US3620730A - Novel products and processes for forming images in silver and in dye - Google Patents

Novel products and processes for forming images in silver and in dye Download PDF

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US3620730A
US3620730A US861767A US3620730DA US3620730A US 3620730 A US3620730 A US 3620730A US 861767 A US861767 A US 861767A US 3620730D A US3620730D A US 3620730DA US 3620730 A US3620730 A US 3620730A
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image
silver halide
silver
layer
color
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Russell P Cook
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Polaroid Corp
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    • GPHYSICS
    • G03PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03CPHOTOSENSITIVE MATERIALS FOR PHOTOGRAPHIC PURPOSES; PHOTOGRAPHIC PROCESSES, e.g. CINE, X-RAY, COLOUR, STEREO-PHOTOGRAPHIC PROCESSES; AUXILIARY PROCESSES IN PHOTOGRAPHY
    • G03C8/00Diffusion transfer processes or agents therefor; Photosensitive materials for such processes
    • G03C8/02Photosensitive materials characterised by the image-forming section
    • G03C8/08Photosensitive materials characterised by the image-forming section the substances transferred by diffusion consisting of organic compounds
    • G03C8/10Photosensitive materials characterised by the image-forming section the substances transferred by diffusion consisting of organic compounds of dyes or their precursors
    • G03C8/12Photosensitive materials characterised by the image-forming section the substances transferred by diffusion consisting of organic compounds of dyes or their precursors characterised by the releasing mechanism

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  • This reaction may also be defined as a ring-closure of the oxidation product resulting in a separation or freeing" of the mobile color-providing moiety from the "anchoring moietyf' US. Pat. No. 3,443,939 issued to Stanley M. Bloom and Robert K. Stephens discloses systems employing the afore- 2 mentioned nondiffusible compounds of oxidized developing agent in obtain negative color transfer images. According to this copending patent application a photosensitive element.
  • the present invention utilizes the aforementioned dyes in a novel manner to obtain an image both in silver and in dye.
  • a dyeable stratum is associated with the silver halide layer and the diffusable dye moiety is transferred to this stratum from a different layer to form the desired image in dye and in silver.
  • the layer containing the nondiffusible compound containing this dye moiety may be on a separate element or simply on a layer separable from the dyeable stratum.
  • FIG. is a partially schematic, compound containing the difl'usible dye moiety is contained initially on sectional view illustrating one previously exposed photographic product contemplated by this invention during processing thereof.
  • the nondiffusible initially on a separate element and development and subsequent image formation is obtained by spreading a processing fluid between this element and a superposed photosensitive element including the exposed silver halide layer containing a developable image and an associated dyeable stratum.
  • this invention relates to novel photographic procedures and systems for preparing visible images and, more particularly, to such procedures and systems for preparing images in both dye and silver.
  • a primary object of this invention is to provide novel products and processes of the foregoing description.
  • Still another object is to provide novel systems wherein an exposed silver halide layer containing a developable image is developed to reduce exposed silver halide to image silver thereby forming a silver image while at substantially the same time transferring an imagewise distribution of dye in terms of the areas of developed sliver to an associated dyeable stratum to impart thereto a dye transfer image, the two images thus formed being viewable together as a single image in silver and in dye.
  • 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.
  • the present invention utilizes as the color image-forming component compounds containing a color-providing moiety and an anchoring or immobilizing moiety, which are described and claimed in the aforementioned copending application Ser. No. 655.338.
  • These compounds are immobile and nondiffusible in an aqueous alkaline medium, but are capable of providing, upon oxidation, an oridation product which may autoreact intramolecularly to form a heterocyclic ring and, as a function of this ring formation, to split ofl a mobile and diffusible colorproviding material.
  • This reaction may also be defined as a ring-closure of the oxidation product resulting in a separation or freeing" of the mobile color-providing moiety from the anchoring moiety.
  • D is a color-providing moiety, e.g., a complete dye such as a monoazo, disazo or anthraquinone dye which may, if desired, be metallized in known manner;
  • Y is any substituent which completes or forms an amide with. and reduces the basic character of the amino group in the 3-position, such as the residue of an acid, linking the colorproviding moiety Dto the S-nitrogen atom, and which is cnpable of being eliminated during the ring formation to be described with more particularity hereinafter, e.g.,
  • R and R each represent an anchoring or immobilizing substituent rendering the compound nondilfusible. e.g.. higher alkyl such as decyl. dodecyl. stearyl. oleyl. etc. linked directly to the aromatic nucleus or linked indirectly thereto through an appropriate linking group. e.g..
  • an aromatic ring e.g., of the benzene or naphthalene series, or a heterocyclic ring. which rings may be either bonded to a single carbon atom of the aromatic nucleus or fused thereto. i.e.. bonded to a pair of adjacent carbon atoms; or R and/or R may be a plurality of short chain radicals which together provide the anchoring moiety, each of said short chain radicals being linked directly or indirectly to a different carbon atom of the aromatic nucleus formed by the A and/or A moieties;
  • X is hydrogen. hydroxy. amino. e.g.. a primary secondary
  • X is hydrogen. hydroxy, an amino group such as may be contained by said X moiety. as previously described. or the anchoring substituent R, provided that one of said X and X moieties must be hydroxy or amino;
  • R' is hydrogen. an alkyl such as methyl, ethyl, propyl. butyl. hexyl. octyl. dodecyl. cyclohexyl. etc.; or a substituted alkyl such as Z-hydroxyethyl. B-dihydroxypropyl. carboxymethyl. carboxyethyl, carboxybutyl, earboxydecyl. hydroxyethylether. polyglycoloxyethyl. furanemeth'yl. benzyl. phenylethyl. carboxyphenylethyl. sulfo-phenylethyl. acylaminophenylethyl. etc.; and
  • n and n each is a positive integer from i to 2. provided that when R and R alone or together comprise one of those heretofore named substituents rendering the compound nondiffusible. either or both oh: and u may be i but when R and R alone or together do not provide such an anchoring moiety at least one ofn and It must be 2.
