US3485628A - Multicolor diffusion transfer process employing a minimum amount of a processing composition - Google Patents

Multicolor diffusion transfer process employing a minimum amount of a processing composition Download PDF

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US3485628A
US3485628A US471665A US3485628DA US3485628A US 3485628 A US3485628 A US 3485628A US 471665 A US471665 A US 471665A US 3485628D A US3485628D A US 3485628DA US 3485628 A US3485628 A US 3485628A
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image
layer
photosensitive element
transfer
acid
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Edwin H Land
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Polaroid Corp
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    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03C—PHOTOSENSITIVE MATERIALS FOR PHOTOGRAPHIC PURPOSES; PHOTOGRAPHIC PROCESSES, e.g. CINE, X-RAY, COLOUR, STEREO-PHOTOGRAPHIC PROCESSES; AUXILIARY PROCESSES IN PHOTOGRAPHY
    • G03C8/00—Diffusion transfer processes or agents therefor; Photosensitive materials for such processes
    • G03C8/42—Structural details
    • G03C8/52—Bases or auxiliary layers; Substances therefor
    • 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
    • G03C8/42—Structural details

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  • 96-29 12 Claims ABSTRACT OF THE DISCLOSURE Diffusion transfer color images are formed by a process wherein a small quantity of processing liquid is absorbed into an exposed photosensitive element, and the wetted photosensitive element is then superposed on a dry image-receiving element which includes a non-diffusible, acid-reacting reagent positioned in a layer adjacent the image-receiving layer, The quantity of processing liquid absorbed by the exposed photosensitive element is sufficient to effect development and transfer.
  • This invention relates to photography and, more particularly, to a method of forming improved photographic images in dyes by diffusion transfer processes.
  • a further object of this invention is to provide diffusion transfer processes wherein a processing composition is allowed to act upon an exposed photosensitive element for a predetermined period prior to superposing said exposed photosensitive element on a dry image-receiving element, which image-receiving element includes a nondiffusible, acid-reacting reagent positioned in a layer adjacent the image-receiving layer.
  • Yet another object of this invention is to provide diffusion transfer processes wherein a minimum quantity of processing composition is employed to effect development and transfer.
  • a further object of this invention is to provide diffusion transfer processes for forming multicolor transfer images having increased dye density and improved color reproduction.
  • Still another object of this invention is to provide a novel diffusion transfer process which employes a highly alkaline, nonviscous processing composition, and wherein the pH of the color transfer image is substantially reduced very rapidly prior to exposing the image dyes to air and will in part appear hereinafter.
  • FIGURE 1 is a diagrammatic enlarged cross-sectional view illustrating the processing of a photosensitive element in a preferred embodiment of this invention
  • FIG. 2 is a diagrammatic enlarged cross-sectional view of a photosensitive element in face-to-face contact with an image-receiving element in a preferred embodiment of this invention
  • FIG. 3 is a graphic illustration of the transfer density versus exposure relationship of each dye in a multicolor dye developer transfer image obtained in accordance with this invention, wherein the image-receiving element contains a layer of a polymeric acid;
  • FIG. 4 is a graphic illustration of the transfer density versus exposure relationship of each dye in a multilayer dye developer transfer image formed in the same manner as the image from which the curves reproduced in FIG. 3 were obtained, except that the image-receiving element did not contain a layer of a polymeric acid.
  • a dye developer is a compound which is both a dye and a silver halide developing agent.
  • Particularly useful and preferred dye developers are azo and anthraquinone dyes which contain one or more hydroquinonyl groups. Numerous examples of useful dye developers and syntheses for preparing dye developers have been set forth in the literature and such information, therefore, is omitted from this application.
  • the dye developer diffusion transfer process has been embodied in commercially available films intended for use in self-developing cameras to obtain a full color transfer image in approximately one minute.
  • the processing composition is supplied in a highly viscous form, and it is applied to the exposed photosensitive element by being spread between said exposed photosensitive element and an image-receiving element as said elements are brought into superposed relationship.
  • the image-receiving element contains a non-diffusible, acid-reacting reagent positioned in a layer adjacent the image-receiving layer; image-receiving elements of this type and color diffusion transfer processes employing such image-receiving elements are disclosed and claimed in the copending application of Edwin H. Land, Ser. No. 234,- 864, filed Nov.
