US3719489A - Novel photographic processes and products - Google Patents

Novel photographic processes and products Download PDF

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US3719489A
US3719489A US00155123A US3719489DA US3719489A US 3719489 A US3719489 A US 3719489A US 00155123 A US00155123 A US 00155123A US 3719489D A US3719489D A US 3719489DA US 3719489 A US3719489 A US 3719489A
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silver
compound
color
reagent
compounds
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F Meneghini
H Rogers
R Cieciuch
R Luhowy
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Polaroid Corp
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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
    • G03C8/02—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
    • 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
    • G03C8/045—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 with the formation of a subtractive dye image
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03C—PHOTOSENSITIVE MATERIALS FOR PHOTOGRAPHIC PURPOSES; PHOTOGRAPHIC PROCESSES, e.g. CINE, X-RAY, COLOUR, STEREO-PHOTOGRAPHIC PROCESSES; AUXILIARY PROCESSES IN PHOTOGRAPHY
    • G03C8/00—Diffusion transfer processes or agents therefor; Photosensitive materials for such processes
    • G03C8/02—Photosensitive materials characterised by the image-forming section
    • G03C8/08—Photosensitive materials characterised by the image-forming section the substances transferred by diffusion consisting of organic compounds
    • G03C8/10—Photosensitive materials characterised by the image-forming section the substances transferred by diffusion consisting of organic compounds of dyes or their precursors

Definitions

  • This invention relates to photographic processes employing photographically inert compounds which are stable in the photographic processing composition but capable of undergoing cleavage in the presence of an image- Wise distribution of silver ions and/or soluble silver compleX containing silver ions made available as a function of development to liberate a reagent in an imagewise distribution corresponding to that of said silver ion and/ or said complex.
  • the photographically inert compound is substantially non-ditfusible in the photographic processing composition and the reagent released therefrom as a function of development is diffusible in the processing composition.
  • the diifusible reagent released is a diifusible dye.
  • Compounds particularly useful for liberating a reagent are 1,3-sulphur-nitrogen compounds, e.g., thiazolidines, and their vinyl and phenylene analogs.
  • This invention relates to photographic processes for providing an imagewise distribution of a reagent, such as a photographically active reagent or a dye and particularly to processes for the formation of color images and to photographic products useful therein.
  • an exposed photosensitive element comprising a light-sensitive silver halide emulsion is developed by treating the emulsion with a processing composition comprising an aqueous alkaline solution of a silver halide developing agent and a silver halide solvent.
  • the developable silver halide of the emulsion is reduced to image silver by the developing agent while the silver halide solvent forms an imagewise distribution of a soluble silver complex with the undeveloped silver halide.
  • This imagewise distribution of soluble silver complex is, at least in part, transferred by imbibition to a superposed image-receiving layer where it is reduced to form a silver transfer image.
  • color-providing materials include (A) normally diifusible color-providing materials that are rendered non-diflusible upon reaction with silver ions and/or a soluble silver complex containing the same and (B) normally non-diffusible color-providing materials that are rendered diffusible upon reaction with silver ions and/or a soluble silver complex containing the same.
  • color-providing materials include complete dyes or dye intermediates which form a complete dye upon subsequent reaction.
  • cleavage reactions assisted by silver ion may be used in photographic processes to liberate a reagent in an imagewise fashion.
  • compounds capable of undergoing cleavage in the presence of ionic silver such as those mentioned above, may be used to release a reagent as a smaller molecule in an imagewise distribution corresponding to the imagewise distribution of silver ions made available as a function of development of an exposed silver halide layer.
  • the primary object of the present invention to provide processes employing photographically inert compounds which are stable in the photographic processing solution but capable of undergoing cleavage in the presence of the imagewise distribution of silver ions made available in the undeveloped and partially developed areas of a silver halide emulsion during processing of the emulsion to liberate a reagent as a smaller molecule, preferably, a photographically active reagent or a dye in an imagewise distribution corresponding to said imagewise distribution of silver ions.
  • the invention accordingly comprises 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 elements, which are exemplified in the following detailed disclosure, and the scope of the application of which will be indicated in the claims.
  • FIG. 1 is an enlarged, diagrammatic, fragmentary sectional view illustrating the preparation of a color image according to one aspect of this invention.
  • FIG. 2 is a similar view illustrating another aspect of the invention.
  • the present invention is concerned with utilizing the imagewise distribution of silver ions and/ or a soluble silver complex containing the same made available as a function of development to etfect cleavage of a photographically inert compound which may be diffusible or non-diifusible in the photographic processing composition to release a reagent as a smaller molecule in an imagewise distribution Corresponding to the imagewise distribution of said silver ions and/ or said soluble silver complex, which reagent also may be ditfusable or substantially non-diffusible in the processing composition.
  • a photographic process for producing an imagewise distribution of a reagent includes the steps of developing a photosensitive element comprising an exposed silver halide emulsion with an aqueous processing composition; forming in undeveloped areas an imagewise distribution of silver ions; contacting said imagewise distribution of silver ions with a photographically inert compound capable of undergoing cleavage in the presence of silver ions to liberate a reagent; and forming as a function of contacting said imagewise distribution of silver ions with said inert compound, a corresponding imagewise distribution of said reagent.
  • a relatively non-diifusible color-providing compound may be present, for example, in a layer associated with a light-sensitive silver halide emulsion which, after being exposed, is developed with an aqueous alkaline processing solution including a silver halide developing agent and a silver halide solvent.
  • the imagewise distribution of silver ions such as contained in the soluble silver complex made available during processing of the emulsion migrates to the associated color-providing material which undergoes cleavage in the presence of the complex to provide an imagewise distribution of a more dilfusible color-providing moiety.
  • the subsequent formation of a color image is the result of the differential in ditfusibility between the parent material and liberated color-providing moiety whereby the imagewise distribution of the more diifusible color-providing moiety released in undeveloped and partially developed areas is free to transfer.