  • U5. Pat. No. 443.940 to Stanley M. Bloom and Howard G. Roger-s describes and claims novel photographic systems for preparing positive dye transfer image with the above-mentioned compounds.
  • a photosensitive element is provided containing at least one light-sensitive silver halide emulsion and an associated layer containing one of the aforementioned compounds and a silver-precipitating agent.
  • an aqueous alkaline processing composition including a rela tively immobile silver halide developing agent and a silver halide solvent.
  • exposed silver halide is reduced to silver while a soluble silver complex is formed I OH wherein the anchoring moiety R or R comprises a long chain amide.
  • nuclear substituted derivatives thereof e.g.. where any of the nuclear carbon atoms not specifically substituted may contain a carboxy. alkyl. alkoxy. amino. chloro. hydroxy or amide substituent.
  • the present invention utilizes the reaction mechanism described and claimed in the aforementioned US. Pat. No. 3.443.939 wherein a redox reaction with oxidized silver halide developing agent is employed to effect ring closure and subsequent release of the diffusible dye moiety.
  • a dyeable stratum is associated with the silver halide layer and the nonditfusible compound having the diffusible dye moiety is contained on a layer separate from and/or separable from this dyeable stratum.
  • a photographic product or assembly for use in the practice of this invention may comprise a photosensitive element having a support 10 carrying thereon a silver halide layer 12 and an associated dyeable stratum l4; and a second element including a support 16 carrying a layer comprising at least one of the previously mentioned compounds.
  • Support 10 may be transparent or opaque. depending upon whether transparencies or reflection prints are contemplated. and may comprise any of the support materials heretofore employed for such purposes. By way of illustration. it may be made of cellulose nitrate. cellulose acetate. polyvinyl acetal. polystyrene. polyethylene terephthalate. polyethylene. polypropylene. polycarbonate. etc.. paper. glass or other materials.
  • Layer l2 likewise comprises any of the known silver halide layers and may. for example. be a conventional gelatino silver halide emulsion. e.g.. silver chloride. silver bromide. silver bromoiodide. silver chlorobromide or silver chlorobromoiodide.
  • Layer 12 may also contain the various additives heretofore employed in such layers. e.g.. sensitizers. antifoggans. hardeners. plasticizers. coating aids. speed-increasing materials. ultraviolet light absorbers. etc.. and may also include the silver halide developing agent employed to form the image.
  • Dyeable stratum 14 also comprises any of the known layers for obtaining color images and may comprise a polymeric material such as polyvinyl alcohol or a mixture of polyvinyl alcohol and a polyvinyl pyridine. e.g.. a poly-4-vinylpyridine. etc. it may also contain a dye mordant and/or other ingredients performing specific desired characteristics. For reasons which will be more apparent hereinafter. layer 14 should be alkali-permeable.
  • Support 16 may be transparent or opaque and may be the same as support 10 or different.
  • Layer 18 comprises one of the aforementioned compounds. i.e.. a compound of formula A or B contained in a suitable matrix or vehicle. e.g.. gelatin.
  • silver halide layer 12 is selectively exposed and the thus exposed element is then developed by spreading an aqueous alkaline processing composition 20 between the respective elements. as shown in the drawing.
  • This composition includes at least an alkaline material such as sodium or potassium hydroxide. and a silver halide developing agent of the type described in U.S. Pat. No. 3.443.939. which upon development. will provide an oxidation product which can undergo a redox reaction with the compound in layer 18.
  • Such developing agents include dihydroxybenezene developers such as the hydroquinones. aminophenol developers such as metol and diaminobenzene developers such as Z-amino-S-diethyl-aminotoluene.
  • any of these ingredients may be present initially in the photographic assembly. in which event the developing composition is obtained by applying the aqueous medium to dissolve the component or components so contained.
  • the processing composition may also contain the other reagents heretofore employed in such compositions such as a viscous reagent, stabilizers. and the like.
  • a silver halide solvent fixer such as sodium or potassium thiosulfate to remove uiiexposed silver halide.
  • a silver halide solvent fixer such as sodium or potassium thiosulfate to remove uiiexposed silver halide.
  • the processing composition permeates through layer 14 to develop the latent image in layer 12. i.e.. to reduce exposed and developable silver halide grains to image silver.
  • the silver halide developing agent is selectively oxidized. thereby forming an imagewise distribution of oxidized developer in terms of exposed and developed areas of layer 12.
  • This oxidized developer is sufficiently mobile and diffusible in the processing fluid to migrate to superposed layer 18 where the aforementioned redox reaction occurs to release an imagewise distribution of mobile and diffusible dye which in turn is transferred. by diffusion. to the dyeable stratum to impart thereto a negative dye transfer image. i.e..
  • support 16 carrying the remainder of the dye, the anchor for the released dye. etc.. may be discarded. It is also contemplated, however. that if desired. substantially all of the dye may be so removed imagewise from layer 18 by the redox reaction with oxidized developer, thereby leaving a usable reverse image. i.e.. a positive image on support 16. In such a procedure. two images are so provided. If not all of the dye is removed imagewise from layer 18 so as to provide a second image. appropriate further steps. e.g.. dye bleach techniques. may be employed to improve the dye image carried on support 16.
  • dyecontaining layer 18 has been shown as being separate from the dyeable stratum 14. i.e.. contained on a separate support. In lieu thereof, it may be applied as a layer on support 10. thereby eliminating support 16.