  • the aforementioned non-diffusible, acid-reacting reagent is effective to substantially reduce the pH of the color transfer image prior to the time at which the photosensitive element and the image-receiving element are separated from their superposed relationship, thereby eliminating post-treatment of said separated imagereceiving element to avoid color changes due to exposing the image dyes to the air.
  • Diffusion transfer images formed on image-receiving elements containing such a non-diffusible, acid-reacting reagent exhibit high optical clarity and luminosity.
  • the efficiency of such diffusion transfer processes as well as the quality of the resulting color transfer image may be substantially improved by treating the exposed photosensitive element with a processing composition for a predetermined period, during which period the photosensitive element absorbs a relatively small quantity of processing solution, and thereafter bringing said exposed photosensitive element into face-to-face contact with a dry image-receiving element containing a non-diffusible, acid-reacting reagent positioned in a layer adjacent the image-receiving layer.
  • Multicolor transfer images formed in accordance with this invention have been found to exhibit improved density and color quality as compared with multicolor transfer images obtained by use of the nonviscous processing composition with a dry image-receiving element which does not contain said nondilfusible, acid-reacting reagent.
  • the diffusion transfer processes of this invention are characterized by the fact that an extremely small quantity of processing solution is employed to process each frame or negative.
  • the processing solution is absorbed into the exposed photosensitive element from a nonviscous processing solution, e.g., by passing the exposed photosensitive element through a container of said processing solution.
  • a nonviscous processing solution e.g., by passing the exposed photosensitive element through a container of said processing solution.
  • Other techniques capable of supplying the requisite small quantity of processing solution substantially uniformly over the negative area also may be used, e.g., a liquid applicator which provides a capillary interspace through which the processing solution is applied, as disclosed in my copending application Ser. No. 242,271, filed Nov. 8, 1962 (now US. Patent No. 3,194,138 issued July 13, 1965).
  • the photosensitive element absorb the requisite quantity of processing solution from a viscous processing composition, provided it is applied in such a way that no layer of polymer or processing composition is present between the subsequently superposed photosensitive element and image-receiving element.
  • a nonviscous processing solution is preferred, since it permits one to employ very simple processing apparatus and handling techniques.
  • the image-receiving element is kept dry until it is brought into faceto-face contact With the wetted photosensitive element, and thus the image-receiving element is wetted essentially only by processing solution extracted from the photosensitive element.
  • face-to-face contact is used herein to denote the absence of any layer of processing composition between the superposed photosensitive element and imagereceiving element.
  • nonviscous processing solution and nonviscous processing composition are intended to refer to processing solutions or compositions having a viscosity substantially the same as that of water.
  • the nonviscous processing composition does not contain a polymeric film-forming material or other viscosityproviding component such as that employed in the commercially practiced color diffusion transfer process.
  • nonviscous processing solutions suitable for use in this invention by simply omitting the film-forming reagent from processing compositions of the types heretofore described in the literature; in certain instances such viscous processing compositions also may contain a reagent whose primary function is to facilitate the adherence of the partially solidified layer of processing composition to either the exposed photosensitive element or image-receiving element when said elements are separated from their superposed relationship, and such reagent also may be omitted since this function is not utilized in the process of the instant invention.
  • the novel processing techniques of this invention have permitted a reduction in the concentration of one or more reagents of the processing composition as compared with the concentration of said reagent which would be employed in a viscous processing composition.
  • concentration of a given reagent which should be employed in a nonviscous processing composition may be readily determined by one skilled in the art by performing routine concentration tests.
  • a nonviscous processing composition may be applied to the photosensitive element by a number of techniques, e.g., by use of a porous applicator block or head, by dipping the exposed photosensitive element into a container of the nonviscous processing composition or by passing the exposed photosensitive element through a container of said nonviscous processing composition.
  • Particularly useful apparatus for practicing the processes of this invention and embodying the latter two techniques are disclosed in the copending application of Edwin H. Land and Vaito K. Eloranta, Ser. No. 509,957 filed Nov. 26, 1965, and the copending application of Edwin H. Land and Albert J. Bachelder, Ser. No. 509,713 filed Nov. 26, 1965.
  • FIG. 1 shows an exposed photosensitive element 1 (containing absorbed processing solution) being removed from a container 5 of a nonviscous processing solution 7 and being brought into face-to-face contact with a dry image-receiving element 3 by passing said elements between pressure rolls 9 and 11.
