US3578449A - Transfer image process utilizing an organic phosphine as silver halide solvent - Google Patents

Transfer image process utilizing an organic phosphine as silver halide solvent Download PDF

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Publication number
US3578449A
US3578449A US699300A US3578449DA US3578449A US 3578449 A US3578449 A US 3578449A US 699300 A US699300 A US 699300A US 3578449D A US3578449D A US 3578449DA US 3578449 A US3578449 A US 3578449A
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Prior art keywords
silver halide
silver
organic
image
halide solvent
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Expired - Lifetime
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US699300A
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English (en)
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Stanley M Bloom
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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
    • G03C8/32—Development processes or agents therefor
    • G03C8/36—Developers
    • G03C8/365—Developers containing silver-halide solvents
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03C—PHOTOSENSITIVE MATERIALS FOR PHOTOGRAPHIC PURPOSES; PHOTOGRAPHIC PROCESSES, e.g. CINE, X-RAY, COLOUR, STEREO-PHOTOGRAPHIC PROCESSES; AUXILIARY PROCESSES IN PHOTOGRAPHY
    • G03C8/00—Diffusion transfer processes or agents therefor; Photosensitive materials for such processes
    • G03C8/02—Photosensitive materials characterised by the image-forming section
    • G03C8/04—Photosensitive materials characterised by the image-forming section the substances transferred by diffusion consisting of inorganic or organo-metallic compounds derived from photosensitive noble metals
    • G03C8/06—Silver salt diffusion transfer