  • a stripping layer of the character heretofore known. e.g.. cellulose acetate hydrogen phthalate. may be disposed between layers l4 and 18 to facilitate separation.
  • the processing composition is spread between the outer layer (layer 18) and a superposed spreader sheet which may be a suitable sheet material such as support 16.
  • layer 18 is separated from layer 14 to reveal the desired image.
  • a stripping layer is employed. this layer along with layer 18 and the spent processing fluid all adhere to the spreader sheet which may then be discarded. It will be appreciated that, where found desirable or expedient to do so.
  • a stripping layer may be disposed over layer l4 in the structure shown in the drawing.
  • dyes of various colors may be employed.
  • the preferred embodiment contemplates use of dyes of a neutral color. i.e.. in the blue-black family.
  • the present invention makes it possible to obtain images of greater density and contrast than can be obtained with dye alone or silver alone.
  • the silver image formed in layer 12 heightens and intensifies the dye image in layer 14. making it possible to obtain appreciably denser images than with either dye or silver alone.
  • a layer thereon containing about I77 mgJft. of dye On a second cellulose triacetate support was provided a layer of a high-speed silver iodobromide emulsion over which was coated a dyeable stratum comprising a mixture of polyvinyl alcohol and poly-4 vinyl-pyridine.
  • the second element containing the silver halide emulsion was photoexposed and then developed by spreading between this element and the dye-containing layer of the other element at a gap of about 0.0030 inch a processing fluid containing the following proportions of ingredients:
  • EXAMPLE 2 The procedure of example 1 was repeated. except that the order of the dyeable stratum and the silver halide emulsion layers on the triacetate support were reversed. A comparable image was obtained.
  • EXAMPLE 4 The procedure of example l was repeated. except that approximately 5.0 g. of sodium thiosulfate was included in the processing fluid.
  • the present invention provides novel systems for preparing visible images in both dye and silver, which images may be viewed either as a transparency or as a reflection print..depending upon the support material employed.
  • a photographic product comprising a first support carrying on one side thereof a light sensitive silver halide layer and a dyeable stratum and a second support adapted to be placed in superposition with said first support and carrying a layer of a nondiffusible material containing a diffusible color providing moiety.
  • which material is capable of forming by a redox reaction an oxidation product which can autoreact intra molecularly to effect ring closure and to eliminate the color providing moiety of said material for transfer to said dyeable stratum.
  • R m-n 3 A product as defined in claim 1 wherein said dy'eable 2s Whmim stratum is disposed between said support and said silver halide layer.
  • a photographic product comprising. in combination. a first element comprising a support carrying on one side thereof a light-sensitive silver halide emulsion layer and a dyeable stratum. and a second element adapted for placement in superposition therewith having a layer containing a compound of the formula:
  • each of A and A represents the atoms necessary to complete an aromatic ring
  • D is a color-providing moiety.
  • Y is a substituent which completes an amide with and reduces the basic character of the J-amino substituent bonded thereto. said Y substituent further being a divalent radical linking said D moiety to said 3-nitrogen atom;
  • X and X each is hydrogen. hydroxy. amino or the substituent R. provided that at least one of X and X must be hydroxy or amino.
  • R and R each represents an anchoring moiety rendering said compound nondifi'usible
  • R is hydrogen. alkyl or substituted alkyl
  • n and a each is l or 2, provided than when R is an alkyl radical or X or X is a secondary or tertiary amino comprising an anchoring moiety rendering said compound nondiffusible or when R.
  • X and X together contribute an anchoring moiety.
  • n and u may be i. but when said substituents alone or together do not contribute an anchoring moiety at least one or n and n must be 2.
  • each of R and R comprises an amide of at least 13 carbon atoms. said amide being bonded directly to a nuclear carbon atom of the shown benzene moiety or linked thereto through a phenylene or alkylene substituent;
  • each of n and n is l or 2. provided that at least one of said I:
  • n 2;
  • D is a monoazo. disazo or anthraquinone dye moiety.
  • a photographic process for preparing visible images com prising the steps of developing an exposed photosensitive layer including a light-sensitive silver halide layer to form a silver image in said layer; as a function of said development selectively releasing a difi'usible color-providing material for transfer in an imagewise pattern corresponding to said silver image; and transferring said imagewise pattern of colorproviding material. at least in part. by diffusion. to a stratum adjacent to said silver imagecontaining layer to impart to said stratum a color transfer image. thereby providing a photographic image which is a composite of said silver image and said color image.
  • a photographic process for preparing visible images comprising the steps of exposing a photosensitive element including a light-sensitive silver halide layer and a dyeable stratum to form a developable image; developing said image in the presence of a layer containing a nondiffusible material containing a diffusible color-providing moiety, which material is capable of forming by a redox reaction an oxidization product which can autoreact intramolecularly to effect ringclosure and to eliminate the diffusible color-providing moiety of said material for transfer.
  • said development being effected by contacting said exposed silver halide developing agent which when oxidized is capable of undergoing said redox reaction with said material.
  • a process as defined in claim 11 including the step of removing unexposed and undeveloped silver halide from said silver halide layer at some time during or subsequent to said development.

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Abstract

Novel procedures for forming an image both in dye and in silver wherein an exposed silver halide layer containing a developable image is developed and as a function of development an imagewise distribution of dye is transferred to a dyeable stratum contiguous with said silver halide layer, whereby to form an image both in developed silver and in transferred dye.