  • the pressure rolls 9 and 10 may be of much simpler construction and mounting than would be the case if the rolls were required to distribute a viscous processing liquid between the two sheets, since the pressure rolls 9 and 11 are required only to press the photosensitive element 1 and the image-receiving element 3 into face-to-face contact with each other.
  • Squeegees or other means may be provided to remove excess processing solution adhering to the front and/or back of the photosensitive element as it is withdrawn from the processing solution 7 prior to being superposed on the dry image-receiving element.
  • Imagereceiving element 3 comprises a support 21 bearing a layer 23 containing a non-difiusible, acid-reacting reagent, a spacer layer 25, and an image-receiving layer 27.
  • the photosensitive element 1 comprises a support 31 carrying a layer 33 of a cyan dye developer, a layer 35 of a red-sensitive silver halide emulsion, a spacer layer 37, a layer 39 of a magenta dye developer, a layer 41 of a green-sensitive silver halide emulsion, a spacer layer 43, a layer 45 of a yellow dye developer, and a layer 47 of a blue-sensitive silver halide emulsion.
  • the blue-sensitive emulsion layer may be overcoated with a layer containing an auxiliary silver halide developing agent, as disclosed and claimed in US. Patent No. 3,192,044 issued June 29, 1965 to Howard G. Rogers and Harriet W. Lutes.
  • this invention provides a transfer process wherein a photosensitive element is allowed to absorb a predetermined, small quantity of processing solution, after which it is brought into faceto-face contact with a dry image-receiving element containing a non-diffusible, acid-reacting reagent in a layer of the image-receiving element adjacent to the imagereceiving layer.
  • the requisite quantity of processing solution is absorbed by allowing the photosensitive element to be in contact for a predetermined period with an appropriate quantity of processing composition, e.g., a container of a nonviscous processing solution.
  • This predetermined period constitutes, as a minimum, a period of time sufiicient for the permeable layers of said photosensitive element, or at least some of such permeable layers, to absorb from said processing composition a quantity of processing solution sufficient to effect diffusion transfer processing of said photosensitive element, and, as a maximum, a period of time after which the unoxidized dye developers would begin to diffuse laterally and/ or out of the photosensitive layer, prior to bein superposed on the dry image-receiving element, to an extent such that the photographic quality of the transfer image (particularly such elements of photographic quality as maximum density, color saturation and color separation) would be adversely affected.
  • this predetermined period will vary as a function of the permeability and swellability of the various layers and hence the rate at which the processing solution or liquid is absorbed, the diffusion rates of the dye developers, etc., and may be readily and quickly determined by one skilled in the art for any given combination of photosensitive element, image-receiving element and viscous processing liquid. It will also be recognized that it is within the ability of one skilled in the art to vary such permeability and/or dilfusibility to facilitate practice of this processing technique. Thus, for example, one may reduce the initial rate of diffusion by employing hydrolyzable derivatives of dye developers, as disclosed and claimed in the copending application of Edwin H. Land and Howard G. Rogers, Ser. No. 194,359, filed May 14, 1962 (now US. Patent No. 3,- 230,082 issued Ian. 18, 1966).
  • the imagereceiving element is not brought into superposed relationship with the wetted negative until after the requisite quantity of processing solution has been absorbed into the negative, there is a delay before the acid-reacting reagent is available to react with alkali dissolved in the processing solution, without a corresponding delay in the ability of the processing solution to initiate development of the photosensitive element.
  • the acid-reacting reagent does have access to the alkaline components of the processing solution, it is effective to reduce the pH at a more rapid rate, in view of the small total quantity of processing solution being used, than if it is used with a viscous processing composition applied simultaneously to both the negative and the image-receiving element.
  • the pHreducing action of the acid-reacting reagent is deferred without having to lower the rate at which pH reduction is effected once it is initiated.
  • the reaction of the alkali with a polymeric acid releases a quantity of water which, though quite small, is significant in relation to the total quantity of processing solution originally absorbed into the photosensitive element. This released Water of reaction is formed imagewise and is believed to aid in the desired transfer of the diifusible dyes.
  • image-receiving elements containing a polymeric acid layer are appreciably thicker than similar elements which do not contain such a polymeric acid layer; this added thickness of permeable layers of the image-receiving element also is believed to have an effect in creating the desired time controlled changes in the concentration gradients of the various reagents, including the alkali and the diffusible dye developers.
