl group.
  • R, and R groups include alkyl, preferably lower alkyl having from one to four carbon atoms in the chain, substituted alkyl as defined above, or when taken together a five, six or seven-member carbocyclic ring.
  • X represents an acid anion, e.g., chloride, bromide, iodide, thiocyanate, sulfamate, perchlorate, p-toluenesulfonate, methyl sulfate, ethyl sulfate, etc.
  • dye developers coming within the scope of the above formula include amethylene )-indocarbocyanine perchlorate 1,1-Bis(2,5-dihydroxybenzyl)-3,3;3,3'-di(pentamethylene)-indocarbocyanine perchlorate 1,1'-Bis(2,5-dihydroxybenzyl)-3,3;3',3-
  • a particularly preferred embodiment of the present invention involves the provision of a photographic film unit which is adapted to be processed by passing the unit between a pair of juxtaposed pressure-applying members comprising:
  • a photosensitive element comprising a support having thereon a silver halide emulsion layer having associated therewith a l-(dihydroxybenzyl) indocarbocyanine dye developer;
  • said rupturable container being adapted to be positioned during processing of said film unit so that a compressive force applied to the container by the pressure applying members will effect a discharge of the containers contents into the film unit.
  • the dye image-receiving layer of the film unit can be located on a separate support adapted to be superposed on the photosensitive element after exposure thereof.
  • imagereceiving elements are disclosed, for example, in U.S. Pat. No. 3,362,819.
  • the rupturable container is usually positioned during processing of said film unit so that a compressive force applied to the container by pressureapplying members in a camera will effect a discharge of the containers contents between the image-receiving element and the outermost layer of the photosensitive element.
  • the dye image-receiving layer can also be located integral with the photosensitive element between the support and the lowermost photosensitive silver halide emulsion layer.
  • integral receiver-negative photosensitive elements are disclosed, for example, in US. Pat. No.
  • 3,415,644 are useful in camera apparatus of the type disclosed in Belgian Pat. Nos. 718,553 and 718,554.
  • the processing composition for such integral elements wherein the receiver is permanently laminated to the negative contain opacifying agents such as titanium dioxide or carbon black.
  • Barrier layers such as those described in Becker U.S. Pat. No. 3,3 84,483, may be used to advantage in such integral elements between the various emulsion and dye developer layers.
  • the color film assembly of the present invention may contain various silver halide emulsion layers disposed in the usual order, i.e., the blue-sensitive silver halide emulsion layer first with respect to the exposure side, followed by the green-sensitive and red-sensitive silver halide emulsion layers.
  • a yellow dye layer or a Carey Lea silver layer may be present between the blue-sensitive and green-sensitive silver halide emulsion layer for absorbing or filtering clue radiation that may be transmitted through the blue-sensitive layer.
  • the selectively sensitized silver halide emulsion layers may be disposed in a different order, e.g., the red-sensitive layer first with respect to the exposure side, followed by the green-sensitive and blue-sensitive layers.
  • Our novel magenta dye developer may be employed in combination with any suitable yellow dye developer and cyan dye developer in a three-color photosensitive element of the invention.
  • Dye developers i.e., compounds which contain in the same molecule both the chromophoric system of a dye and in color diffusion transfer systems in general are well known in the art as shown, for example, by US. Pat. Nos. 2,983,606; 2,992,106; 3,047,386; 3,076,808; 3,076,820; 3,077,402; 3,126,280; 3,131,061; 3,134,762; 3,134,765; 3,135,604; 3,135,605; 3,135,606; 3,135,734; 3,141,772; and 3,142,565.
  • An alkaline processing or activating composition is conveniently employed in a rupturable container or pod of the film assembly of the present invention. After exposure of the element, the alkaline processing composition is released from the pod to permeate the emulsion layers and initiate development of the latent images contained therein.
  • the dye developers are immobilized in exposed areas as a consequence of the development of the latent images. This immobilization is due at least in part, to a change in the solubility characteristics of the dye developers upon oxidation. ln unexposed areas of the emulsion layers, the dye developers remain diffusible and thus provide imagewise distributions of unoxidized dye developer dissolved in the liquid processing composition as a function of the point-to-point degree of exposure of the silver halide emulsion layers. At least part of these imagewise distributions of unoxidized dye developer are transferred, by diffusion, to the image-receiving layer.