  • the imagewise distribution of diifusible color-providing moiety is a complete dye, it may be simply washed away to leave an image associated with the emulsion, or it may be transferred by imbibition to an image-receiving layer, e.g., a dyeable stratum of the character heretofore known in the art to provide a color transfer image thereon.
  • the smaller molecule liberated from the parent compound upon cleavage may be any one of various reagents and preferably is photo graphically active, such as, a gelatin hardener, a development restrainer, toning agent or antifoggant.
  • the appropriate moiety may be substituted on the parent compound, or the parent compound itself upon cleavage may provide a fragment possessing the desired photographic activity.
  • the respective mobility characteristics of the parent compound and of the liberated reagent may be substantially the same, or they may be different as appropriate for a given photographic process.
  • a dilferential in dilfusibility between the parent compound and the reagent liberated therefrom may be achieved in various ways, for example, by using a normally immobile and non-diifusible parent compound which upon cleavage releases a diffusible reagent, or conversely, by using a normally mobile parent compound which upon cleavage releases a reagent that is substantially non-diffusible.
  • the parent compound should be photographically inert and stable in the processing solution, i.e., should remain intact in the processing composition in the absence of silver ion at least during the processing interval, but should be capable of undergoing cleavage in the presence of the imagewise distribution of silver ions and/ or the imagewise distribution of soluble silver complex containing silver ions made available as a function of development to release a reagent, such as, a dye or a photographically active reagent. Its rate of cleavage in the presence of silver ion, however, should be such that an imagewise distribution of reagent is obtained that corresponds to the imagewise distribution of silver ions or soluble silver complex formed in the partially exposed and unexposed areas of the emulsion. If the rate of cleavage is excessive, reagent may be released to some extent in the exposed areas.
  • a reagent such as, a color-providing moiety and the silver accelerated cleavage reactions which they undergo.
  • the above compounds may be appropriately substituted with the desired colorproviding or other moiety it is desired to liberate and with other group(s) as may be necessary to achieve a diiferential in diifusibility between the uncleaved parent compound and the reagent released therefrom.
  • the parent compound may be substituted with an immobilizing group or anchor, that renders the compound substantially nondiffusible in the processing solution, or, rather than a single immobilizing group, the parent compound may be substituted with two or more groups which together preclude migration of the compound from its position in the photographic element.
  • one or more of the groups maybe on the fragment to be released as a diffusible reagent so long as the group(s) does not reduce to any appreciable extent the mobility and diflusibility of the fragment subsequent to cleavage.
  • immobilizing group(s) for anchoring the parent compound will depend primarily on whether it is desired to employ only one immobilizing group or to employ two or more groups which together are capable of anchoring the compound. Where two or more groups are employed to immobilize the compound, lower alkyl groups, butyl or hexyl, for example, may be used to achieve the requisite differential in diifusibility between the parent compound and the reagent released. Where only one group is used to immobilize the compound, it is more effective to employ, for example, a higher alkyl radical such as octyl, decyl, dodecyl, stearyl, and oleyl or a carbocyclic or heterocyclic ring having six members or more.
  • a higher alkyl radical such as octyl, decyl, dodecyl, stearyl, and oleyl or a carbocyclic or heterocyclic ring having six members or more.
  • the carbocyclic or heterocyclic immobilizing group may be bonded to a single atom or to adjacent atoms of the parent molecule and may be bonded to a single atom by a valence or ionic bond or through a spiro union.
  • the color-providing moiety in forming color images according to the present invention there may be used a complete dye or a dye intermediate capable of yielding a complete dye upon subsequent reaction, for example, upon reaction with a suitable coupler to form a complete dye.
  • the coupling reaction may take place directly in the image-receiving layer, or it may take place in the emulsion layer or in the layer of processing composition after which the complete dye formed diffuses to the image-receiving layer.
  • Complete dyes which may be used as the color-providing moiety may comprise any of the general classes of dyes heretofore known in the art, for example, nitro, azo, thiazole, diand triphenyl methane, cyanine and anthraquinone dyes.
  • Dye intermediates include any molecule which when released is capable of forming a dye upon reaction with another molecule.
  • a dye intermediate may be released from a sulfur-nitrogen compound, e.g. a thiazolidine, which intermediate in turn reacts With another molecule to produce a complete dye.
  • Photographic processes and products utilizing dye-forming systems wherein an imagewise distribution of a complete dye is produced by the reaction of an aldehyde or ketone dye intermediate and a color-forming reagent comprises the subject matter of copending US. Pat. application Ser. No. 155,000 of Louis Locatell, Jr., Frank A. Meneghim' and Howard G. Rogers filed concurrently herewith.
  • the color-providing moiety may be linked directly to an atom of the parent molecule by a valence or ionic bond or through a spiro union, or it may be linked indirectly to the parent molecule through an appropriate linking group either acyclic or cyclic.
  • Typical linking groups include cycloalkyl, such as cyclohexyl; CONH; alkylene-CONH-; arylene-CONH-; alkylene; and arylene wherein alkylene may be ethylene, propylene, butylene and arylene may be phenylene.
  • color-providing moiety as used herein includes any linking group and the moiety may contain on the color-providing and/or linking portion various solubilizing substituents, e.g., sulfo, hydroxyl or carboxyl groups to adjust its solubility characteristics.
  • useful dyes include those which are colorless or of a color other than that ultimately desired in a certain environment, such as at a particular pH level, but upon a change in environment, e.g., from acid to alkaline conditions, take on a color change.
  • Color-providing materials of this nature include indicator dyes and leuco dyes.
  • dyes may be employed which undergo a color shift or change in spectral absorption characteristics during or after processing. Such dyes may be referred to as temporarily shifted dyes.
  • the temporary shift may, for example, be effected by acylation, the acyl group being removable by hydrolysis in the alkaline processing composition.
  • the compounds enumerated above may cleave in the absence of silver ion under extreme conditions, such as strong heating, they are sufiiciently stable under neutral, acid and alkaline conditions at ambient temperatures to remain intact under the processing conditions encountered in conventional and dilfusion transfer photography until silver ion becomes available as a function of development.