Description

vuauwu ueutva I. abclll, I [H] [72] inventor Russell P. Cook 2,686,716 8/1954 Land 96/29 y. Mm 2,834,676 /1958 Stanley etal. 96/66 [21] Appi. No. 861,767 2,944,894 7/!960 Land 96/3 [22] Filed Sept. 29, 1969 3.203.796 8/1965 Lodewijk... 96/76 [45] Patented Nov. 16, 1971 3,345,166 /1967 Land et 96/29 [73] Assignee Polaroid Corporation 3,443,939 5/1969 Bloom etal... 96/3 ia 3,443,940 5/1969 Bloom et al 96/66 Primary Examiner-John T. Goolkasian [s41 NOVEL PRODUCTS AND PROCESSES FOR 413m" FORMING IMAGES [N SILVER AND m DYE Attorneys-Brown and Mikulka and Alvin lsaacs 16 Claims, 1 Drawing Fig.
[ m 96/3, 96/29 D, 96/77 [51] FL G03: 5/54 ABSTRACT: Novel procedures for forming an image both in M dye and in silver wherein an exposed silver halide layer con- A 77 mining a developable image is developed and as a function of development an imagewise distribution of dye is transferred to [56] Rd I I CM a dyeable stratum contiguous with said silver halide layer,
UNITED STATES PATENTS whereby to form an image both in developed silver and in 2,544,268 3/ Land 96/29 transferred dye.
NOVEL PRODUCTS AND PROCESSES FOR FORMING IMAGES IN SILVER AND IN DYE BACKGROUND OF THE INVENTION The copending application of Stanley M. Bloom, Ser. No. 655,338 filed July 24, I967, describes and claims novel compounds containing a color-providing moiety and an "anchoring" or immobilizing moiety. These compounds are immobile and nondiffusible in an aqueous alkaline medium, but are capable of providing, upon oxidation, an oxidation product which may autoreact intrarnolecularly to form a heterocyclic ring and, as a function of this ring formation, to split off a mobile and diffusible color-providing material. This reaction may also be defined as a ring-closure of the oxidation product resulting in a separation or freeing" of the mobile color-providing moiety from the "anchoring moietyf' US. Pat. No. 3,443,939 issued to Stanley M. Bloom and Robert K. Stephens discloses systems employing the afore- 2 mentioned nondiffusible compounds of oxidized developing agent in obtain negative color transfer images. According to this copending patent application a photosensitive element. containing at least one light-sensitive silver halide ClIlI-IISIOII and associated compound of the foregoing description is exposed and then developed with an aqueous alkaline processing composition including a silver halide developing agent which upon development provides an oxidation product capable of being reduced by a redox reaction with the aforementioned compound, the developer further being sufficiently mobile in its oxidized state so as to be capable of migrating to the layer containing the colorproviding compound; oxidizing the developing agent as a function of development to provide an imagewise distribution of oxidized developing agent in terms of exposed and developed areas of the emulsion; transferring this imagewise distribution at least in part, to contact the color-providing compound, whereby a redox reaction takes place to reduce the developing agent and to oxidize the colorproviding compound to form an oxidation product which then ring closes to split off the mobile color-providing moiety in turn to form an imagewise distribution of mobile and diffusible color-providing compound in terms of exposed areas of the emulsion; and transferring this latter imagewise distribution, at least in part, by inhibition to a superposed dyeable stratum to impart thereto a negative color transfer image.
SUMMARY OF THE INVENTION The present invention utilizes the aforementioned dyes in a novel manner to obtain an image both in silver and in dye.
According to the present invention a dyeable stratum is associated with the silver halide layer and the diffusable dye moiety is transferred to this stratum from a different layer to form the desired image in dye and in silver. The layer containing the nondiffusible compound containing this dye moiety may be on a separate element or simply on a layer separable from the dyeable stratum.
BRIEF DESCRIPTION OF DRAWING The FIG. is a partially schematic, compound containing the difl'usible dye moiety is contained initially on sectional view illustrating one previously exposed photographic product contemplated by this invention during processing thereof.
DESCRIPTION OF PREFERRED EMBODIMENT In the preferred embodiment, the nondiffusible initially on a separate element and development and subsequent image formation is obtained by spreading a processing fluid between this element and a superposed photosensitive element including the exposed silver halide layer containing a developable image and an associated dyeable stratum.
As was mentioned previously, this invention relates to novel photographic procedures and systems for preparing visible images and, more particularly, to such procedures and systems for preparing images in both dye and silver.
A primary object of this invention, therefore. is to provide novel products and processes of the foregoing description.
Another objectis to prepare visible images having image areas both in silver and dye.
Still another object is to provide novel systems wherein an exposed silver halide layer containing a developable image is developed to reduce exposed silver halide to image silver thereby forming a silver image while at substantially the same time transferring an imagewise distribution of dye in terms of the areas of developed sliver to an associated dyeable stratum to impart thereto a dye transfer image, the two images thus formed being viewable together as a single image in silver and in dye.
Other objects of the invention will in part be obvious and will in part appear hereinafter.
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.
For a fuller understanding of the nature and objects of the invention, reference should be had to the following detailed description taken in connection with the accompanying drawing.
As was mentioned previously, the present invention utilizes as the color image-forming component compounds containing a color-providing moiety and an anchoring or immobilizing moiety, which are described and claimed in the aforementioned copending application Ser. No. 655.338. These compounds are immobile and nondiffusible in an aqueous alkaline medium, but are capable of providing, upon oxidation, an oridation product which may autoreact intramolecularly to form a heterocyclic ring and, as a function of this ring formation, to split ofl a mobile and diffusible colorproviding material. This reaction may also be defined as a ring-closure of the oxidation product resulting in a separation or freeing" of the mobile color-providing moiety from the anchoring moiety.