  • the image-receiving layer contains materials adapted to mordant or otherwise fix the diffused, unoxidized dye developers
  • the dye developers are employed in separate layers contiguous to each silver halide emulsion layer.
  • Such layers can be applied by using coating solutions containing about 0.5 to about 8 percent, by weight, of the dye developer distributed in a hydrophililic film-forming natural material or synthetic polymer such as gelatin, polyvinyl alcohol, etc., which is adapted to be permeated by aqueous alkaline processing composition.
  • the preparation of a dye developer dispersion can also be obtained by dissolving the dye developer in an appropriate solvent or mixture of solvents, dispersing the resultant solution in the polymeric binder, with optional subsequent removal of the solvent or solvents employed. Further details concerning these dispersing techniques and the solvents employed are found, for example, in US. Pat. Nos. 2,269,158; 2,322,027; 2,304,939; 2,304,940; 2,801,171, and the like.
  • each silver halide emulsion layer containing a dye developer or having the dye developer present in a contiguous layer may be separated from the other silver halide emulsion layers in the film unit by materials including gelatin, calcium alginate, or any of those disclosed in US. Pat. No. 3,384,483, polymeric materials such as polyvinylamides as disclosed in US. Pat. No. 3,421,892, or any of those disclosed in US. Pat. Nos. 2.992,104; 3,043,692; 3,044,873; 3,061,428; 3,069,263; 3,069,264; 3,121,011; and 3,427,158.
  • the silver halide emulsion layers in the invention comprise photosensitive silver halide dispersed in gelatin and are about 0.6 to 6 microns in thickness; the dye developers are dispersed in an aqueous alkaline solutionperrneable polymeric binder, such as gelatin, as a separate layer about 1 to 7 microns in thickness; and the alkaline solution-permeable polymeric interlayers, e.g., gelatin, are about 1 to 5 microns in thickness.
  • these thicknesses are approximate only and can be modified according to the product desired.
  • polymeric acid layer in the film unit of the present invention will enhance the results obtained.
  • the polymeric acid layer will effect a reduction in the pH of the image layer from about 13 or 14 to at least 1 l and preferably 5-8 within a short time after imbibition.
  • Such polymeric acids reduce the pH of the film unit after development to terminate further dye transfer and thus stabilize the dye image
  • Such polymeric acids comprise polymers containing acid groups, such as carboxylic acid and sulfonic acid groups, which are capable of forming salts with alkali metals, such as sodium or potassium, or with organic bases particularly quaternary ammonium bases, such as tetramethyl ammonium hydroxide.
  • the polymers can also contain potentially acid-yielding groups such as anhydrides or lactones or other groups which are capable of reacting with bases to capture and retain them.
  • acid-yielding groups such as anhydrides or lactones or other groups which are capable of reacting with bases to capture and retain them.
  • the most useful polymeric acids contain free carboxyl groups, being insoluble in water in the free acid form and which form water-soluble sodium and/or potassium salts.
  • the polymeric acid layer is usually about 0.3 to about 1.5 mils in thickness. Although the polymeric acid layer is usually located in the receiver portion of the film unit between the support and the image-receiving layer, it can also be located in the negative portion of the film unit, as disclosed in U.S. Pat. No. 3,362,821.
  • An inert timing or spacer layer coated over the polymeric acid layer may also be used to time" or control the pH reduction of the film unit as a function of the rate at which the alkali diffuses through the inert spacer layer.
  • timing layers include gelatin, polyvinyl alcohol or any of those disclosed in U.S. Pat. No. 3,455,686.
  • the timing layer is also effective in evening out the various reaction rates over a wide range of temperatures, e.g., premature pH reduction is prevented when imbibition is effected at temperatures above room temperature, for example, at 95 to 100 F.
  • the timing layer is usually about 0.1 to about 0.7 mil in thickness.
  • the liquid processing composition that may be employed in this invention is, for example, the conventional aqueous solution of an alkaline material, e.g., sodium hydroxide, sodium carbonate or an amine such as diethylamine, preferably possessing a pH in excess of 12.
  • the composition also preferably contains a viscosity-increasing compound such as a high molecular weight polymer, e.g., a water-soluble ether inert to alkaline solutions such as hydroxyethyl cellulose or alkali metal salts of carboxyrnethyl cellulose such as sodium carboxyrnethyl cellulose.
  • a concentration of viscosity-increasing compound of about 1 to about 5 percent by weight of the processing composition is preferred which will impart thereto a viscosity ofabout 100 to about 200,000 c.p.s.