  • the reactivities of the various compounds toward silver ion may vary and thus, some compounds may cleave more rapidly in the presence of silver ion than others. Accordingly, it will be appreciated that the particular compound selected should have the cleavage rate necessary for obtaining an imagewise distribution of the desired reagent, such as a colorproviding moiety, under the particular processing conditions employed.
  • the parent compound cleave in the presence of silver ion and/or soluble silver complex containing silver ion to release a dilfusible color-providing moiety such that a transfer image is obtained within a reasonable processing time.
  • the 1,3- sulfur-nitrogen compounds have been found especially satisfactory. As discussed above, these compounds may be linear, or they may be cyclic in structure with either or both of the S and N atoms being constituents of the ring which should contain at least four atoms. The compounds may be saturated or unsaturated provided the S and N atoms each are bonded to the common, i.e., intermediate, carbon atom by a single bond.
  • 1,3-sulfur-nitrogen compounds that may be used in the present invention are those represented in the following formulae:
  • R and R each are a monovalent organic radical and R R and R each are hydrogen or a monovalent wherein R R and R have the same meaning as in Formula I above;
  • R and R, on the same or different atoms each are hydrogen or a monovalent organic radical and taken together represent a substituted or unsubstituted carbocyclic or heterocyclic ring;
  • Z represents the atoms, preferably carbon atoms, necessary to complete a ring system having up to 20 members;
  • R R R R R R and Z have the same meaning as in Formula II above;
  • R R R R and Z have the same meaning as in Formula II above.
  • Examples of cyclic compounds which may be used in tion may be obtained by selecting as the R or R group, a
  • the desired configuration may be obtained with compounds of Formula III by selecting as R a monovalent organic radical or by selecting as the R or R group, a monovalent organic radical -SR wherein R has the same meaning given above.
  • R a monovalent organic radical
  • R group a monovalent organic radical -SR wherein R has the same meaning given above.
  • the compound may contain more than one sulfur-nitrogen configuration if it is desired to release several smaller molecules.
  • the compound of Formula II may be substituted with a cyclic 1,3-sulfur-nitrogen substituent in the 2-position through a linking group, such as a methylene group, to give, e.g., a his compound.
  • At least one of the substituents of the compounds illustrated in the above formulae will be the color-providing. or other moiety it is desired to release as the reagent from the parent compound, which moiety may be released as an amine, aldehyde, ketone, etc., depending upon the position of the substituent on the parent.
  • one or more of the R substituents may be selected to immobilize the compound in' processes where it is desired to render the uncleaved parent compound substantially non-ditfusible in the processing solution, or one or more of the R substituents may be selected to enhance the solubility of the compound in processes where it is desired to render the parent compound diffusible in the processing solution.
  • Suitable immobilizing and solubilizing groups have been enumerated above.
  • the positioning of these groups on the parent compound will depend upon the diifusibility characteristics desired for the parent compound and for the smaller molecule released upon cleavage in a given process.
  • the parent and the reagent liberated therefrom may exhibit the same or different diflusibility characteristics in the photographic processing solution. Both may be nondiifusible, both may be diffusible or one may be diflusible and the other non-diffusible.
  • R groups may comprise other substituents which do not interfere with the use of the compound to liberate a selected reagent, such as, a color-providing moiety or a photographically active reagent.
  • substituents that may be used in the above formulae include carboxy, sulfo, nitro, hydroxy, halo, e.g., chloro and bromo, cyano and hydrocarbon radicals including aliphatic, cycloaliphatic, aromatic and heterocyclic radicals.
  • the radicals may possess ethylenic or acetylenic unsaturation, and the carbon chains may be interrupted by heteroatoms or heteroatom groups, such as S, O, N, SO, NH and so forth.
  • the radicals may contain substituents, e.g., phenyl, alkyl, alkyl ether,
  • radicals are substituted and unsubstituted alkyl groups, such as methyl, ethyl, octyl, dodecyl; substituted and unsubstituted cycloalkyl radicals, such as, cyclohexyl, cyclopentyl, cyclooctyl; substituted and unsubstituted alkenyl groups, such as, vinyl, allyl, butenyl, decenyl, octadienyl, hexatrienyl; substituted and unsubstituted cycloalkenyl groups, such as, cyclopentenyl, cycloheptenyl, cyclohexadienyl; substituted and unsubstituted alkynyl groups, such as, ethynyl, hexynyl, octynyl; substituted and unsubstituted aryl radicals, such as, phenyl radical
  • X is As in the compounds illustrated in Formulae I-IV, the above analogs may be substituted with an immobilizing group and/or a solubilizing group and with a moiety it is desired to release as the reagent, e.g., a color-providing moiety.
  • Compounds found especially suitable for forming images by difi'usion transfer are certain cyclic sulfurnitrogen compounds where both the S and N atoms are included in the ring, particularly thiazolidines and benzothiazolines. These compounds exhibit the desired stability in the processing composition, and in the presence of silver ions undergo cleavage at the desired rate to release a reagent, e.g., a color-providing moiety in an imagewise distribution corresponding to that of the silver ions and/ or soluble silver complex containing the same made available in the undeveloped areas of the emulsion. Besides exhibiting these characteristics under the highly alkaline conditions ordinarily employed in diffusion transfer processes, they may be employed under neutral and acid conditions as well.
  • 1,3-sulfur-nitrogen compounds both cyclic and linear, and their vinyl and phenylene analogs may be used to liberate an aldehyde in an imagewise fashion to produce relief or transfer images by utilizing the harden ing effect of aldehydes on gelatin and similar emulsion binders.
  • Illustrative of the aforementioned cyclic compounds particularly useful in forming dye images are those represented in the following Formulae V and VI, and preferably VI.
  • R R R and Z have the same meaning given above. It will be appreciated that the ring system represented by Z may be substituted if desired as in the illustrative compounds of Formulae I to IV.
