US2751300A - Photographic solvent transfer reproduction process - Google Patents

Photographic solvent transfer reproduction process Download PDF

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Publication number
US2751300A
US2751300A US443536A US44353654A US2751300A US 2751300 A US2751300 A US 2751300A US 443536 A US443536 A US 443536A US 44353654 A US44353654 A US 44353654A US 2751300 A US2751300 A US 2751300A
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United States
Prior art keywords
silver halide
pyrazolidone
silver
developer
ascorbic acid
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Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired - Lifetime
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US443536A
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English (en)
Inventor
Thomas H James
Leonard W Tregillus
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Eastman Kodak Co
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Eastman Kodak Co
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Publication date
Priority to BE539816D priority Critical patent/BE539816A/xx
Application filed by Eastman Kodak Co filed Critical Eastman Kodak Co
Priority to US443536A priority patent/US2751300A/en
Priority to GB19785/55A priority patent/GB778792A/en
Priority to FR1146552D priority patent/FR1146552A/fr
Application granted granted Critical
Publication of US2751300A publication Critical patent/US2751300A/en
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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
    • G03C8/04—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

  • EMULSION 3 'PYIPAZOL IDONE-ASCORB/C ACID A gX SOL VEN T DEVELOPER Slage] Tbomasli James leonardm'egifils IN VEN TORS' .AT romvs PHOTOGRAPHIC SOLVENT TRANSFER REPRODUCTIUN PROCESS Thomas H. James and Leonard W. Tregillus, Rochester,
  • This invention relates to a photographic solvent transfer reproduction process of the type in which an exposed silver halide emulsion is developed in the presence of a silver halide solvent such as sodium thiosulfate in contact with a receiving sheet with the result that a silver image is developed in the emulsion layer and thereafter the residual silver halide is dissolved by the silver solvent and transferred imagewise by diffusion to a receiving sheet where it is transformed to metallic silver or other silver compound of high optical density. Processes of this type have been described at some length in the patent and periodical literature.
  • the development system we employ in the solvent transfer processes for development in the presence of silver halide solvents is a combination of a 3-pyrazolidone silver halide developing agent and an ascorbic acid developing agent such as l-ascorbic acid and d-iso-ascorbic acid.
  • the 3-pyrazolidone silver halide developing agents and ascorbic acids alone are very low-energy silver halide developing agents, yet in combination give the desired high-energy developing system.
  • the 4,4-dialkyl-3-pyrazolidone compounds are described and claimed in the Allen et a1.
  • the w-hydroxyalkyl-3-pyrazolidones, for example, compounds 18 and 24 above, are also useful. Compounds 18 and 24 are described in the Reynolds et a1.
  • a particularly efiicacious group of 3-pyrazolidone developing agents for use in combination with ascorbic acid and a silver halide solvent in the developer compositions of the invention are compounds Nos. 1, 2, 14, 18, 21, 24 and 27 of the above tabulation.
  • the undesirable staining properties of a typical highcnergy silver halide developer composition was demon strated by exposing a negative-speed bromoiodide emulsion layer of conventional hardness to a line, halftone or continuous-tone subject and developing the exposed emulsion layer in the following composition:
  • stage 1 shows the two sheets at the moment of contact.
  • Example 2 A negative film carrying a bromoiodide emulsion was processed as in the above example except that the following developer composition was employed:
  • Example 3 The procedure of Example 1 was carried out with the I 4 bromoiodide negative film and the following developer composition:
  • Example 4 The procedure of Example 1 was carried out with a silver chloride negative paper and a developer solution having the following composition:
  • the stain density on the print obtained after incubation was 0.02.
  • Example 5 An emulsion coating on paper was prepared which contained 0.287 gram of silver chloride, 0.74 gram of gelatin, 0.20 gram of di-isoascorbic acid, and 0.01 gram of lphenyl-3-pyrazolidone per square foot. Using this material as the negative, it and the receiving sheet above were immersed in an activator solution consisting of:
  • Example 6 A silver chloride-sensitized negative paper and the same receiving sheet were utilized as in Example 1 with the following developer composition:
  • Example 7 The procedure of Example 6 was carried out except utilizing the following developer composition:
  • Example 8 The bromoiodide negative film and receiving sheet were processed as above with the following developer composition:
  • the stain density of the resulting incubated print was 0.02.
  • Example 9 The procedure of Example 1 was carried out with a silver chloride paper and the following developer composition:
  • the stain density of the print obtained after incubation was 0.03.
  • Example 10 The following developer compositions were provided:
  • Example 16 Additional examples (11 to 16) illustrating our invention are provided by the table following.
  • the procedure of Example 1 was carried out using samples of a silver chloride-sensitized negative paper and the same receiving sheet in each case with the respective developers of compositions shown in the table.
  • Sample A and Sample B indicate that duplicate tests were conducted with the respective developers.
  • Examples 13 and 14 demonstrate the use of 1-phenyl-3-pyrazolidone and ascorbic acid alone as developing agents.
  • 1-phenyl-3-pyrazolidone itself is a very weak developing agent yet when employed in the process of the example gave a useful image with stain density of 0.08 to 0.06 after incubation of the prints.
  • the minimum density values of 0.32, 0.33 and 0.35 of Example 14 represents silver density and do not represent stain on the incubated samples. This silver density results from the fact that as mentioned, ascorbic acid is such a weak developing agent in the absence of the 3-pyrazolidone compounds that the negative image is incompletely developed in the process and therefore appreciable silver halide transfers to the receiving sheet at the same time as the silver halide from the unexposed area of the sheet is transferring.
  • Examples 15 and 16 compare the use of 1-phenyl-3- pyrazolidone and hydroquinone respectively, in an ascorbic acid developer container hypo as the silver halide solvent. It is apparent from the results that the 1-phenyl- 3-pyrazolidone-ascorbic acid system is more effective in reducing stain.
  • Example 11 duplicates, for comparison, the developer of Example 1, and Example 15 duplicates Example 4.
  • Examples l2, 13, 14 and 16 were prepared to resemble Example 15 in all respects (including pH) except for the developing agents.
  • Example 12 there is used hydroquinone as the developing agent, and the high stain densities of 0.12 and 0.18 were obtained upon incubation of the prints.
  • the 3-pyrazolidone developing agent and the ascorbic acid developing agent may be contained in a colloid layer of the light-sensitive negative element and the alkaline activating bath then contains principally the silver halide solvent. If desired, either one of the developing agents may be incorporated into the emulsion while the other is contained in the alkaline developer with the silver halide solvent.
  • a second group of these silver precipitants including the guanidine derivatives, arsenous oxide, stannite, hydrazines and stannous chloride have reducing properties and react with dissolved silver transferring to the receiving sheet to form colloidal particles on which physical development can take place.
  • the third group of silver precipitants including the alkali metal sulfides, selenides and tellurides, Zinc sulfide, thiourea and its derivatives, mercaptans, Xanthatcs and colloidal sulfur, react with dissolved silver transferring to the receiving layer to form thereon an insolubl precipitate such as silver sulfide on which physical development can take place.