Definitions

  • the present invention relates to photography and, more particularly, is concerned with photographic compositions and processes.
  • an aqueous composition containing a silver halide solvent is applied to a photoexposed silver halide emulsion stratum and a silver-receiving stratum which are maintained in superimposed relation for at least a portion of the developing period.
  • the developing agent reduces the exposed silver halide to silver, and concurrently therewith, the silver halide solvent reacts with unexposed silver halide to form a water-soluble complex silver salt which is transferred by diffusion to the silverreceiving stratum where it forms a visible image.
  • the primary object of the present invention is to provide silver halide solvents that are free from many of the disadvantages associated with those solvents previously used and to provide compositions and processes employing said solvents.
  • the invention accordingly comprises processes involving the several steps and the relation and order of one or 3,578,449 Patented May 11, 1971 more of such steps with respect to each of the others, and the compositions and products possess-ing 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.
  • organic derivatives of the trihydrides of Group V-A elements having an atomic number greater than 7 and less and 83 exhibit unexpected properties as silver halide solvents for use in photographic processing compositions.
  • Such compounds are effective with the different silver halides and mixtures thereof commonly used in photosensitive emulsions; may be used in either aqueous or organic solution to form soluble, diffusible complex silver salts; and produce good transfer images.
  • the compounds of the present invention are oxidized in air to give a pale or colorless residue which is not deleterious to the transfer image and are effective complexing agents under less alkaline conditions than normally employed.
  • the aliphatic derivatives of said elements particularly, are readily oxidized in air and especially in the presence of alkali.
  • Preferred organic derivatives of Group V-A elements to be employed in accordance with the present invention include primary, secondary and tertiary organic phosphines, arsines and stibines as represented by the following general formula wherein X is a member selected from the group consisting of P, As+ and Sb+ R are individually selected from the group consisting of hydrogen and a monovalent organic radical; m is a whole number 0 or 1, and not more than two of said R are hydrogen when m is 0; Y represents a group having the formula wherein Z is a divalent organic radical; and X and R are defined as above.
  • monovalent organic radicals are useful as the R groups of the compounds employed in the present invention.
  • monovalent organic radical is intended to include both cyclic and acyclic organic radicals whether homogeneous or heterogeneous in nature.
  • radicals useful as the R moiety are alkyl, substituted and unsubstituted; cycloalkyl, substituted and unsubstituted; alkenyl, substituted and unsubstituted; cycloalkenyl, substituted and unsubstituted; aryl, substituted and unsubstituted; and
  • the substituents of the substituted monovalent organic radicals are solubilizing groups, i.e., groups selected to make the compound soluble in the particular liquid vehicle used. Typical of such substituents are SO H, OH, and COOH, particularly where the liquid vehicle is aqueous. Among other substituents that may be present, if desired, are halo, nitro, cyano, mercapto, amino, alkenyl, alkyl and alkoxy.
  • Preferred R radicals are electron rich groups, i.e., groups with negative sigma (a) constants as defined by the Hammett 3 Equation (Physical Organic Chemistry, L. P. Hammett, McGraw-Hill, 1940, p. 256) and examplified by the mentioned above.
  • divalent or ganic radicals may comprise the Z- component of the compounds used in accordance with the present invention.
  • Typical of the preferred radicals that may comprise the Z- component are arylene and groups represented by the formula (CR wherein q equals a whole number 1 to 3, inclusive.
  • the organic phosphines and arsines are preferred and especially the organic phosphines because of their high affinity for silver ion.
  • Typical compounds corresponding to the foregoing general formula include:
  • triphenylstiblne H5 2--Slb C 2115 triethylstibine HnCs-AS-CBHU di-n-octylarsine H-AS- 0 H2 C 6E5 benzylarsine H 0 2-As C 2H trlethylarslne triphenylarslne trls-(ortho-hydroxyphenyl)phosphine N,N-dlethauolaminodiphenylphosphine ortho-dimethylphosphinophenylenedimethylarslne CH3P (CHzCHzC O OH)2 bis (fi-carboxyethybmethylphosphine 2,3'bis (dimethylphosphino)-N,N,N-trimethylanilinium bisulfate
  • the total amount of the compounds(s) used may vary widely with the quantity added to the processing composition being sufiicient to give a satisfactory transfer print under the particular processing conditions employed. Ordinarily, the total quantity of these compound(s) incorporated into such compositions ranges between about 1 and 25% by weight of the processing composition.
  • the processing compositions formulated may vary from acid to very alkaline, e.g., from a hydrogen ion concentration of l N to a hydroxyl ion concentration of 5 N.
  • bases capable of imparting the desired alkalinityl to the processing compositions are alkali metal hydroxides, such as sodium and potassium hydroxide, and amines, such as diethylamine and allylamine.
  • acids capable of imparting the desired acidity include inorganic acids, such as hydrochloric and nitric acids and organic acids, such as citric and acetic acids.
  • a suitable buffer system may be employed to maintain the pH of the composition within a predetermined range.
  • a composition embodying the present invention is broadly useful in a variety of photographic processes of the type in which silver complexes are formed from the unreduced silver halide of a photoexposed and at least partially developed silver halide stratum.
  • the silver complexes formed should be soluble in the liquid vehicle of the composition which is usually water but it may be an organic liquid, preferably a volatile organic liquid, or a mixture of water and an organic liquid.
  • organic liquids that may be employed are alcohols, e.g., methanol; ethers, e.g., diisopropyl ether; ketones, e.g., acetone; and aromatic solvents, e.g., toluene.