  • the image-receiving element includes a layer containing a non-diffusible, acid-reacting reagent.
  • a layer containing an acid-reacting polymer, and particularly a polymer containing free carboxyl O (&-OH) groups is provided between the image-receiving layer [i.e., the layer in which the dye image is formed, and frequently referred to simply as the image layer] and the support.
  • this layer is sometimes refererd to herein as a polymeric acid layer or as an acid polymer layer.
  • the pH of the processing composition preferably is at least 12, and more preferably is of the order of at least 13 to 14.
  • the acid polymer layer contains at least sufficient acid groups to effect a reduction in the pH of the image layer from a pH of about 12 or 13 to 14 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 image layer should be kept at a level of pH 12 to 14 until the positive dye image has been formed after which the pH should be reduced very rapidly to at least about pH 11, and preferably about pH 8 to 10, before the positive image is separated and exposed to air.
  • Unoxidized dye developers containing hydroquinonyl developing radicals diffuse from the negative to the positive as the sodium, potassium or other alkali salt. The diffusion rate of such dye developers thus is at least partly a function of the alkali concentration, and it is necessary that the pH of the image layer remain on the order of 12 to 14 until transfer of the necessary quantity of dye developer has been accomplished.
  • the subsequent pH reduction serves a highly valuable photographic function by substantially teminating further dye transfer, thus effectively minimizing changes in color balance as a result of longer imbibition times in multicolor processes using multilayer negatives.
  • the acid groups are so distributed in the acid polymer layer that the rate of their availability to the alkali is controllable, e.g., as a function of the rate of swelling of the polymer layer, which rate in turn has a direct relationship to the diffusion rate of the alkali ions.
  • the desired distribution of the acid groups in the acid polymer layer may be effected by mixing the acid polymer with a polymer free of acid groups, or lower in concentration of acid groups, and compatible therewith, or by using only the acid polymer but selecting one having a relatively lower proportion of acid groups.
  • the layer containing the polymeric acid thus may also contain a water-insoluble polymer, preferably a cellulose ester, which acts to control or modulate the rate at which the alkali salt of the polymer acid is formed.
  • a water-insoluble polymer preferably a cellulose ester
  • cellulose esters contemplated for use in this invention mention may be made of cellulose acetate, cellulose acetate butyrate, etc.
  • Such a polymer also may be added to provide increased wet adhesion to prevent separation of the image-receiving layer or other layers of the imagereceiving element during processing.
  • the particular polymers and combinations of polymers employed in any given embodiment are, of course, selected so as to have adequate wet and dry strength. Where necessary or desirable, suitable subcoats may be employed to help the various polymeric layers adhere to each other during storage and use.
  • polymeric acid is intended to mean 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 acid-yielding 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, non-diifusible from the acid polymer layer.
  • the acid polymer contains free carboxyl groups and the processing composition contains a large concentration of sodium or potassium ions.
  • the acid polymers found 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 salts.
  • dibasic acid halfester derivatives of cellulose which derivatives contain free carboxyl groups, e.g., cellulose acetate hydrogen phthalate, cellulose acetate hydrogen glutarate, cellulose acetate hydrogen succinate, ethyl cellulose hydrogen succinate, ethyl cellulose acetate hydrogen succinate, cellulose acetate hydrogen succinate hydrogen phthalate; ether and ester derivatives of cellulose modified with sulfoanhydrides, e.g., with ortho-sulfobenzoic anhydrides; polystyrene sulfonic acid; carboxymethyl cellulose; polyvinyl hydrogen phthalate; polyvinyl acetate hydrogen phthalate; polyacrylic acid; acetals of polyvinyl alcohol with carboxyor sulfo-substituted aldehydes, e.g., m-, or pbenzaldehyde s
  • an inert interlayer between the image layer and the polymeric acid layer substantially improves the control of the pH reduction by the polymeric acid layer.
  • this spacer layer preferably is composed of a polymer such as polyvinyl alcohol, other polymers, such as gelatin, which are inert to alkali but through which the alkali may diffuse to the polymeric acid layer, may be used.