  • Development of a diffusion transfer element of the invention may also be effected in the presence of an onium compound particularly a quaternary ammonium compound, such as disclosed in U.S. Pat. Nos. 3,146,102; 3,253,915 and 3,173,786.
  • the silver halide emulsions used with this invention can comprise silver chloride, silver bromide, silver bromoiodide, silver chlorobromoiodide or mixtures thereof.
  • the emulsions may be coarse or fine grain and can be prepared by any of the well-known procedures, e.g., single jet emulsions, double jet emulsions, such as Lippmann emulsions, ammoniacal emulsions, thiocyanate or thioether ripened emulsions such as those described in Nietz et al. U.S. Pat. No. 2,222,264; lllingsworth U.S. Pat. No. 3,320,069; and McBride U.S. Pat. No.
  • Negative type emulsions can be used or direct positive emulsions can be used such as those described in Leermakers U.S. Pat. No. 2,184,013; Kendall et al. U.S. Pat. No. 2,541,472; Berriman U.S. Pat. No. 3,367,778; Schouwenaars British Pat. No. 723,019; lllingsworth et al. French Pat. No. 1,520,821; lves U.S. Pat. No. 2,563,785; Knott et al. U.S. Pat. No. 2,456,953 and Land U.S. Pat. No. 2,861,885.
  • the silver halide emulsions may be unwashed or washed to remove soluble salts.
  • the soluble salts may be removed by chill-setting and leaching or the emulsion may be coagulation washed, e.g., by .the procedures described in Hewitson et al. U.S. Pat. No. 2,618,556; Yutzy et al. U.S. Pat.
  • the silver halide emulsions may contain speed increasing compounds such as polyalkylene glycols, cationic surface active agents and thioethers or combinations of these as described in Piper U.S. Pat. No. 2,886,437; Dann et al. U.S. Pat. No. 3,046,134; Carroll et a1. U.S. Pat. No. 2,944,900; and Goffe U.S. Pat. No. 3,294,540.
  • the silver halide emulsions can be protected against the production of fog and can be stabilized against loss of sensitivity during keeping.
  • Suitable antifoggants and stabilizers each used alone or in combination include thiazolium salts described in Brooker et al. U.S. Pat. No. 2,131,038 and Allen et al. U.S. Pat. No. 2,694,716; the azaindenes described in Piper U.S. Pat. No. 2,886,437 and Heimbach et al. U.S. Pat. No. 2,444,605; the mercury salts as described in Allen et al. U.S. Pat. No. 2,728,663; the urazoles described in Anderson et al. U.S.
  • Any suitable material can be employed as the image-receiving layer in this invention as long as the desired function of mordanting or otherwise fixing the dye developer images will be obtained.
  • Suitable image-receiving materials include N-methoxymethyl polyhexylmethylene adipamide; partially hydrolyzed polyvinyl acetate; polyvinyl alcohol with or without plasticizers; cellulose acetate; gelatin; and other materials of a similar nature.
  • Polyvinyl alcohol or gelatin containing a dye mordant such as poly-4-vinylpyridine as disclosed in U.S. Pat. No. 3,148,061 can also be employed in the invention with good results.
  • the image-receiving layer is from about 0.25 to about 0.04 mil in thickness. This thickness, of course, may be modified depending upon the result desired.
  • the image-receiving layer may also contain ultraviolet absorbing materials to protect the mordanted dye images from fading due to ultraviolet light.
  • the layers of the photographic element employed and described herein may be coated on a wide variety of supports.
  • Typical supports include cellulose nitrate film, cellulose ester film, poly(vinyl acetal) film, polystyrene film, poly(ethylene terephthalate) film, polycarbonate film and related films or resinous materials, as well as glass, paper, metal and the like.
  • a flexible support is employed, especially a paper support, which can be partially acetylated or coated with baryta and/or an alpha-olefin polymer, particularly a polymer of an alpha-olefin containing two to ten carbon atoms such as polyethylene, polypropylene, ethylenebutene copolymers and the like.
  • the photographic elements of this invention can contain incorporated developing agents such as hydroquinones, catechols, aminophenols, 3-pyrazolidones, ascorbic acid and its derivatives, reductones and phenylenediamines. Combinations of developing agents can be employed in the practice of the invention.
  • the developing agents can be in a silver halide emulsion and/or in another suitable location in the photographic element.