  • the colorproviding moiety is preferably but not necessarily substituted on the carbon atom common to the sulfur and nitrogen atoms. If the color providing moiety selected as the organic radical R and/or R is a diifusible dye then R, and/or a group or groups substituted on the ring Z should be capable of rendering the parent compound substantially immobile in the photographic processing solution. Alternatively, if the color-providing moiety is a nondiffusible dye, the R and/or a group or groups substituted on Z should be capable of rendering the parent compound diffusible in the processing solution.
  • the parent compound may be present initially in the photosensitive element in a layer or layers other than the layer containing the light-sensitive silver halide emulsion.
  • it may be in a layer over the emulsion, in a layer between the support and the emulsion, or in two layers, one on either side of the emulsion.
  • It may be present in the photosensitive layer itself if the compound is inert, that is photographically innocuous in that it does not adversely affect or impair image formation to any appreciable or unacceptable extent. If not photographically innocuous, the compound may be modified in a manner which does not interfere with the development process in any way, but which deactivates the compound so that it does not affect adversely the light-sensitive emulsion.
  • the parent compound is contained in a layer separate from the silver halide emulsion. If desired, it may be separated from the emulsion layer by one or more spacer layers, or it may be contained in a layer associated with the image-receiving layer in processes such as diffusion transfer where receiving elements are employed.
  • the processing compositions customarily employed in silver dilfusion transfer processes comprise an aqueous alkaline solution of a silver halide solvent and a silver halide developing agent.
  • the named ingredients may be present initially in the aqueous medium or may be present initially elsewhere in the photographic product, for example, in the emulsion and/ or image-receiving and/or spacer layers as heretofore suggested in the art.
  • the processing composition is formed by contacting the product with a suitable aqueous medium to form a solution containing these ingredients.
  • a silver halide solvent is preferred in the processes of the present invention, it is not essential since cleavage may be assisted by the silver ion contained in the unexposed portions of the emulsion.
  • the alkali employed in the processing composition may be any of the alkaline materials heretofore used, such as sodium or potassium hydroxide.
  • the silver halide solvent also may be any of the heretofore known materials, such as sodium or potassium thiosulfate, sodium thiocyanate and uracil.
  • a silver halide solvent precursor may be used, such as described in copending U.S. patent application Ser. No. 99,310 filed Dec. 17, 1970.
  • the silver halide developing agent may be selected from those commonly employed, such as the diamino benzenes, e.g., paraphenylenediamine; aminophenols, e.g., methyl-paminophenol; and dihydroxybenzenes, e.g., hydroquinone.
  • the composition may contain antifoggants, preservatives, viscos ity-imparting reagents, and other adjuncts as conventionally used in the art. It will be understood that the selection of the above materials is not critical to the practice of this invention.
  • FIG. 1 illustrates the processing of a photosensitive element to prepare a color transfer image in accordance with one embodiment of the present invention.
  • an exposed photosensitive element including a support 10, a layer of colorproviding material 11 and a light-sensitive silver halide emulsion layer 12 is placed in superposition with a receiving element comprising an image-receiving layer, e.g., a dyeable stratum 13 and a support 14 therefor.
  • a processing composition 15 is distributed between the two elements as they are brough into superposition.
  • silver halide is reduced to image silver while an imagewise distribution of soluble silver complex is formed in terms of unexposed areas.
  • This imagewise distribution is, at least in part, transferred by imbibition to layer 11 where it accelerates cleavage of the color-providing material to release a ditfusible color-providing moiety, e.g. a dye, in areas corresponding to unexposed areas of emulsion layer 12.
  • a ditfusible color-providing moiety e.g. a dye
  • Processing composition 15 may be applied to the emulsion layer by coating, dipping, spraying or any or all of the ingredients thereof may be confined initially in a frangible container such as disclosed in U .8. Pat. No. 2,543,181, the container being positioned in the film unit so as to be capable upon rupturing of spreading its contents in a substantially uniform layer between the superposed layers. It will be appreciated that the respective elements may be placed in superposition following impregnation with the processing composition according to procedures known in the art.
  • Negative color images also may be obtained by employing a film unit where the layer of cleavable color-providing compound is associated with the receiving element, such as illustrated in FIG. 2.
  • a film unit where the layer of cleavable color-providing compound is associated with the receiving element, such as illustrated in FIG. 2.
  • an exposed silver halide emulsion 12 on a support is processed by spreading a processing composition between the emulsion layer and a layer of a colored color-providing material 11 on a support 14.
  • exposed areas of emulsion layer 12 silver halide is reduced to image silver, while an imagewise distribution of soluble silver complex is formed in terms of undeveloped areas of silver halide.
  • This imagewise distribution is transferred, at least in part, by imbibition, to layer 11 where it accelerates cleavage of the cleavable color-providing compound to provide a ditfusible color-providing moiety, e.g., dye, in areas corresponding to undeveloped areas of the emulsion-layer. Diffusion of the diifusible color-providing moiety from the image-receiving element into the processing composition leaves a negative color image in layer 11.
  • a ditfusible color-providing moiety e.g., dye
  • the film stuctures shown in the figures may be varied, for example, by employing one or more interlayers between those of the emulsion and cleavable parent compound as suggested above or by varying the order of the layers and is intended to be illustrative only of product structures useful in the preparation of color images according to the present invention.
  • EXAMPLE 1 A solution containing 0.4 g. cellulose acetate hydrogen phthalate; 10.0 cc. methanol; 10.0 cc. Z-methoxyethano and 0.4 g. of color-providing compound,
  • one portion of the photosensitive element prepared above was processed without exposure using the processing composition designated Solution A and the other portion processed without exposure using the processing composition designated Solution B.
  • a silver halide solvent e.g., sodium thiosulfate
  • Processing was carried out by spreading each solution in a layer 0.0016 inch thick between the photosensitive element and the receiving element containing a dyeable stratum that had been superposed therewith.