  • the presence of such an interlayer has been found quite effective in evening out the various reaction rates over a wide range of temperatures, e.g., by preventing premature pH reduction when imbibition is effected at temperatures above room temperature, e.g., at 95l00 F.
  • the rate at which alkali is available for capture in the polymeric acid layer becomes a function of alkali diffusion rates.
  • the pH reduction thus is made relatively independent of chemical reaction rates which would show a greater variation over similar wide changes in imbibition temperature.
  • the spacer layer referred to above comprises a polymer which exhibits a permeability to alkali ions which is inversely temperature dependent, i.e., it exhibits decreasing permeability to solubilized alkali ions, such as alkali metal and quaternary ammonium ions, under conditions of increasing temperature.
  • alkali ions which is inversely temperature dependent, i.e., it exhibits decreasing permeability to solubilized alkali ions, such as alkali metal and quaternary ammonium ions, under conditions of increasing temperature.
  • the use as spacer layers of polymers which exhibit such inverse temperature dependent permeability to alkali is disclosed and claimed in the copending application of Leonard C. Farney, Howard G. Rogers and Richard W. Young, Ser. No. 447,100, filed Apr. 9, 1965 and now abandoned.
  • polyvinyl methyl ether polyethylene oxide, polyvinyl oxazolidinone, hydroxypropyl methylcellulose, and partial acetals of polyvinyl alcohol, such as the partial acetals. butyrals, formals and propionals of polyvinyl alcohol.
  • Particularly useful partial acetals of polyvinyl alcohol have molecular weights of about 1000 to 50,000 and have from about 10 to of the available hydroxyl groups acetalized.
  • Mixed acetals also may be used, and the aldehyde may itself be substituted, e.g., methoxypropionaldehyde.
  • the inert spacer layer e.g., the polyvinyl alcohol or partial polyvinyl butyral interlayers, acts to time control the pH reduction by the polymeric acid layer. This timing is a function of the rate at which the alkali diffuses through this inert spacer layer. It has been found that the pH does not drop until the alkali has passed through this spacer layer, i.e., the pH is not reduced to any significant extent by the mere diffusion of alkali into the polyvinyl alcohol interlayer, but the pH drops quite rapidly once the alkali diffuses through the polyvinyl alcohol layer.
  • reaction of the polymeric acid with the diffusing alkali releases water.
  • This water of reaction appears to have an accelerating effect upon the rate at which the pH is reduced.
  • the equilibria Prior to permeation of the alkali through the inert spacer layer, the equilibria favor the alkali remaining close to the negative and close to the image layer. Once alkali has permeated through to the polymeric acid layer, the equilibria are shifted by the trapping of that alkali.
  • the water formed by reaction of the acid polymer with the alkali helps to remove alkali ions from the image layer and helps swell the insert polymer, thereby increasing the rate at which the alkali diffuses through the inert layer to the polymeric acid layer.
  • These factors help to keep the pH high until the image is formed, and then to cause the pH to drop rapidly after the image has been formed.
  • the pH may be kept high during development and transfer, and rapidly dropped after the transfer image has been formed.
  • This also helps to effect the pH reduction within the same imbibition periods which otherwise would be employed.
  • the released water of reaction permits the positive and negative to remain in superposed relationship for much longer imbibition times without sticking which is caused by drying out. In turn, this released water permits one to continue imbibition for periods long enough to assure more than the minimum desired pH reduction.
  • the fact that the pH reduction also acts to create a self-limiting transfer density permits such continued imbibition to proceed without undesired color balance changes.
  • image-receiving layers comprising polyvinyl alcohol and poly-4-vinylpridine in ratios, by weight, for example, of from 1:3 to 3:1.
  • a preferred image-receiving layer is such a mixture of polyvinyl alcohol and poly-4-vinylpyridine (such receiving layers are disclosed and claimed in U.S. Patent No. 3,148,061 issued to Howard C. Haas on Sept. 8, 1964), the invention is not limited thereto.
  • Other image-receiving layers such as the partial acetals of polyvinyl alcohol with trialkylammonium benzaldehyde quaternary salts, e.g., the p-trimethylammonium benzaldehyde p-toluene sulfonate partial acetal of polyvinyl alcohol [as disclosed and claimed in the copending application of Howard C. Haas, Ser. No.
  • the polymeric acid layer is preferably relatively thick as compared, e.g., with the image-receiving layer.