  • the developing agents may be added form suitable solvents or in the form of dispersions as described in Yackel U.S. Pat. No. 2,592,368 and Dunn et al. French Pat. No. 1,505,778.
  • the photographic emulsions and elements described in the practice of the present invention may contain various colloids alone or in combination as vehicles, binding agents and various layers.
  • Suitable hydrophilic materials include both naturally occurring substances such as proteins, for example, gelatin, gelatin derivatives, cellulose derivatives,
  • polysaccharides such as dextran, gum arabic and the like
  • synthetic polymeric substances such as water soluble polyvinyl compounds like poly(vinylpyrrolidone), acrylamide polymers and the like.
  • the described photographic emulsion layers and other layers of the present photographic elements of this invention may also contain alone or in combination with hydrophilic, water permeable colloids, other synthetic polymeric compounds such as dispersed vinyl compounds such as in latex form and particularly those which increase the dimensional stability of the photographic materials.
  • Suitable synthetic polymers include those described, for example, in Nottorf U.S. Pat. No. 3,142,568, issued July 28, 1964; White U.S. Pat. No. 3,193,386, issued July 6, 1965; Houck et a1. U.S. Pat. No. 3,062,674, issued Nov. 6, 1962; Houck et a].
  • the various photographic layers may contain plasticizers and lubricants such as polyalcohols, e.g., glycerin and diols of the type described in Milton et al. U.S. Pat. No. 2,960,404; fatty acids or esters such as those described in Robijns U.S. Pat. No. 2,588,765 and Duane U.S. Pat. No. 3,l2l,060; and silicone resins such as those described in DuPont British Pat. No. 955,061.
  • plasticizers and lubricants such as polyalcohols, e.g., glycerin and diols of the type described in Milton et al. U.S. Pat. No. 2,960,404; fatty acids or esters such as those described in Robijns U.S. Pat. No. 2,588,765 and Duane U.S. Pat. No. 3,l2l,060; and silicone resins such as those described in DuPont British Pat. No. 9
  • the photographic layers used in the practice of this invention can be coated by various coating procedures including dip coating, air knife coating, curtain coating, or extrusion coating using hoppers of the type described in Beguin U.S. Pat. No. 2,681,294. lf desired, two or more layers may be coated simultaneously by the procedures described in Russell U.S. Pat. No. 2,761,791 and Wynn British Pat. No. 837,095.
  • This invention also can be used for silver halide layers coated by vacuum evaporation as described in British Pat. No. 968,453 and LuValle et al. U.S. Pat. No. 3,219,451.
  • the photographic and other hardenable layers used in the practice of this invention can be hardened by various organic or inorganic hardeners, alone or in combination, such as the aldehydes, and blocked aldehydes, ketones, carboxylic and carbonic acid derivatives, sulfonate esters sulfonyl halides and vinyl sulfonyl ethers, active halogen compounds, epoxy compounds, aziridines, active olefins, isocyanates, carbodiimides, mixed function hardeners and polymeric hardeners such as oxidized polysaccharides like dialdehyde starch and oxyguargum and the like.
  • various organic or inorganic hardeners such as the aldehydes, and blocked aldehydes, ketones, carboxylic and carbonic acid derivatives, sulfonate esters sulfonyl halides and vinyl sulfonyl ethers, active halogen compounds, epoxy compounds, aziridines, active
  • EXAMPLE 1 The compound, 2,3,3-trimethyl-3H-indole, in the amount of 15.9 grams is mixed with 28.7 grams of 2,5-diacetoxybenzyl bromide and the mixture is heated on a steam bath overnight.
  • the 2,5-diacetoxybenzyl bromide is produced in the manner described by D. L. Fields, J. B. Miller and D. D. Reynolds J. Org. Chem, Vol. 29', page 2640 (1964).
  • the crude product is then washed with hot ether.
  • EXAMPLE 2 Thirteen grams of the diacetoxybenzyl quaternary salt prepared in the manner described in Example 1 are admixed with 8 grams of anhydrous sodium acetate and 35 milliliters of diethoxymethyl acetate. The mixture is heated in 30 milliliters of acetic anhydride for a period of 10 minutes. Next, the mixture is cooled and poured into 500 milliliters of a saturated potassium perchlorate solution. Qne hundred milliliters of ether are added and the mixture is stirred vigorously. After a period of two hours, the solution is filtered. The crude product is hydrolyzed in the manner described in Example 1.