  • the imagereceiving elements used with the two portions of photosensitive material comprised a layer of a 2:1 mixture by weight, of polyvinyl alcohol and poly-4-vinyl pyridine over a layer of polyvinyl alcohol coated on a baryta paper support. After an imbibition period of about 30 seconds each of the image-receiving and photosensitive elements were separated and the transfer densities measured. The resulting transfer densities for the units processed with Solution A and Solution B were 1.56 and 0.26, respectively.
  • EXAMPLE 2 A further experiment was conducted to demonstrate the cleavage of the color-providing compound used in Example 1.
  • a photosensitive element was prepared in the same manner as in Example 1 above except that an interlayer comprising 100 mgs. per square foot of gelatin was provided between the gelatino silver iodobromide emulsion layer and the underlying layer of cellulose acetate hydrogen phthalate.
  • the outer silver halide emulsion layer was then removed from the element with an enzyme solution after which the element was divided into three portions. Each of the three portions was superposed with an image-receiving element and treated with Solutions C, D and E, respectively, by spreading solution, between the superposed materials in a layer 0.0016 inch thick.
  • the image-receiving element was prepared in the same manner as that in Example 1 above except that an additional layer of a half-butyl ester of poly-(ethylene/maleic anhydride) was provided between the layer of polyvinyl alcohol and the baryta support.
  • Hydrdxyethyl cellulose g. 3. 9 8. 9 Sod um hydroxide, g 5.0 5.0 5.0 Sodium thiosuliate, g. 4. 0 4.0 Silver chloride, g 0. 7
  • processing composition comprised the following:
  • EXAMPLE 3 A photosensitive element was prepared by coating a cellulose acetate support with 186 mgs. per squarefoot of the color-providing compound used in Example 1 above. On top of the layer of compound there was applied a layer containing 100 mgs. per square foot gelatin, and finally there was applied a blue-sensitive layer of silver iodobromide emulsion containing 33 mgs. per square foot of silver and 30 mgs. per square foot of gelatin. This element was exposed for one one-hundredth of a second to blue light through a density step tablet. Thereafter, the exposed element was superposed with an imagereceiving element and a 0.0016 inch layer of processing composition was spread therebetween. The image-receiving element was the same as that used in Example 2. The
  • dye images may be prepared in accordance with Example 6 above using different color-forming reagents, e.g., difierent methylene couplers and different dye intermediates, e.g., different aldehydes.
  • color-forming reagents e.g., difierent methylene couplers
  • dye intermediates e.g., different aldehydes.
  • dye images may be produced by the reaction of an aldehyde or a ketone with a color-forming reagent, e.g., a methylene coupler.
  • a color-forming reagent e.g., a methylene coupler.
  • Typical cyclic sulfur-nitrogen compounds are illustrated in the following formulae:
  • Z represents the atoms, preferably carbon atoms necessary to complete a ring-system containing at least 4 members and usually containing up to about 20 members and X has the same meaning given above and preferably is tive methyl group are quaternary ammonium compounds,
  • pyridinium quaternary ammonium compounds having a methyl substituent in the 2 and 4 positions of the heterocyclic ring.
  • 2 and 4 methyl-substituted pyridinium compounds are those wherein the nitrogen atom is substituted by groups, such as, alkyl, e.g., methyl, ethyl and propyl; aryl, e.g., phenyl; and aralkyl, e.g., phenethyl and benzyl.
  • alkyl e.g., methyl, ethyl and propyl
  • aryl e.g., phenyl
  • aralkyl e.g., phenethyl and benzyl.
  • anion is a derivative of any acid, e.g., a tosylate.
  • the couplers containing an active methylene group may be characterized as compounds containing a methylene '(CH group bonded directly to at least one activating group, such as, a keto, aldehyde, ester or nitrile group and usually a carbonyl or nitrile group.
  • the methylene group also may be bonded to two such activating groups, the same or different, and the methylene group may be part of an open chain structure or a member of a ring system.
  • any of the methylene couplers commonly used for this purpose may be employed in the present invention such as the acylacetic esters; acylacetoacetic esters; malonic acid esters; acetom'triles; acylacetonitriles, aroylacetonitriles; cyanacetic esters; cyanacetophenones; cyanacetyl coumarones; cyanacetyl hydrazones; acetoacetamides; cyanoacetarnides, 1,3-indandiones; thioindoxyls; oxindoles; indazoline-S-ones; isoxazole-S-ones; pyrimidazolones; and homophthalimides.
  • the coupler employed preferably is colorless, though it may be colored depending upon its location in the photographic element.
  • the layer of color-providing compound and coupler may be associated with the emulsion layer in the photosensitive element, e.g., to yield a dye capable of diffusing in the processing composition to form a transfer image.
  • the resulting image when stripped from the photosensitive element, may be viewed by transmitted light as a transparency.
  • the photosensitive element and/or processing composition contains a translucent layer of a material providing the requisite background, e.g., a white pigment such as titanium dioxide, the image may be viewed as a reflection print without separating the image-receiving and photosensitive elements.
  • Color transparencies and reflection prints of this type also may be produced in this manner where the diffusible color-providing moiety released in a complete dye.
  • silver halide emulsions such as silver chloride, silver bromide, silver bromoiodide, silver chlorobromide and silver chlorobromoiodide.
  • direct positive silver halide emulsions may be employgd.
  • a negative rather than a positive transfer image may be produced.
  • Typical materials that may be used as the support for the emulsion are paper, glass and plastic materials, e.g., cellulose nitrate, cellulose acetate, polyvinyl acetal, polystyrene, polyethyleneterephthalate, polyethylene and polypropylene.
  • the above-described colorproviding compounds may be employed in photographic systems utilizing integral multilayer photosensitive elements comprising at least two selectively sensitized silver halide emulsion strata with associated color-providing material which are processed simultaneously and without separation to provide a multicolor image on a single common image-receiving element.
  • a barrier interlayer ofsilver complex scavenger e.g., silver precipitant, to confine difiusioniof soluble silver complex to the appropriate thiazolidine stratum.
  • the system of the present invention may be used to form an imagewise distribution of another reagent, preferably a photographically active reagent, in the same manner as color images were formed in the foregoing examples.