  • a composition embodying the present invention specifically suitable for use in the production of transfer images comprises, in addition to complexing agents of the above-described type, a suitable silver halide developing agent.
  • a suitable silver halide developing agent commonly used are benzene and naphthalene compounds having hydroxy or amino substituents ortho or para to one another, e.g., hydroquinone, chlorohydroquinone, bromohydroquinone, toluhydroquinone, Metol (p-methyl aminophenol sulfate), glycin (p-hydroxyphenylaminoacetic acid), pyrocatechin, pyrogallol and bis-N,N-methoxyethyl hydroxylamine.
  • the processing solution is applied in a uniformly thin layer between the superposed surfaces of a photoexposed gelatino silver halide element and an image-receiving element, for example, by advancing the elements between a pair of pressure-applying rollers.
  • the elements are maintained in superposed relation for a predetermined period, preferably for a duration of to 120 seconds, during which exposed silver halide is reduced to silver and unreduced silver halide forms a water-soluble, complex salt which diffuses through the layer of solution to the image-receiving element, there to be reduced to an argental image.
  • the silver halide element is separated from the imagereceiving element.
  • the silver halide element may be any of those conventionally used in silver diffusion transfer processes and generally comprises a silver halide emulsion carried on a base, e.g., glass, paper or plastic film.
  • the silver halide may be a silver chloride, iodide, bromide, iodobromide, chlorobromide, etc.
  • the binder for the halide though usually gelatin, may be a suitable polymer such as polyvinyl alcohol, polyvinyl pyrrolidone and their copoymers.
  • the image-receiving element preferably includes certain materials, the presence of which, during the transfer process has a desirable effect on the amount and character of silver precipitated on the image-receiving element.
  • Materials of this type are specifically described in U.S. Pat. Nos. 2,690,237 and 2,698,245, both issued in the name of Edwin H. Land on Dec. 28, 1954.
  • Separating of the silver halide element from the imagereceiving element may be controlled so that the layer of processing composition is removed from the imagereceiving element or the layer of processing composition is caused to remain in contact with the image-receiving element, e.g., to provide it with a protective coating.
  • Techniques which enable such results to be accomplished as desired are described in US. Pat. No. 2,647,056 issued to Edwin H. Land on July 28, 1953.
  • the processing reagents are selected so that traces remaining after the solidified processing layer has been separated from the silver image or which remain in said layer adhered as a protective coating on the silver image, as indicated above, are colorless or pale, so as not to appreciably affect the appearance of the image and to have little or no tendency to adversely react with the silver image.
  • a unique and most desirable property possessed by the silver solvents of the present invention is their ability to be readily oxidized in air to a stable residue which has no tendency to react with the silver of the transfer image.
  • the residue besides being non-reactive with the argental image, is pale or colorless and thus, has little or no tendency to obscure the image.
  • EXAMPLE 1 A photosensitive element having a gelatino silver iodobromide emulsion on film base was exposed to a step wedge and then processed by spreading a layer of processing composition approximately mils thick between the thus-exposed emulsion and a superposed image-receiving element comprising a stratum of regenerated cellulose containing colloidal nickel sulfide as the silver precipitant.
  • the processing composition comprised:
  • the imagereceiving and photosensitive elements were separated to reveal a good image of moderate contrast on the imagereceiving sheet.
  • the silver halide solvent(s) added to the base formulation for each of the Examples 2-4 is given in Table I below.
  • the organic phosphines, arsines, stibines and mixtures thereof capable of reacting with a silver halide to form a complex silver salt soluble in the liquid medium employed are useful in both conventional and diffusion transfer processes and, as illustrated, may be used in conjunction with another silver halide solvent.
  • the processing composition may include preservatives or other components commonly used in the art and may be modified by the substitution of ingredients for those specifically mentioned.
  • a photographic processing composition comprising a liquid vehicle having dissolved therein, a silver halide developing agent and, as a silver halide solvent, at least one compound represented by the formula wherein X is a member selected from the group consisting of P, As+ and Sb+ R are individually selected from the group consisting of hydrogen and a monovalent organic radical; m is a whole number 0 or 1, and not more than two of said R are hydrogen when m is 0; Y represents a group having the formula Z-XR wherein Z is a divalent organic radical; and X and R are defined as above, said compound being capable of reacting with silver halide to form a complex silver salt that is soluble in said vehicle.
  • a photographic processing composition according to claim 3 which ranges from a hydrogen ion concentration of 1 N to a hydroxyl ion concentration of 5 N.
  • a photographic processing composition according to claim 4 wherein said compound is tris-(para-hydroxyphenyl)phosphine.
  • a photographic method comprising the steps of (1) reacting exposed silver halide of a photosensitive silver halide emulsion with a silver halide developing agent in solution in a liquid vehicle,
  • X is a member selected from the group consisting of P, As+ and Sb' R are individually selected from the group consisting of hydrogen and a monovalent organic radical; m is a whole number 0 or 1, and not more than two of said R are hydro- 8 gen when m is 0; Y represents a group having the formula -ZXR wherein Z is a divalent organic radical; and X and R are defined as above, said compound 'being capable of reacting with silver halide to form a complex silver salt thatis soluble in said vehicle,
  • a photographic method according to claim 1 wherein said compound is tri-(para-hydroxyphenyl)phosphine.