  • Green-sensitive photosensitive elements are prepared by coating a gelatin subbed film support comprising cellulose acetate with suitable hardened gelatin layers as follows:
  • magenta Dye Developer Layer The magenta dye developer, 4-isopropoxy-2-[p-(B- hydroquinonylethyl)-phenylazo]-l-naphthol, is dissolved in a mixture of cyclohexanone and Nn-butylacetanilide and is dispersed in an aqueous gelatin solution with a sodium alkylnaphthalene sulfonate dispersing agent. The mixture is passed through a colloid mill several times, coated on the film support and dried to volatilize the cyclohexanone to give a coverage of 64 mg. of the dye developer and 150 mg. of gelatin per square foot of element.
  • Green-Sensitive Emulsion Layer A green-sensitive silver bromoiodide emulsion is then coated on the magenta dye developer layer at a coverage of 103 mg. of silver and mg. of gelatin per square foot of element.
  • overcoat Layer A gelatin overcoat layer is the provided on the foregoing layers at a coverage of mg. per square foot of element.
  • Example 3 Additional green-sensitive coatings are prepared in the foregoing manner of Example 3 with the exception that the novel magenta dye developers of Examples 1 and 2 are substituted for the magenta dye developer, 4-isopropoxy-2-l p-(flhydroquinonylethyl)-phenylazo]-l-naphthol at coverages, respectively, of 81.5 and 97.5 mg. per square foot of element.
  • EXAMPLE 4 Samples of the film coatings produced in Example 3 are air dried and exposed on an Eastman 1B Sensitometer #2 inch to a 500-watt positive lamp a 4.08 Corning filter and are processed with a processing solution disposed in a processing pod and having the composition set forth in Table 1 below:
  • the processing solution is spread between the film and a receiving sheet.
  • the exposed film is processed at a gap of 0.0044 inch for a period of 60 seconds at about 25 C. between a pair of pressure rollers in order to spread the EXAMPLE 8
  • Three grams of the dye developer of Example 7 are dissolved in 25 ml. of dimethyl sulfoxide under nitrogen and processing solution.
  • the receiving sheet is a cellulose acetate heated with of 20 percent Sodium hydroxide at 600 butyrate f ls; suppfort Cgrymgull the followmg Order for two hours.
  • the reaction mixture is chilled in ice and zgg if gm jg fiig g f g acidified with HCl.
  • the product is filtered off, dissolved in a mordam layer comprising y py and acetone and poured into sodium perchlorate solution. After p y y alcohol and 10 filtration, a yield of 1.4 grams of the magenta dye developer 1- 4. a polyvinyl alcohol protective layer.
  • the 610 and 410 mp. are the red and blue regions of the spectrum, respectively, while the 560 and 535 mp. is the green b region.
  • Table ll there is more absorption in the green region and less absorp- N tion in the red and blue regions for the novel magenta dye H developer of the present invention (Example 6) as compared 2 with the prior art dye developer (Example 5
  • Such results in- 01F dicate that much of the unwanted absorption in the red and blue regions is eliminated with an increase of green absorption H0 thereby resulting in less color contamination.
  • Similar good results are obtained employing the l-(2,5'-dihydroxybenzyl)- l,3,3,3',3'-pentamethyl-3H indocarbocyanine perchlorate dye developer of Example 1.
  • the crude yield is 60 g. Twenty grams of hyflwqumgnylethgl*phenylawl'""apthm ls dls.s?lved m this product are dissolved in 100 ml. of methanol saturated :l cyclo exanone 9 N'n 'butyl acetamh de and is with no and then diluted 1:10 with methanol. The reaction spewed aquewigelatln alky" mixture is then stirred overnight and poured into a saturated naphthalene sulfonfne dlsperslng agent The mlxture passed sodium chloride solution.
  • the product is then filtered off, through aconold ⁇ W several nmes coated the film support dried and triturated with acetone.
  • the acetone insoluble fracand dned to volanhze the cyclohexanone to coverage of tion is dissolved in 20 ml. of dimethylformamide and poured 60 of the dye develop and 150 of gelatm Per Square slowly into a sodium perchlorate solution.
  • Overcoat Layer A gelatin overcoat layer is then provided on the foregoing layers at a coverage of 256 mg. per square foot of element.