  • the parent compound such as the compounds illustrated in Equations 1 to 8 above may be appropriately substituted to yield the desired photographic reagent upon cleavage in the presence of silver ing'the group I V particularly where X is
  • Such compounds as exemplified by thiazolidine, may be employed in aqueous media in the presence of silver ion, to liberate, for example:
  • This compound also may be used to produce a secondary amine or a tertiary amine, depending upon the N-substituent, and as illustrated above, may be used to produce an'aldehy'de, 'or'where' the hydrogen on the common carbon atom is replaced by phenyl or other substituent, to liberate a ketone.
  • Releasing in imagewise distribution of active reagent in this manner affords many advantages. For example, relief images may be prepared by liberating a gelatin hardener in the unexposed areas, and as noted previously, fogging may be controlled more effectively by releasing the antifoggant in an imagewise fashion during processing.
  • the photographic system of the present invention may be used to liberate reagents other than those specifically mentioned and that the present system for releasing a reagent in an imagewise fashion may be used with film structures other than those illustrated.
  • the negative component comprising at least one light-sensitive layer and the positive component comprising an imagereceiving layer may be separate elements as shown above which are brought together during processing and thereafter either retained together as the final print or separated following image formation.
  • the photosensitive layer and the imagereceiving layer may be in the same element.
  • the image-receiving layer is coated on a support and the photosensitive layer is coated on the upper surface of the image-receiving layer.
  • the liquid processing composition is applied between the combined negative-positive element and a spreading sheet which assists in spreading the liquid composition in a uniform layer adjacent the surface of the photosensitive layer.
  • the negative and positive components together may comprise a unitary structure, e.g., integral negative-positive film units wherein the negative and positive components are laminated and/ or otherwise physically retained together at least prior to image formation.
  • such film units comprise a plurality of essential layers including a negative component comprising at least one light-sensitive layer, e.g. a silver halide layer and a positive component comprising an image-receiving layer which components may be laminated together or otherwise secured together in physical juxtaposition as a single structure.
  • the dye image-providing compounds of the present invention may be associated with the silver halide layer or layers of the negative component.
  • Such film units include means for providing a reflecting layer between the image-receiving and negative components in order to mask effectively the silver image or images formed as a function of development of the silver halide layer or layers and any remaining associated dye image-providing material and also to provide a background for viewing the transfer image in the receiving component, without separation, by reflected light.
  • This reflecting layer may comprise a preformed layer of a reflecting agent included in the essential layers of the film unit or the reflecting agent may be provided subsequent to photoexposure, e.g. by including the reflecting agent in the processing composition.
  • These essential layers are preferably contained on a transparent support closest to the image-receiving layer and preferably include another support positioned on the opposed surface of the essential layers so that the layers are sandwiched or confined between the support members, at least one of which is transparent to permit viewing of the final image.
  • Such film units usually are employed in conjunction with means, such as, a rupturable container containing the requisite processing composition and adapted upon application of pressure of applying its contents to develop the exposed film unit.
  • those compounds comprising a complete dye and a cyclic moiety containing the group included in the ring wherein the cyclic moiety is capable of undergoing cleavage in the presence of silver ions are novel compounds.
  • the dye portion may comprise any one of the various classes of dyes, such as, azo, anthraquinone and the other dyes enumerated above.
  • the cyclic moiety may be derived from any cyclic 1,3-s11lfur-nitrogen compound containing at least four members in the ring system and containing the aforementioned group as part of the ring, the cyclic compound being capable of undergoing cleavage in the presence of ionic silver.
  • the dye may be linked directly to an atom of the cyclic 1,3-sulfur-nitrogen ring system by a valence or ionic bond or through a spiro union, or the dye may be linked indirectly to the ring system through an appropriate linking group either cyclic or acyclic.
  • the dye is substituted in the 2-position of the ring system, i.e., on the carbon atom common to the sulfur and nitrogen atoms.
  • the novel dyes may be diffusible or non-diffusible in aqueous processing solution and if nondiffusible, may contain a bulky group linked directly or indirectly to the molecule, usually on the cyclic portion.
  • the novel dyes may contain solubilizing groups to adjust the solubility characteristics, as may be desired.
  • novel dyes containing the specified cyclic moiety are the dye-substituted compounds of Formula VI above, as exemplified by dye-substituted thiazolidines and benzothiazolines.
  • Specific examples of novel dyes within the scope of the present invention are as fol- COOH
  • the novel dyes may be synthesized in a known manner by condensing an aldehyde, for example, a dye-substituted aldehyde, such as, DYE-CHO with a compound HSZNH wherein Z represents the atoms, preferably carbon atoms to complete a cyclic 1,3-sulfur-nitrogen moiety having up to about 20 members in the ring system.
  • the novel dyes may be prepared by condensing an aldehyde,
  • a dye-substituted ketone may be substituted for the aldehyde in the above condensation including cyclic ketones, such as, cyclohexanone where it is desired to prepare spiro derivatives.
  • step (b) 15.2 grams of N-decylamino ethanethiol and 15.8 grams of Z-hydroxy-p-phenylazo benzaldehyde prepared in step (a) was dissolved in 250 ml. of ethanol. The solution was stirred overnight. The title compound, which precipitated out, was recrystallized from ethanol, melting range 65 -66.5 C.
  • dyes either aldehyde or ketone dyes, for example, other azo dyes or anthraquinone dyes, azomethine dyes, etc., such as, those commonly employed in photographic processes for producing color images may be condensed with the amino-ethanethiol according to the above procedure.
  • amino-thiophenol or other appropriate aminomercapto compound may be used in the condensation reaction to obtain the desired cyclic 1,3-sulfur-nitrogen moiety.