These compounds may be represented by the formula:
stituted;
D is a color-providing moiety, e.g., a complete dye such as a monoazo, disazo or anthraquinone dye which may, if desired, be metallized in known manner;
Y is any substituent which completes or forms an amide with. and reduces the basic character of the amino group in the 3-position, such as the residue of an acid, linking the colorproviding moiety Dto the S-nitrogen atom, and which is cnpable of being eliminated during the ring formation to be described with more particularity hereinafter, e.g.,
R and R each represent an anchoring or immobilizing substituent rendering the compound nondilfusible. e.g.. higher alkyl such as decyl. dodecyl. stearyl. oleyl. etc. linked directly to the aromatic nucleus or linked indirectly thereto through an appropriate linking group. e.g..
an aromatic ring. e.g., of the benzene or naphthalene series, or a heterocyclic ring. which rings may be either bonded to a single carbon atom of the aromatic nucleus or fused thereto. i.e.. bonded to a pair of adjacent carbon atoms; or R and/or R may be a plurality of short chain radicals which together provide the anchoring moiety, each of said short chain radicals being linked directly or indirectly to a different carbon atom of the aromatic nucleus formed by the A and/or A moieties;
X is hydrogen. hydroxy. amino. e.g.. a primary secondary;
or tertiary amino substituent of the formula:
X is hydrogen. hydroxy, an amino group such as may be contained by said X moiety. as previously described. or the anchoring substituent R, provided that one of said X and X moieties must be hydroxy or amino;
R' is hydrogen. an alkyl such as methyl, ethyl, propyl. butyl. hexyl. octyl. dodecyl. cyclohexyl. etc.; or a substituted alkyl such as Z-hydroxyethyl. B-dihydroxypropyl. carboxymethyl. carboxyethyl, carboxybutyl, earboxydecyl. hydroxyethylether. polyglycoloxyethyl. furanemeth'yl. benzyl. phenylethyl. carboxyphenylethyl. sulfo-phenylethyl. acylaminophenylethyl. etc.; and
n and n each is a positive integer from i to 2. provided that when R and R alone or together comprise one of those heretofore named substituents rendering the compound nondiffusible. either or both oh: and u may be i but when R and R alone or together do not provide such an anchoring moiety at least one ofn and It must be 2.
U5. Pat. No. 443.940 to Stanley M. Bloom and Howard G. Roger-s describes and claims novel photographic systems for preparing positive dye transfer image with the above-mentioned compounds. According to the procedures described and claimed in this patent a photosensitive element is provided containing at least one light-sensitive silver halide emulsion and an associated layer containing one of the aforementioned compounds and a silver-precipitating agent. When such a photosensitive element is exposed and then developed with an aqueous alkaline processing composition including a rela tively immobile silver halide developing agent and a silver halide solvent. in known manner exposed silver halide is reduced to silver while a soluble silver complex is formed I OH wherein the anchoring moiety R or R comprises a long chain amide. e.g.. of at least l3 carbon atoms; and nuclear substituted derivatives thereof. e. g.. where any of the nuclear carbon atoms not specifically substituted may contain a carboxy. alkyl. alkoxy. amino. chloro. hydroxy or amide substituent.
Suitable illustrative compounds within the scope of the aforementioned formulas are disclosed. for example, in the aforementioned copending application, Ser. No. 655.338. as well as U.S. Pat. Nos. 3.443.939 and 3.443.940.
The present invention utilizes the reaction mechanism described and claimed in the aforementioned US. Pat. No. 3.443.939 wherein a redox reaction with oxidized silver halide developing agent is employed to effect ring closure and subsequent release of the diffusible dye moiety.
According to the present invention. a dyeable stratum is associated with the silver halide layer and the nonditfusible compound having the diffusible dye moiety is contained on a layer separate from and/or separable from this dyeable stratum.
The invention will be more readily understood by reference to the accompanying drawing.
As shown in the drawing. a photographic product or assembly for use in the practice of this invention may comprise a photosensitive element having a support 10 carrying thereon a silver halide layer 12 and an associated dyeable stratum l4; and a second element including a support 16 carrying a layer comprising at least one of the previously mentioned compounds.
Support 10 may be transparent or opaque. depending upon whether transparencies or reflection prints are contemplated. and may comprise any of the support materials heretofore employed for such purposes. By way of illustration. it may be made of cellulose nitrate. cellulose acetate. polyvinyl acetal. polystyrene. polyethylene terephthalate. polyethylene. polypropylene. polycarbonate. etc.. paper. glass or other materials.
Layer l2 likewise comprises any of the known silver halide layers and may. for example. be a conventional gelatino silver halide emulsion. e.g.. silver chloride. silver bromide. silver bromoiodide. silver chlorobromide or silver chlorobromoiodide. Layer 12 may also contain the various additives heretofore employed in such layers. e.g.. sensitizers. antifoggans. hardeners. plasticizers. coating aids. speed-increasing materials. ultraviolet light absorbers. etc.. and may also include the silver halide developing agent employed to form the image.
Dyeable stratum 14 also comprises any of the known layers for obtaining color images and may comprise a polymeric material such as polyvinyl alcohol or a mixture of polyvinyl alcohol and a polyvinyl pyridine. e.g.. a poly-4-vinylpyridine. etc. it may also contain a dye mordant and/or other ingredients performing specific desired characteristics. For reasons which will be more apparent hereinafter. layer 14 should be alkali-permeable.
Support 16 may be transparent or opaque and may be the same as support 10 or different.
Layer 18 comprises one of the aforementioned compounds. i.e.. a compound of formula A or B contained in a suitable matrix or vehicle. e.g.. gelatin.