  • the photographic layers employed in the practice of this invention may contain surfactants such as saponin; anionic compounds such as the alkyl aryl sulfonates described in Baldsiefen US. Pat. No. 2,600,831; amphoteric compounds such as those described in Ben-Ezra US. Pat. No. 3,133,816; and water soluble adducts of glycidol and an alkyl phenol such as those described in Olin Mathieson British Pat. No. 1,022,878.
  • the photographic elements may contain matting agents such as starch, titanium dioxide, zinc oxide, silica, polymeric beads including beads of the type described in Jelley et al. US. Pat. No. 2,992,101 and Lynn US. Pat. No. 2,701,245.
  • the emulsions used in this invention may be sensitized with chemical sensitizers, such as with reducing agents; sulfur, selenium or tellurium compounds; gold, platinum, or palladium compounds; or combinations of these. Suitable procedures are described in Sheppard et al. US. Pat. No. 1,623,499;
  • Spectral sensitizing dyes can be used conveniently to confer additional sensitivity to the light-sensitive silver halide emulsion of the multilayer photographic elements of the invention.
  • additional spectral sensitization can be obtained by treating the emulsion with a solution of a sensitizing dye in an organic solvent or the dye may be added in the form of a dispersion as described in Owens et al. British Pat. No. 1,154,781.
  • the dye may either be added to the emulsion as a final step or at some earlier stage.
  • sensitizing dyes useful in sensitizing such emulsions are described, for example, in Brooker et al. US. Pat. No. 2,526,632, issued Oct. 24, 1950; Sprague US. Pat. No. 2,503,776, issued Apr. 11, 1950; Brooker et al. US. Pat No. 2,493,748; and Taber et al. US. Pat. No. 3,384,486.
  • Spectral sensitizers which can be used include the cyanines, merocyanines, complex (tri or tetranuclear) merocyanines, complex (tri or tetranuclear) cyanines, holopolar cyanines, styryls, hemicyanines (e.g., enamine hemicyanines), oxonols and hemioxonols.
  • Dyes of the cyanine classes may contain such basic nuclei as the thiazolines, oxazolines, pyrrolines, pyridines, oxazoles, thiazoles, selenazoles and imidazoles.
  • Such nuclei may contain alkyl, alkylene, hydroxyallcyl, sulfoalkyl, carboxyalkyl, aminoalkyl and enamine groups and may be fused to carbocyclic or heterocyclic ring systems either unsubstituted or substituted with halogen, phenyl, alkyl, haloalkyl, cyano, or alkoxy groups.
  • the dyes may be symmetrical or unsymmetrical and may contain alkyl, phenyl, enamine or heterocyclic substituents on the methine or polymethine chain.
  • the merocyanine dyes may contain the basic nuclei mentioned above as well as acid nuclei such as thiohydantoins, rhodanines, oxazolidenediones, thiazolidenediones, barbituric acids, thiazolineones, and malononitrile. These acid nuclei may be substituted with alkyl, alkylene, phenyl, carboxyalkyl, sulfoalkyl, hydroxyalkyl, alkoxyalkyl, alkylamino groups, or heterocyclic nuclei. Combinations of these dyes may be used, if desired.
  • the various layers, including the photographic layers. employed in the practice of this invention can contain light absorbing materials and filter dyes such as those described in Sawdey US. Pat. No. 3,253,921; Gaspar US. Pat. No. 2,274,782; Silberstein et al. US. Pat. No. 2,527,583 and Van- Campen US. Pat. No. 2,956,879. if desired, the dyes can be mordanted, for example, as described in Jones et al. US. Pat. No. 3,282,699.
  • the photographic elements used in this invention may contain brightening agents including stilbenes, triazines, oxazoles and coumarin brightening agents.
  • Brightening agents including stilbenes, triazines, oxazoles and coumarin brightening agents.
  • Water soluble brightening agents may be used such as those described in Albers et al. German Pat. No. 972,067 and McFall et al. US. Pat. No. 2,933,390 or dispersions of brighteners may be used such as those described in Jansen German Pat. No. 1,150,274, Oetiker et al. US. Pat. No. 3,406,070 and Heidke French Pat. No. 1,530,244.
  • the sensitizing dyes and other addenda used in the practice of this invention may be added from water solutions or suitable organic solvent solutions may be used.
  • the compounds can be added using various procedures including those described in Collins et al. US. Pat. No. 2,912,343; McCrossen et al. US. Pat. No. 3,342,605; Audran U.S. Pat. No. 2,996,287 and Johnson et al. US. Pat. No. 3,425,835.