  • a photographic process for producing an imagewise distribution of a reagent including the steps of developing a photosensitive element comprising an exposed silver halide emulsion with an aqueous processing composition; forming in undeveloped areas an imagewise distribution of silver ions and/ or soluble silver complex; contacting said imagewise distribution of silver ions and/or said complex with an initially photographically inert compound capable of undergoing cleavage in the presence of said silver ions and/or said complex to liberate a reagent; and forming as a function of contacting said imagewise distribution of silver ions and/or said complex with said compounds, a corresponding imagewise distribution of said reagent.
  • processing composition is an aqueous alkaline solution of a silver halide developing agent and a silver halide solvent.
  • one of said initially inert compound and said reagent is difiusible in said processing composition and the other is substantially non-diffusible in said processing composition.
  • a process according to claim 1 wherein said initially photographically inert compound is a compound containing a group selected from 8.
  • a process according to claim 9 wherein the reagent liberated is an aldehyde.
  • a photographic process for producing an imagewise distribution of a color-providing moiety including the steps of developing a photosensitive element comprising an exposed silver halide emulsion with an aqueous processing composition; forming in undeveloped areas an imagewise distribution of silver ions and/0r soluble silver complex; contacting said imagewise distribution of silver ions and/ or said complex with an initially photographically inert compound capable of undergoing cleavage in the presence of said silver ions and/or said complex to liberate a colorproviding moiety; and forming as a function of contacting said imagewise distribution of silver ions and/ or said complex with said compound, a corresponding imagewise distribution of said color-providing moiety.
  • a process according to claim 14 wherein one of said initially inert compound and said color-providing moiety is diffusible in said processing composition and the other is substantially non-diifusible in said processing composition.
  • a process according to claim 16 wherein said colorproviding moiety is a difiusible dye.
  • processing composition is an aqueous alkaline solution of a silver halide developing agent and a silver halide solvent.
  • said inert compound contains the group S X 1t 22.
  • X is 23.
  • said com- 25 pound is a cyclic compound having a ring system containing up to members and said -SXl I- group is included in the ring.
  • a photographic product comprising first and second sheetlike elements, said first element comprising a plurality of layers including a support; a photosensitive silver halide emulsion in a layer on said support; in a layer in one of said first and second sheet like elements, an initially photographically inert compound capable of undergoing cleavage in the presence of an imagewise distribution of silver ions and/ or soluble silver complex to liberate a reagent in an imagewise distribution corresponding to said distribution of silver ions and/or said complex; and means for applying a photographic processing composition comprising an aqueous alkaline solution of a silver halide developing agent and a silver halide solvent in a substantially uniform layer between said emulsion layer and said second sheet like element in superposed relationship therewith.
  • a product as defined in claim 26 wherein said initially inert compound is a compound containing a group selected from 31.
  • a product as defined in claim 33 wherein said cyclic compound is a benzothiazoline.
  • a photographic product comprising a photosensitive element comprising a plurality of layers including a support; a silver halide emulsion in a layer on said support; and in a layer on the same side of said support as said silver halide emulsion, an initially photographically inert compound capable of undergoing cleavage in the presence of an imagewise distribution of silver ions and/or solubie silver complex to liberate a color-providing moiety in an imagewise distribution corresponding to said distribution of silver ions and/ or said complex.
  • a product as defined in claim 38 wherein said initially inert compound is a compound containing a group selected from 40.
  • a product as defined in claim 39 wherein said initially compound contains the group -s X-1 I 41.
  • a product as defined in claim 41 wherein said compound is a cyclic compound having a ring system containing up to 20 members and said s X 1I group is included in the ring.
  • a photographc product as defined in claim 47 including a superposed image-receiving layer so positioned as to be capable of receiving by diffusion transfer an imagewise distribution of said difiusible dye and means for applying a photographic processing composition comprising an aqueous alkaline solution of a silver halide developing agent and a silver halide solvent in a substantially uniform layer between said silver halide and said imagewise receiving layer.

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US3862117A (en) * 1971-02-11 1975-01-21 Bayer Ag Cyanoaryl-thiodiazole-azo dyestuff
US4060417A (en) * 1974-04-30 1977-11-29 Polaroid Corporation Diffusion transfer elements comprising color-providing compounds capable of cleavage upon reaction with silver ions and silver ion barrier layers
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US4264507A (en) * 1979-04-24 1981-04-28 Polaroid Corporation Novel xanthene dye developers
US4264701A (en) * 1979-04-24 1981-04-28 Polaroid Corporation Magenta dye developers
US4332950A (en) * 1981-03-02 1982-06-01 Polaroid Corporation Thiazolidine-substituted phenyl sulfonic acids
US4336387A (en) * 1981-03-02 1982-06-22 Polaroid Corporation Thiazolidine-substituted phenyl sulfonyl chlorides
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US4355169A (en) * 1981-03-02 1982-10-19 Polaroid Corporation Thiazolidinyl-substituted phenyl sulfonamides
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US4634773A (en) * 1983-07-18 1987-01-06 Polaroid Corporation Thiazolidinylethylchlorocarbonates
US4740448A (en) * 1986-03-31 1988-04-26 Polaroid Corporation Hybrid color films with dye developer and thiazolidine dye releaser
US5021329A (en) * 1988-01-29 1991-06-04 Fuji Photo Film Co., Ltd. Silver halide photographic material containing a dye precursor residue