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  • Physics & Mathematics (AREA)
  • General Physics & Mathematics (AREA)
  • Chemical & Material Sciences (AREA)
  • Inorganic Chemistry (AREA)
  • Silver Salt Photography Or Processing Solution Therefor (AREA)
  • Photosensitive Polymer And Photoresist Processing (AREA)
US699300A 1968-01-22 1968-01-22 Transfer image process utilizing an organic phosphine as silver halide solvent Expired - Lifetime US3578449A (en)

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US69930068A 1968-01-22 1968-01-22

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JP (1) JPS4832127B1 (en))
BE (1) BE727186A (en))
DE (1) DE1903103B2 (en))
FR (1) FR2000539A1 (en))
GB (1) GB1232774A (en))
NL (1) NL161590C (en))

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3901714A (en) * 1974-07-29 1975-08-26 Eastman Kodak Co Silver halide emulsions and elements including sensitizers of adamantane structure
US3954473A (en) * 1974-06-24 1976-05-04 Polaroid Corporation Method of bleaching metallic silver
US4003746A (en) * 1975-07-01 1977-01-18 E. I. Du Pont De Nemours And Company Organic heterocyclic and thioaryl phosphines in silver halide emulsions and developers therefor
US4014699A (en) * 1973-05-17 1977-03-29 Ciba-Geigy Ag Preparation for the processing of photographic materials
US4138256A (en) * 1975-11-17 1979-02-06 Ciba-Geigy Ag Method of processing photographic silver dye bleach materials
US4346154A (en) * 1981-06-22 1982-08-24 Eastman Kodak Company Antistain agent or antistain agent precursor in photographic silver halide element

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS5499730U (en)) * 1977-12-24 1979-07-13
JPS5987975U (ja) * 1982-12-06 1984-06-14 アイシン高丘株式会社 プリンタ用記録紙

Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4014699A (en) * 1973-05-17 1977-03-29 Ciba-Geigy Ag Preparation for the processing of photographic materials
US3954473A (en) * 1974-06-24 1976-05-04 Polaroid Corporation Method of bleaching metallic silver
US3901714A (en) * 1974-07-29 1975-08-26 Eastman Kodak Co Silver halide emulsions and elements including sensitizers of adamantane structure
US4003746A (en) * 1975-07-01 1977-01-18 E. I. Du Pont De Nemours And Company Organic heterocyclic and thioaryl phosphines in silver halide emulsions and developers therefor
US4138256A (en) * 1975-11-17 1979-02-06 Ciba-Geigy Ag Method of processing photographic silver dye bleach materials
US4357280A (en) * 1975-11-17 1982-11-02 Ciba-Geigy Ag Use of tertiary phosphines in photographic silver dye bleach materials
US4346154A (en) * 1981-06-22 1982-08-24 Eastman Kodak Company Antistain agent or antistain agent precursor in photographic silver halide element

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Publication number Publication date
DE1903103B2 (de) 1978-05-03
GB1232774A (en)) 1971-05-19
NL161590B (nl) 1979-09-17
DE1903103A1 (de) 1969-09-25
DE1903103C3 (en)) 1979-01-11
JPS4832127B1 (en)) 1973-10-04
FR2000539A1 (en)) 1969-09-12
BE727186A (en)) 1969-07-22
NL6901049A (en)) 1969-07-24
NL161590C (nl) 1980-02-15

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