  • silver precipitants of the latter class such as zinc sulfide, contain a reactive sulfur atom and can be used on the receiving element in minor quantities to catalyze the reduction of the silver halide transferring to the sheet, to precipitate metallic silver, or in increased quantities to react with the silver halide in the presence of the silver halide solvent to precipitate a silver sulfide image on the receiving element.
  • Silver halide solvents useful in the developer compositions are, for example, ammonium hydroxide, ammonium chloride, ammonium sulfate, ammonium nitrate, sodium thicsulfate, sodium sulfite, a hall metal thiocyanates, sodium bisullite, potassium metabisulfite.
  • the amount of silver halide solvent used in the developer compositions will naturally depend upon a number of factors. Since it is desired that thetransfer of silver halide to the receiving sheet take place in a reasonably short period of time, quantities of the order of from about 15 to 75 grams per liter of developer give good results.
  • Quantities of active solvent such as sodium thiosulfate in concentrations of as little as 3 to 5 grams per liter are useful but give less desirable results.
  • the developer compositions of the invention containing a S-pyraZolidone silver halide developing agent, ascorbic acid and a silver solvent such as hypo may contain the latter in a concentration of the order of from about 25 to 50 or more grams per liter of solution.
  • Such developer compositions have interesting applications elsewhere in the photographic art. That is, it has been discovered that such developer compositions can be used tor the development of ordinary silver halide emulsion layers with the result that no subsequent washing of the developed emulsion layer is necessary since the silver halide solvent stabilizes the silver image.
  • a suitable composition for this purpose contains one gram of l-phenyl- 3- pyrazolidone, 50 grams of sodium thiosulfate, 10 grams of d-isoascorbic acid, 2 grams of potassium bromide and 20 grams of sodium carbonate per liter of solution. If desired, 15 grams of potassium iodide may be substituted for the sodium thiosulface in the formula for the same purpose with even better results.
  • a photographic reproduction process which comprises exposing a supported silver halide emulsion layer to a subject, developing the exposed emulsion layer in the presence of a 3-pyrazolidone silver halide developing agent and an ascorbic acid developing agent by means of an alkaline developing solution containing a silver halide solvent while said emulsion layer is in intimate contact for a portion of the development period with the surface of a receiving layer containing a silver precipitant, allowing development to proceed until a silver image has been formed in the exposed region of the emulsion layer and until at least a portion of the residual undeveloped silver halide has been dissolved by the silver halide solvent and has been transferred imagewise to the receiving sheet and silver has been precipitated thereon to. form an image of appreciable optical density, then removing the emulsion layer from the receiving layer to obtain said image on the receiving layer.
  • the 3-pyrazolidone silver halide developing agent is selected from the class consisting of 1-(p-fi-hydroxyethylphenyl)-3-pyrazolidone, l-(p-fi-hydroxyethylphenyl)-4,4-dimethyl-3-pyrazolidone, l p tolyl 3 pyrazolidone, 1-phenyl-3-pyrazolidone, l phenyl 4,4-dimethyl-3-pyrazolidone, l-p-tolyl-4,4-dimethyl-3-pyrazolidone and l-phenyl-4-methyl-3-pyrazolidone, and the silver halide solvent is in the developer solution.
  • the exposed emulsion layer contains a 3-pyrazolidone silver halide developing agent and an ascorbic acid developing agent
  • the alkaline developer solution contains a silver halide solvent
  • a photographic developer composition containing an alkaline material, ascorbic acid, a 3-pyrazolidone silver halide developing agent and at least about 15 grams per liter of a member of the class consisting of alkali metal thiosulfates, ammonium thiosulfate, sodium sulfite, sodium bisulfite, and potassium metabisulfite.