US5176972A (en) * 1991-09-11 1993-01-05 Polaroid Corporation Imaging medium with low refractive index layer
US5177262A (en) * 1991-07-19 1993-01-05 Polaroid Corporation Process and composition for use in photographic materials containing hydroquinones
US5187282A (en) * 1991-04-08 1993-02-16 Polaroid Corporation Sulfonated xanthene dyes, and photographic products and processes employing these dyes
US5204213A (en) * 1990-02-14 1993-04-20 Fuji Photo Film Co., Ltd. Silver halide photographic material
US5264322A (en) * 1991-04-08 1993-11-23 Polaroid Corporation Sulfonated xanthene dyes, and photographic products and processes employing these dyes
US5316887A (en) * 1992-07-31 1994-05-31 Polaroid Corporation Thermally developable photosensitive material
US5319143A (en) * 1992-07-31 1994-06-07 Polaroid Corporation Bis(aminoethanethiols)
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US5328799A (en) * 1992-07-31 1994-07-12 Polaroid Corporation Thermographic and photothermographic imaging materials
US5340689A (en) * 1992-07-31 1994-08-23 Polaroid Corporation Image-recording materials with cyclic 1,3-sulfur-nitrogen dye providing compounds
US5368979A (en) * 1994-01-27 1994-11-29 Polaroid Corporation Thermally developable photosensitive element
US5414091A (en) * 1992-07-31 1995-05-09 Polaroid Corporation Dye-providing compounds
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US5547810A (en) * 1994-09-16 1996-08-20 Konica Corporation Image forming method with alkali precursor
US5556740A (en) * 1994-11-24 1996-09-17 Konica Corporation Heat-developable photosensitive material
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US5658705A (en) * 1996-02-26 1997-08-19 Polaroid Corporation Image-recording materials with 1,3-sulfur-nitrogen dye releasers
US5691458A (en) * 1996-09-18 1997-11-25 Polaroid Corporation Benzoisothiazole azo dyes
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US3565625A (en) * 1967-05-17 1971-02-23 Du Pont Photographic elements having thiazolidine compounds in light-in-sensitive layers
US3751406A (en) * 1967-07-24 1973-08-07 Polaroid Corp Azo compounds useful in photographic processes

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US3862117A (en) * 1971-02-11 1975-01-21 Bayer Ag Cyanoaryl-thiodiazole-azo dyestuff
US4060417A (en) * 1974-04-30 1977-11-29 Polaroid Corporation Diffusion transfer elements comprising color-providing compounds capable of cleavage upon reaction with silver ions and silver ion barrier layers
WO1980002334A1 (en) * 1979-04-24 1980-10-30 Polaroid Corp Magenta dye developers
US4264507A (en) * 1979-04-24 1981-04-28 Polaroid Corporation Novel xanthene dye developers
US4264701A (en) * 1979-04-24 1981-04-28 Polaroid Corporation Magenta dye developers
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US4336387A (en) * 1981-03-02 1982-06-22 Polaroid Corporation Thiazolidine-substituted phenyl sulfonyl chlorides
WO1982003131A1 (en) * 1981-03-02 1982-09-16 Corp Polaroid Cleavable polymers and photographic products and processes employing same
US4355169A (en) * 1981-03-02 1982-10-19 Polaroid Corporation Thiazolidinyl-substituted phenyl sulfonamides
US4332950A (en) * 1981-03-02 1982-06-01 Polaroid Corporation Thiazolidine-substituted phenyl sulfonic acids
US4481277A (en) * 1983-02-02 1984-11-06 Polaroid Corporation Photographic products and processes with scavengers for silver ions or silver complexes
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US4503139A (en) * 1983-05-09 1985-03-05 Polaroid Corporation Photographic products and processes and novel compounds
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US5021329A (en) * 1988-01-29 1991-06-04 Fuji Photo Film Co., Ltd. Silver halide photographic material containing a dye precursor residue
US5204213A (en) * 1990-02-14 1993-04-20 Fuji Photo Film Co., Ltd. Silver halide photographic material
US5187282A (en) * 1991-04-08 1993-02-16 Polaroid Corporation Sulfonated xanthene dyes, and photographic products and processes employing these dyes
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US5338644A (en) * 1991-07-19 1994-08-16 Polaroid Corporation Process and composition for use in photographic materials containing hydroquihones
US5177262A (en) * 1991-07-19 1993-01-05 Polaroid Corporation Process and composition for use in photographic materials containing hydroquinones
US5176972A (en) * 1991-09-11 1993-01-05 Polaroid Corporation Imaging medium with low refractive index layer
US5414091A (en) * 1992-07-31 1995-05-09 Polaroid Corporation Dye-providing compounds
US5328799A (en) * 1992-07-31 1994-07-12 Polaroid Corporation Thermographic and photothermographic imaging materials
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US5430156A (en) * 1992-07-31 1995-07-04 Polaroid Corporation Color-providing compound having two or more cyclic 1,3 sulfur-nitrogen groups and two or more color-providing moieties
US5424427A (en) * 1992-12-22 1995-06-13 Polaroid Corporation Triazine including substituted color-providing moiety
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US5368979A (en) * 1994-01-27 1994-11-29 Polaroid Corporation Thermally developable photosensitive element
US5547810A (en) * 1994-09-16 1996-08-20 Konica Corporation Image forming method with alkali precursor
US5556740A (en) * 1994-11-24 1996-09-17 Konica Corporation Heat-developable photosensitive material
US5569574A (en) * 1995-11-13 1996-10-29 Polaroid Corporation Image-recording materials
US5674986A (en) * 1995-11-13 1997-10-07 Polaroid Corporation Photographically useful compounds including at least one 1,3-sulfur-oxygen ring system
US5658705A (en) * 1996-02-26 1997-08-19 Polaroid Corporation Image-recording materials with 1,3-sulfur-nitrogen dye releasers
US5717079A (en) * 1996-02-26 1998-02-10 Polaroid Corporation Color-providing compounds
US5691458A (en) * 1996-09-18 1997-11-25 Polaroid Corporation Benzoisothiazole azo dyes
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US5811530A (en) * 1996-09-18 1998-09-22 Polaroid Corporation Image-recording materials

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NL172374C (nl) 1983-08-16
NL172374B (nl) 1983-03-16
NL7208486A (xx) 1972-12-27
GB1400792A (en) 1975-07-23
FR2143075A1 (xx) 1973-02-02
AU4330472A (en) 1973-12-13
BE785120A (fr) 1972-12-20
DE2230014A1 (de) 1972-12-28
JPS557576B1 (xx) 1980-02-26
FR2143075B1 (xx) 1978-06-02
DE2230014C2 (de) 1983-08-25
CA997613A (en) 1976-09-28
AU454622B2 (en) 1974-10-14
IT958602B (it) 1973-10-30

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