  • a photosensitive element comprising a support coated with a silver halide emulsion layer having associated therewith a 1-(dihydroxybenzyl)indocarbocyanine dye developer.
  • a photosensitive element comprising a support having thereon the following layers in sequence:
  • magenta dye developer layer comprising a l-(dihydroxybenzyl)indocarbocyanine
  • magenta dye developer has the formula:
  • R represents ahydrogen atom, aria lfyl grou p or 55 aryl group
  • R and R represent alkyl groups or when taken together constitute the number of carbon atoms necessary to form a carbocyclic ring having five, six or seven members
  • X represents an acid anion
  • R represents a methyl group or a 2,5-dihydroxy benzyl group, each R is a methyl group and each R is a methyl group.
  • R is hydrogen or a 2,5-dihydroxy benzyl group and each R and R taken together form a six-member carbocyclic ring.
  • a photographic film unit which is adapted to be processed by passing said unit between a pair of juxtaposed pressure-applying members comprising:
  • a photosensitive element comprising a support having thereon a silver halide emulsion layer having associated therewith a l-(dihydroxybenzyl)indocarbocyanine dye developer;
  • said rupturable container being adapted to be positioned during processing of said film unit so that a compressive force applied to said container by said pressure-applying members will effect a discharge of the containers contents within said film unit.
  • said photosensitive element comprises a support having thereon the following layers in sequence:
  • magenta dye developer layer comprising a l-(dihydroxybenzyl)indocarbocyanine.
  • magenta dye developer has the formula:
  • R represents a hydrogen atom, an alkyl group or an aryl group
  • R and R represent alkyl groups or when taken together constitute the number of carbon atoms necessary to form a carbocyclic ring having five, six or seven members
  • X represents an acid anion
  • R represents a methyl group or a 2,5-dihydroxy benzyl group, each R is a methyl group and each R is a methyl group.
  • a process for producing a photographic transfer image comprising:
  • a photosensitive element comprising a support having thereon a silver halide emulsion layer E- having associated therewith a l-(dihydroxybenzyl)indocarbocyanine dye developer;
  • a process for producing a photographic transfer image in color comprising:
  • a. imagewise exposing a photosensitive element comprising a support having thereon the following layers in sequence:
  • a yellow dye developer layer e. a yellow dye developer layer, and f. a blue-sensitive silver halide emulsion layer.
  • magenta dye developer has the formula:
  • R represents a methyl dihydroxy benzyl group and each R, and R taken together group or a 2,5-dihydroxy benzyl group, each R is a methyl form m r ca yclic ringgroup and each R is a methyl group.

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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3976489A (en) * 1972-03-24 1976-08-24 Polaroid Corporation Silver halide photographic products with semiconductor sensitizers
US4029503A (en) * 1973-03-28 1977-06-14 Konishiroku Photo Industry Co., Ltd. Diffusible-dye releasing type dyes which couple to form colorless products
US20050214833A1 (en) * 2004-02-04 2005-09-29 Biosearch Technologies, Inc. Cyanine dyes

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB1573134A (en) * 1976-06-02 1980-08-13 Gaf Corp Dyedeveloper diffusion transfer photographic element, process for its production, process of development of the element and composition

Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3146102A (en) * 1960-08-22 1964-08-25 Eastman Kodak Co Photographic multicolor diffusion transfer process using dye developers

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3146102A (en) * 1960-08-22 1964-08-25 Eastman Kodak Co Photographic multicolor diffusion transfer process using dye developers

Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3976489A (en) * 1972-03-24 1976-08-24 Polaroid Corporation Silver halide photographic products with semiconductor sensitizers
US4029503A (en) * 1973-03-28 1977-06-14 Konishiroku Photo Industry Co., Ltd. Diffusible-dye releasing type dyes which couple to form colorless products
US20050214833A1 (en) * 2004-02-04 2005-09-29 Biosearch Technologies, Inc. Cyanine dyes
US7705150B2 (en) 2004-02-04 2010-04-27 Biosearch Technologies, Inc. Cyanine dyes
US20100136567A1 (en) * 2004-02-04 2010-06-03 Biosearch Technologies, Inc. Cyanine dyes
US8436153B2 (en) 2004-02-04 2013-05-07 Biosearch Technologies, Inc. Cyanine dyes
US9435796B2 (en) 2004-02-04 2016-09-06 Biosearch Technologies, Inc. Cyanine dyes

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