  • the image-receiving layer is preferably about 0.25 to 0.4 mil thick, and the polymeric acid layer is preferably 0.5 to 1.5 mil thick. If an inert spacer layer is present, that layer is preferably about 0.1 to 0.7 mil thick.
  • Plasticizers may be added to one or more layers to increase flexibility, and subcoats may be employed to facilitate adhesion of various of the layers.
  • Processing preferably is effected in the presence of an auxiliary or accelerating silver halide developing agent which is substantially colorless, at least in the unoxidized form.
  • an auxiliary or accelerating silver halide developing agent which is substantially colorless, at least in the unoxidized form.
  • Particularly useful are substituted hydroquinones, such as phenylhydroquinone, 4'-methylphenyl-hydroquinone, toluhydroquinone, tertiary-butyl-hydroquinone, and 2,5-triptycene diol.
  • These hydroquinones may be employed as components of the processing composition or they may be incorporated in one or more layers of the negative.
  • Particularly useful results are obtained when 4- methylphenylhydroquinone is dispersed in one or more of the gelatin interlayers of the negative and/or in a gelatin layer coated over the blue-sensitive emulsion layer.
  • the support for the image-receiving layer may be transparent or opaque.
  • Suitable opacifying agents may be incorporated in the negative and/ or positive to permit imbibition to be completed outside of a camera, i.e., in an area exposed to light actinic to the silver halide emulsion.
  • the addition of small quantities of a white pigment, such as titanium dioxide, to the polymeric acid layer, spacer layer, etc., is efifective to prevent edge leakage of light during processing outside of a camera.
  • Suitable hardening agents may be employed in the image-receiving layer coating solution.
  • Particularly useful hardening agents are acrolein condensates, such as that sold by Shell Development Corporation under the trade name Aldocryl Resin X-12, and disclosed in the copending application of Lloyd D. Taylor, Ser. No. 229,- 194, filed Oct. 8, 1962.
  • the processing composition contains a substantial concentration of potassium ions, e.g., at least 50% and more preferably at least 75 to of the alkali metal ions (by weight) present are potassium ions.
  • potassium ions e.g., at least 50% and more preferably at least 75 to of the alkali metal ions (by weight) present are potassium ions.
  • Use of such potassium containing processing compositions has effected a substantial reduction in imbibition time in processes of the type with which this invention is concerned.
  • other alkali metal ions also are present, e.g., sodium, lithium, or cesium
  • particularly useful r sults are obtained when at least part of such additional alkali metal ions are lithium ions, and the lithium ion concentration preferably is from 1 to 15%, by weight, of the total alkali metal ions present.
  • potassium hydroxide is used in a concentration at least equivalent to the normally used sodium hydroxide concentrations, the pH of the processing composition being of the order of at least pH 12 to 14.
  • Useful results may be obtained by the use of potassium hydroxide concentrations within the range of about 2 to 15%, by weight.
  • image-receiving elements e.g., polyvinyl alcohol or gelatin containing a dye mordant such as poly-4-vinylpyridine.
  • the image-receiving element also may contain a development restrainer or arrestor, e.g., l-phenyl-5-mercaptotetrazole, as disclosed in the copending application of Howard G. Rogers and Harriet W. Lutes, Ser. No. 50,849, filed Aug. 22, 1960 (now U.S. Patent No. 3,265,498 issued Aug. 9, 1966).
  • pH as used throughout the specification and the attached claims represents the logarithm of the reciprocal of the hydrogen ion concentration.
  • the pH of the transfer image is determined by the use of pH paper wet with distilled water and measured at the surface of the image-receiving layer.
  • the photosensitive element employed was a commercially available integral multilayer negative of the type commercially available under the designation Polaroid Polacolor Type 108 Land film; the total thickness of the various permeable layers coated on the support was approximately 0.00075.” Concentrations of reagents are given as percent by weight.
  • EXAMPLE 1 A photosensitive element was exposed to a color step wedge. The exposed photosensitive element was then dipped into a container of a nonviscous aqueous alkaline solution containing:
  • the photosensitive element was r moved from the container and immediately pressed into face-toface contact with a dry image-receiving element by passing the two elements between pressure rolls adjusted to firmly press them together without squeezing absorbed processing solution of the photosensitive element. Any excess liquid on the surface of the photosensitive element also was removed by the rolls.