To prepare an image in accordance with this invention. silver halide layer 12 is selectively exposed and the thus exposed element is then developed by spreading an aqueous alkaline processing composition 20 between the respective elements. as shown in the drawing. This composition includes at least an alkaline material such as sodium or potassium hydroxide. and a silver halide developing agent of the type described in U.S. Pat. No. 3.443.939. which upon development. will provide an oxidation product which can undergo a redox reaction with the compound in layer 18. Such developing agents include dihydroxybenezene developers such as the hydroquinones. aminophenol developers such as metol and diaminobenzene developers such as Z-amino-S-diethyl-aminotoluene. Any of these ingredients may be present initially in the photographic assembly. in which event the developing composition is obtained by applying the aqueous medium to dissolve the component or components so contained. The processing composition may also contain the other reagents heretofore employed in such compositions such as a viscous reagent, stabilizers. and the like.
if desired. it may also contain a silver halide solvent fixer such as sodium or potassium thiosulfate to remove uiiexposed silver halide. In lieu thereof, if found desirable or expedient to remove unexposed silver halide and thereby fix the silver image formed in layer 12. such a reagent may be'applied in a separate step after image formation.
In any event; upon contacting the exposed element'in the foregoing manner, the processing composition permeates through layer 14 to develop the latent image in layer 12. i.e.. to reduce exposed and developable silver halide grains to image silver. As a function of such development. the silver halide developing agent is selectively oxidized. thereby forming an imagewise distribution of oxidized developer in terms of exposed and developed areas of layer 12. This oxidized developer is sufficiently mobile and diffusible in the processing fluid to migrate to superposed layer 18 where the aforementioned redox reaction occurs to release an imagewise distribution of mobile and diffusible dye which in turn is transferred. by diffusion. to the dyeable stratum to impart thereto a negative dye transfer image. i.e.. a dye image corresponding areawise to the underlying silver image. After a suitable inhibition period, the two elements are separated to reveal on support a negative image in both dyeand silver. which image is viewable either as a transparency or as a reflection print, de' pending upon the nature of support 10. While reference has been made to transparent or opaque supports. it will be appreciated that if the support is translucent. the image may be viewed either as a reflection print or by transmitted light.
If only a single image is contemplated, support 16 carrying the remainder of the dye, the anchor for the released dye. etc.. may be discarded. It is also contemplated, however. that if desired. substantially all of the dye may be so removed imagewise from layer 18 by the redox reaction with oxidized developer, thereby leaving a usable reverse image. i.e.. a positive image on support 16. In such a procedure. two images are so provided. If not all of the dye is removed imagewise from layer 18 so as to provide a second image. appropriate further steps. e.g.. dye bleach techniques. may be employed to improve the dye image carried on support 16.
In the illustrative drawing, dyecontaining layer 18 has been shown as being separate from the dyeable stratum 14. i.e.. contained on a separate support. In lieu thereof, it may be applied as a layer on support 10. thereby eliminating support 16. In such a procedure, a stripping layer of the character heretofore known. e.g.. cellulose acetate hydrogen phthalate. may be disposed between layers l4 and 18 to facilitate separation. In such a photographic product, the processing composition is spread between the outer layer (layer 18) and a superposed spreader sheet which may be a suitable sheet material such as support 16. Following processing. layer 18 is separated from layer 14 to reveal the desired image. Where a stripping layer is employed. this layer along with layer 18 and the spent processing fluid all adhere to the spreader sheet which may then be discarded. It will be appreciated that, where found desirable or expedient to do so. a stripping layer may be disposed over layer l4 in the structure shown in the drawing.
While dyes of various colors may be employed. the preferred embodiment contemplates use of dyes of a neutral color. i.e.. in the blue-black family.
Since the image formed in the photosensitive element is both in silver and in dye. the present invention makes it possible to obtain images of greater density and contrast than can be obtained with dye alone or silver alone. In other words. the silver image formed in layer 12 heightens and intensifies the dye image in layer 14. making it possible to obtain appreciably denser images than with either dye or silver alone.
The foregoing examples shown by way of illustration and not by way of limitation the practice of this invention.
EXAMPLE 1 On a cellulose triacetate support sheet was coated a gelatin: dye solution having a l:l ratio of gelatin to a dye of the formu' la:
CH: r
to provide a layer thereon containing about I77 mgJft. of dye. On a second cellulose triacetate support was provided a layer of a high-speed silver iodobromide emulsion over which was coated a dyeable stratum comprising a mixture of polyvinyl alcohol and poly-4 vinyl-pyridine. The second element containing the silver halide emulsion was photoexposed and then developed by spreading between this element and the dye-containing layer of the other element at a gap of about 0.0030 inch a processing fluid containing the following proportions of ingredients:
Water I000 ec.
Hydrolyethyl cellulose 3.9 g. Sodium Hydroxide 5.0 g. Sodium Bromide 5.0 g. Zine Nitrate 0.5 g. Metal L6 g.
After about a 3-minute development time. the respective elements were separated to reveal a transparent image in dye and in silver in the photosensitive element.
EXAMPLE 2 The procedure of example 1 was repeated. except that the order of the dyeable stratum and the silver halide emulsion layers on the triacetate support were reversed. A comparable image was obtained.
EXAMPLE 3 The procedure of example l was repeated. except that after image formation. the resulting image was fixed with a standard sodium thiosulfate fixing solution. 1
EXAMPLE 4 The procedure of example l was repeated. except that approximately 5.0 g. of sodium thiosulfate was included in the processing fluid.
From the foregoing description and illustrative examples it will be seen that the present invention provides novel systems for preparing visible images in both dye and silver, which images may be viewed either as a transparency or as a reflection print..depending upon the support material employed.
Since certain changes may be made in the above product and process without departing from the scope of the invention herein involved. it is intended that all matter contained in the above description or shown in the accompanying drawing shall be interpreted as illustrative and not in a limiting sense.