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  • Chemical & Material Sciences (AREA)
  • Inorganic Chemistry (AREA)
  • Physics & Mathematics (AREA)
  • General Physics & Mathematics (AREA)
  • Silver Salt Photography Or Processing Solution Therefor (AREA)
  • Photosensitive Polymer And Photoresist Processing (AREA)
US443536A 1954-07-15 1954-07-15 Photographic solvent transfer reproduction process Expired - Lifetime US2751300A (en)

Priority Applications (4)

Application Number Priority Date Filing Date Title
BE539816D BE539816A (de) 1954-07-15
US443536A US2751300A (en) 1954-07-15 1954-07-15 Photographic solvent transfer reproduction process
GB19785/55A GB778792A (en) 1954-07-15 1955-07-08 Improvements in photographic reproduction processes and in developers and sensitive emulsions therefor
FR1146552D FR1146552A (fr) 1954-07-15 1955-07-13 Procédé de reproduction photographique et révélateur pour sa mise en oeuvre

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Cited By (17)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2855299A (en) * 1955-06-07 1958-10-07 Polaroid Corp Photographic processes
US2965482A (en) * 1955-09-08 1960-12-20 Haloid Zerox Inc Method for fixing xerographic images
US2983606A (en) * 1958-07-14 1961-05-09 Polaroid Corp Processes and products for forming photographic images in color
US3015562A (en) * 1958-05-07 1962-01-02 Gen Aniline & Film Corp Receiving sheet for use in photographic silver transfer process
US3039869A (en) * 1957-04-24 1962-06-19 Polaroid Corp Photographic color processes and compositions
US3149970A (en) * 1959-01-10 1964-09-22 Agfa Ag Production of photographic silver images by physical development
US3234022A (en) * 1960-08-08 1966-02-08 Polaroid Corp Diffusion-transfer reversal processes and elements useful in such processes
US3253923A (en) * 1962-08-31 1966-05-31 Eastman Kodak Co Process for intensifying and fixing print-out images
US3257205A (en) * 1960-10-12 1966-06-21 Gevaert Photo Prod Nv Method for heat development
US3278307A (en) * 1961-11-21 1966-10-11 Eastman Kodak Co Photographic process for producing prints stabilized against print-out
US3312550A (en) * 1959-04-10 1967-04-04 Eastman Kodak Co Processing photographic elements containing developing agent
US3330661A (en) * 1962-11-13 1967-07-11 Eastman Kodak Co Photographic development precursors
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
US3464822A (en) * 1965-09-13 1969-09-02 Du Pont Process for making electrically conductive images
US3854948A (en) * 1971-05-15 1974-12-17 Minnesota Mining & Mfg New development composition for radiographic film
US4049450A (en) * 1976-03-30 1977-09-20 Polaroid Corporation 4-Hydroxypyrazole developing agents
EP0723203A1 (de) * 1994-12-28 1996-07-24 Agfa-Gevaert N.V. Verfahren zur Herstellung einer lithographischen Druckplatte

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS5310856B2 (de) * 1971-10-15 1978-04-17

Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2688549A (en) * 1953-08-03 1954-09-07 Eastman Kodak Co Photographic developer composition

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2688549A (en) * 1953-08-03 1954-09-07 Eastman Kodak Co Photographic developer composition

Cited By (18)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2855299A (en) * 1955-06-07 1958-10-07 Polaroid Corp Photographic processes
US2965482A (en) * 1955-09-08 1960-12-20 Haloid Zerox Inc Method for fixing xerographic images
US3039869A (en) * 1957-04-24 1962-06-19 Polaroid Corp Photographic color processes and compositions
US3015562A (en) * 1958-05-07 1962-01-02 Gen Aniline & Film Corp Receiving sheet for use in photographic silver transfer process
US2983606A (en) * 1958-07-14 1961-05-09 Polaroid Corp Processes and products for forming photographic images in color
US3149970A (en) * 1959-01-10 1964-09-22 Agfa Ag Production of photographic silver images by physical development
US3312550A (en) * 1959-04-10 1967-04-04 Eastman Kodak Co Processing photographic elements containing developing agent
US3234022A (en) * 1960-08-08 1966-02-08 Polaroid Corp Diffusion-transfer reversal processes and elements useful in such processes
US3257205A (en) * 1960-10-12 1966-06-21 Gevaert Photo Prod Nv Method for heat development
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
US3278307A (en) * 1961-11-21 1966-10-11 Eastman Kodak Co Photographic process for producing prints stabilized against print-out
US3253923A (en) * 1962-08-31 1966-05-31 Eastman Kodak Co Process for intensifying and fixing print-out images
US3330661A (en) * 1962-11-13 1967-07-11 Eastman Kodak Co Photographic development precursors
US3464822A (en) * 1965-09-13 1969-09-02 Du Pont Process for making electrically conductive images
US3854948A (en) * 1971-05-15 1974-12-17 Minnesota Mining & Mfg New development composition for radiographic film
US4049450A (en) * 1976-03-30 1977-09-20 Polaroid Corporation 4-Hydroxypyrazole developing agents
US4102684A (en) * 1976-03-30 1978-07-25 Polaroid Corporation 4-Hydroxypyrazole developing agents
EP0723203A1 (de) * 1994-12-28 1996-07-24 Agfa-Gevaert N.V. Verfahren zur Herstellung einer lithographischen Druckplatte

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Publication number Publication date
GB778792A (en) 1957-07-10
BE539816A (de)
FR1146552A (fr) 1957-11-13

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