  • the image-receiving element prepared by coating cellulose nitrate subcoated baryta paper with a polymeric acid layer approximately 0.00075" thick comprising the n-butyl half-ester of poly- (ethylene/maleic anhydride), followed by a spacer layer approximately 0.0003" thick comprising polyvinyl alcohol, followed by an image-receiving layer approximately 0.0003" thick comprising a 2:1 mixture, by weight, of polyvinyl alcohol and poly-4-vinylpyridine and also containing a small amount of l-phenyl-5-mercaptotetrazole.
  • the photosensitive and image-receiving elements were 11 held in contact for 60 seconds, after which they were separated.
  • Example 2 The procedure described in Example 1 was repeated except that the processing solution also contained 0.5% potassium thiosulfate.
  • the resulting multicolor transfer image exhibited substantially the same color balance but a higher exposure index or faster film speed than the transfer image obtained in Example 1.
  • the integral blue, green and red H and D curves, taken from the neutral column of the step wedge, of the multicolor transfer image of this example are reproduced in FIG. 3; the following reflection densities were measured in the neutral column:
  • Blue Green R ed Pictures made in accordance with the procedure described in this example exhibit better reds, better flesh tones, and at least twice the resolution as transfer images prepared using the same photosensitive element and imagereceiving element and a viscous processing composition.
  • EXAMPLE 4 The procedure described in Example 2 was repeated, except that the benzotriazole concentration was reduced to 1.5%. The resulting multicolor transfer image exhibited a lower D and better greens than the image obtained in Example 2.
  • the resulting multicolor transfer image exhibited greater cyan density.
  • EXAMPLE 6 The procedure described in Example 2 was repeated, adding 0.5% lithium nitrate to the processing solution. This resulted in improved color balance in room temperature processing, and substantially increased cyan transfer. Very good quality multicolor transfer images were made even when the time the photosensitive and image-receiving elements were in face-to-face contact was reduced to 20 seconds.
  • Example 8 The procedure described in Example 2 was repeated at a temperature of F. by conditioning all the components for 2 hours at 95 F. Very good transfer images were obtained with the photosensitive element dipped into the processing solution for 6 seconds, employing an imbibition or transfer time of 60 seconds.
  • EXAMPLE 9 When the procedure described in Example 8 was repeated at 50 F., good transfer images were obtained by dipping the photosensitive element into the solution for 15 seconds, and allowing the photosensitive and image receiving elements to imbibe for seconds. Addition of 0.5% lithium nitrate to the processing solution permitted shortening the time the photosensitive element was in the solution to 12 seconds.
  • EXAMPLE 10 The procedure described in Example 2 was repeated with all components conditioned at 72 F., but the superposed photosensitive element and image-receiving element were immediately subjected to a temperature of 43 F.
  • the transfer image obtained in 60 seconds in this manner exhibited only very slightly less density, primarily cyan density, than the transfer image obtained when imbibition was effected at 72 F.
  • This example like Example 7. shows the importance of the temperature at which development is initiated.
  • this invention may be utilized to process individual sheets of film, or it may be employed 13 in continuous processing of long strips of film, e.g., movie film.
  • the sheet materials employed may be substantially plain sheets or webs, requiring none of the masks, traps, containers or other arrangements for providing the processing liquid, controlling the distribution of the processing composition, or the trapping and retaining of the processing composition, as are utilized with viscous processing solutions.
  • a white border on the transfer image may be provided by a white light exposure of a marginal strip of each frame prior to photoexpsoure, or by other techniques obvious to one skilled in the art.
  • a diffusion transfer process for forming a transfer image in color comprising the steps of: (a) exposing a photosensitive element containing at least one silver halide emulsion, each said silver halide emulsion having associated therewith a dye developer; (b) contacting said exposed photosensitive element with a nonviscous aqueous alkaline processing solution for a short period whereby a relatively small quantity of said processing solution is absorbed by said exposed photosensitive element and development of said exposed photosensitive element is thereby initiated; (c) bringing said exposed photosensitive element containing said absorbed processing solution into face-to-face contact with a dry image-receiving element, said image-receiving element including an image-receiving layer and a non-diffusible, acid-reacting reagent positioned in a layer adjacent to said image-receiving layer; (d) forming, as a function of said development, an imagewise distribution of diffusible dye developer in undeveloped areas of each said silver halide emulsion
  • said photosensitive element contains a layer of a blue-sensitive silver halide emulsion, a layer of a greensensitive silver halide emulsion, and a layer of, a redsensitive silver halide emulsion, said silver halide emulsions being superposed on the same support and having associated therewith, respectively, a yellow dye developer, a magenta dye developer, and a cyan dye developer, each of said dye developers containing a hydroquinonyl radical.