What is claimed is:
l. A photographic product comprising a first support carrying on one side thereof a light sensitive silver halide layer and a dyeable stratum and a second support adapted to be placed in superposition with said first support and carrying a layer of a nondiffusible material containing a diffusible color providing moiety. which material is capable of forming by a redox reaction an oxidation product which can autoreact intra molecularly to effect ring closure and to eliminate the color providing moiety of said material for transfer to said dyeable stratum.
2. A product as defined in claim 1 wherein said silver halide layer is disposed between said support and said dyeable stratum.
R m-n 3. A product as defined in claim 1 wherein said dy'eable 2s Whmim stratum is disposed between said support and said silver halide layer.
4. A photographic product comprising. in combination. a first element comprising a support carrying on one side thereof a light-sensitive silver halide emulsion layer and a dyeable stratum. and a second element adapted for placement in superposition therewith having a layer containing a compound of the formula:
R nd-niwherein:
each of A and A represents the atoms necessary to complete an aromatic ring;
D is a color-providing moiety.
Y is a substituent which completes an amide with and reduces the basic character of the J-amino substituent bonded thereto. said Y substituent further being a divalent radical linking said D moiety to said 3-nitrogen atom;
X and X each is hydrogen. hydroxy. amino or the substituent R. provided that at least one of X and X must be hydroxy or amino.
R and R each represents an anchoring moiety rendering said compound nondifi'usible;
R is hydrogen. alkyl or substituted alkyl; and
n and a each is l or 2, provided than when R is an alkyl radical or X or X is a secondary or tertiary amino comprising an anchoring moiety rendering said compound nondiffusible or when R. X and X together contribute an anchoring moiety. n and u may be i. but when said substituents alone or together do not contribute an anchoring moiety at least one or n and n must be 2.
each of R and R comprises an amide of at least 13 carbon atoms. said amide being bonded directly to a nuclear carbon atom of the shown benzene moiety or linked thereto through a phenylene or alkylene substituent;
each of n and n is l or 2. provided that at least one of said I:
and n is 2; and
D is a monoazo. disazo or anthraquinone dye moiety.
8. A photographic process for preparing visible images com prising the steps of developing an exposed photosensitive layer including a light-sensitive silver halide layer to form a silver image in said layer; as a function of said development selectively releasing a difi'usible color-providing material for transfer in an imagewise pattern corresponding to said silver image; and transferring said imagewise pattern of colorproviding material. at least in part. by diffusion. to a stratum adjacent to said silver imagecontaining layer to impart to said stratum a color transfer image. thereby providing a photographic image which is a composite of said silver image and said color image.
9. A process as defined in claim 8 wherein said development is effected by contacting said exposed silver halide with an aqueous alkaline composition including a silver halide developing agent and said color-providing material is selectively released by a reaction with oxidized silver halide developing agent formed as a function of said development.
10. A process as defined in claim 8 whereas said colorproviding material is a diffusible dye moiety of a nondiffusible compound.
11. A photographic process for preparing visible images comprising the steps of exposing a photosensitive element including a light-sensitive silver halide layer and a dyeable stratum to form a developable image; developing said image in the presence of a layer containing a nondiffusible material containing a diffusible color-providing moiety, which material is capable of forming by a redox reaction an oxidization product which can autoreact intramolecularly to effect ringclosure and to eliminate the diffusible color-providing moiety of said material for transfer. said development being effected by contacting said exposed silver halide developing agent which when oxidized is capable of undergoing said redox reaction with said material. thereby reducing exposed silver halide to image silver to form a negative silver image and. as a function of development. providing an imagewise distribution of oxidized developing agent in terms of exposed and developed areas of said silver halide layer; contacting said nondiffusible material with said imagewise distribution of oxidized developing agent whereby said material is selectively oxidized by a redox reaction with said oxidized silver halide developing agent to effect said ring-closure and to release said difi'usible dyeable stratum whereby to impart thereto a negative dye image corresponding imagewise to said silver image. and to form a negative photographic image which is a composite of said silver image and said dye image.
12. A process as defined in claim 11 wherein said image is viewable as a transparency.
13. A process as defined in claim 11 including the step of removing unexposed and undeveloped silver halide from said silver halide layer at some time during or subsequent to said development. a
14. A process as defined in claim 10 wherein said unexposed and undeveloped silver halide is removed during development by including a silver halide solvent in said processing composition.
15. A process as defined in claim 13 wherein said unexposed and undeveloped silver halide is removed at some time subsequent to image formation by applying a fixing solution to said image.
16. A process as defined in claim 11 wherein said dye is of a neutral color.
i i i U U UNITED STATES PATENT OFFICE CERTIFICATE OF CORRECTION Patent No. 730 Dated November 16, 1971 Inventor-(s) Russell P Ok It is certified that error appears in the above-identified patent and that said Letters Patent are hereby corrected as shown below:
The sheet of drawing should be inserted as part of Letters Patent.
vs/suppom' xs g ovc-cow'mmms LAYER DEVELOPING composmow DYEABLE STRATUM SILVER HALIDE LAYER x SUPPORT INVENTOR. RUSSELL P COOK allow n, Mwfi 7721M UNITED STATES PATENT OFFICE CERTIFICATE OF CORRECTION Page 12 Patent 3.620l730 Dated flovember l6 1971 Inventofls) Russell P. Cook It is certified that error appears in the above-identified patent and that said Letters Patent are hereby corrected as shown below: Column 1, line 21, after compounds delete "of oxidized developing agent in" and insert to.
Column 1, line 44, "inhibitionf' should read as --imbibition-.
Column 1, line 60, after schematic delete "compound containing the diffusible dye moiety is contained initially on".
Column 1, line 65, after non-diffusible insert compound containing the diffusible dye moiety is contained--.