  • a diffusion transfer process for forming a transfer image in color comprising the steps of: (a) exposing a photosensitive element containing at least one silver halide emulsion, each said silver halide emulsion having associated therewith a dye developer; (b) absorbing a relatively small quantity of a non-viscous processing solution into said exposed photosensitive element, thereby initiating development of said exposed photosensitive element; (c) bringing said exposed photosensitive element containing said absorbed processing solution into face-toface contact with a dry image-receiving element, said image-receiving element including an image-receiving layer and a non-diffusible, acid-reacting reagent positioned in a layer adjacent to said image-receiving layer; (d) forming, as a function of said development, an imagewise distribution of diffusible dye developer in undeveloped areas of each said silver halide emulsion, and transferring at least a portion of each said imagewise distribution of diffusible dye developer, by diffusion, to
  • a diffusion transfer process for forming a multicolor transfer image comprising the steps of: (a) exposing a photosensitive element comprising a layer of a bluesensitive silver halide emulsion, a layer of a green-sensitive silver halide emulsion, and a layer of a red-sensitive silver halide emulsion, said silver halide emulsions being superposed on the same support and having associated therewith, respectively, a yellow dye developer, 9.
  • a diffusion transfer process for forming a transfer image in color comprising the steps of: (a) exposing a photosensitive element containing at least one silver halide emulsion, each said silver halide emulsion having associated therewith a dye developer; (b) absorbing a relatively small quantity of a processing solution into said exposed photosensitive element, thereby initiating development of said exposed photosensitive element; (c) bringing said exposed photosensitive element containing said absorbed processing solution into face-to-face contact with a dry image-receiving element, said image-receiving element including an image-receiving layer and a non-difiusible, acid reacting reagent positioned in a layer adjacent to said image-receiving layer; (d) forming, as a function of said development, an imagewise distribution of diffusible dye developer in undeveloped areas of each said silver halide emulsion, and transferring at least a portion of each said imagewise distribution of diffusible dye developer, by ditfusion, to said image-

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US471665A 1965-07-13 1965-07-13 Multicolor diffusion transfer process employing a minimum amount of a processing composition Expired - Lifetime US3485628A (en)

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Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US1907252A (en) * 1929-01-31 1933-05-02 Debrie Andre Leon Vict Clement Method for treating films arranged in strips
US2500421A (en) * 1944-11-03 1950-03-14 Polaroid Corp Photographic silver halide transfer process
US3345172A (en) * 1964-12-01 1967-10-03 Polaroid Corp Photographic processing method utilizing frozen aqueous solutions
US3362819A (en) * 1962-11-01 1968-01-09 Polaroid Corp Color diffusion transfer photographic products and processes utilizing an image receiving element containing a polymeric acid layer
US3362821A (en) * 1963-05-01 1968-01-09 Polaroid Corp Diffusion transfer processes utilizing photosensitive elements containing polymeric acid spacer layers

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US1907252A (en) * 1929-01-31 1933-05-02 Debrie Andre Leon Vict Clement Method for treating films arranged in strips
US2500421A (en) * 1944-11-03 1950-03-14 Polaroid Corp Photographic silver halide transfer process
US3362819A (en) * 1962-11-01 1968-01-09 Polaroid Corp Color diffusion transfer photographic products and processes utilizing an image receiving element containing a polymeric acid layer
US3362821A (en) * 1963-05-01 1968-01-09 Polaroid Corp Diffusion transfer processes utilizing photosensitive elements containing polymeric acid spacer layers
US3345172A (en) * 1964-12-01 1967-10-03 Polaroid Corp Photographic processing method utilizing frozen aqueous solutions

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AT280782B (de) 1970-04-27
BE684056A (nl) 1967-01-13
CH476330A (de) 1969-07-31
SE339167B (nl) 1971-09-27
DE1572002A1 (de) 1970-01-02
NL6609842A (nl) 1967-01-16
GB1112284A (en) 1968-05-01

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