Column 2, line 38, "anchoring moiety" should read as V "anchoring moiety'f- Column 3, line 10, after the formula insert -etc.--. Column 3, line 58, after R delete "and" and insert -or-. Column 3, line 63, "443, 940" should read as 3, 443, 940.
Column 5, line 8, "dihydroxybenezene" should read as dihydroxybenzene.
Column 5, line 39, "inhibition" should read as imbibition-.
Column 6, line 11, 2E!!!" should read as -show--.
Column 7, line 69, "than" should read as --that-.
Drawing omitted.
Signed and sealed this 1st day of August 1972.
(SEAL) Attest:
EDWARD M.FLETCHER,JR. ROBERT GOTTSCHALK Attesting Officer Commissioner of Patents mm 90-1050 (10-69} uscoMM-oc cos-romeo ".5. BOVIINIII'I IIINHIG OFHCI I... O-Jii-Il

Claims (15)

  1. 2. A product as defined in claim 1 wherein said silver halide layer is disposed between said support and said dyeable stratum.
  2. 3. A product as defined in claim 1 wherein said dyeable stratum is disposed between said support and said silver halide layer.
  3. 4. A photographic product comprising, in combination, a first element comprising a support carrying on one side thereof a light-sensitive silver halide emulsion layer and a dyeable stratum, and a second element adapted for placement in superposition therewith having a layer containing a compound of the formula:
  4. 5. A product as defined in claim 4 wherein said silver halide emulsion layer is disposed between said support and said dyeable stratum of said first element.
  5. 6. A product as defined in claim 4 wherein said support is substantially transparent.
  6. 7. A product as defined in claim 6 wherein said compound is of the formula:
  7. 8. A photographic process for preparing visible images comprising the steps of developing an exposed photosensitive layer including a light-sensitive silver halide layer to form a silver image in said layer; as a function of said development selectively releasing a diffusible color-providing material for transfer in an imagewise pattern corresponding to said silver image; and transferring said imagewise pattern of color-providing material, at least in part, by diffusion, to a stratum adjacent to said silver image-containing layer to impart to said stratum a color transfer image, thereby providing a photographic image which is a composite of said silver image and said color image.
  8. 9. A process as defined in claim 8 wherein said development is effected by contacting said exposed silver halide with an aqueous alkaline composition including a silver halide developing agent and said color-providing material is selectively released by a reaction with oxidized silver halide developing agent formed as a function of said development.
  9. 10. A process as defined in claim 8 whereas said color-providing material is a diffusible dye moiety of a nondiffusible compound.
  10. 11. A photographic process for preparing visible images comprising the steps of exposing a photosensitive element including a light-sensitive silver halide layer and a dyeable stratum to form a developable image; developing said image in the presence of a layer containing a nondiffusible material containing a diffusible color-providing moiety, which material is capable of forming by a redox reaction an oxidization product which can autoreact intromolecularly to effect ring-closure and to eliminate the diffusible color-providing moiety of said material for transfer, said development being effected by contacting said exposed silver halide developing agent which when oxidized is capable of undergoing said redox reaction with said material, thereby reducing exposed silver halide to image silver to form a negative silver image and, as a function of development, providing an imagewise distribution of oxidized developing agent in terms of exposed and developed areas of said silver halide layer; contacting said nondiffusible material with said imagewise distribution of oxidized developing agent whereby said material is selectively oxidized by a redox reaction with said oxidized silver halide developing agent to effect said ring-closure and to release said diffusible color-providing moiety in an imagewise pattern corresponding to said silver image, and transferring said imagewise distribution of diffusible color-providing moiety, by diffusion, to said dyeable stratum whereby to impart thereto a negative dye image corresponding imagewise to said silver image, and to form a negative photographic image which is a composite of said silver image and said dye image.
  11. 12. A process as defined in claim 11 wherein said image is viewable as a transparency.
  12. 13. A process as defined in claim 11 including the step of removing unexposed and undeveloped silver halide from said silver halide layer at some time during or subsequent to said development.
  13. 14. A process as defined in claim 10 wherein said unexposed and undeveloped silver halide is removed during development by including a silver halide solvent in said processing composition.
  14. 15. A process as defined in claim 13 wherein said unexposed and undeveloped silver halide is removed at some time subsequent to image formation by applying a fixing solution to said image.
  15. 16. A process as defined in claim 11 wherein said dye is of a neutral color.
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US4390606A (en) * 1981-07-06 1983-06-28 Eastman Kodak Company Color-forming para-sulfonamidodiphenylamine dye precursor and sulfonimide dye in photographic material and process

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US2834676A (en) * 1955-07-19 1958-05-13 Sperry Rand Corp Photographic diffusion transfer process for producing multiple direct positive copies
US2944894A (en) * 1955-09-28 1960-07-12 Polaroid Corp Photographic processes utilizing screen members
US3203796A (en) * 1962-04-27 1965-08-31 Gevaert Photo Prod Nv Use of starch ether layers in diffusion transfer processes
US3345166A (en) * 1961-03-09 1967-10-03 Polaroid Corp Photographic process whereby a fully developed and fixed negative is formed concurrently with a positive silver transfer image
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US2834676A (en) * 1955-07-19 1958-05-13 Sperry Rand Corp Photographic diffusion transfer process for producing multiple direct positive copies
US2944894A (en) * 1955-09-28 1960-07-12 Polaroid Corp Photographic processes utilizing screen members
US3345166A (en) * 1961-03-09 1967-10-03 Polaroid Corp Photographic process whereby a fully developed and fixed negative is formed concurrently with a positive silver transfer image
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US4390606A (en) * 1981-07-06 1983-06-28 Eastman Kodak Company Color-forming para-sulfonamidodiphenylamine dye precursor and sulfonimide dye in photographic material and process

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