US2740717A - Photographic transfer process - Google Patents

Photographic transfer process Download PDF

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Publication number
US2740717A
US2740717A US285856A US28585652A US2740717A US 2740717 A US2740717 A US 2740717A US 285856 A US285856 A US 285856A US 28585652 A US28585652 A US 28585652A US 2740717 A US2740717 A US 2740717A
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US
United States
Prior art keywords
emulsion
silver halide
layer
silver
solution
Prior art date
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
Application number
US285856A
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English (en)
Inventor
Henry C Yutzy
Edward C Yackel
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Eastman Kodak Co
Original Assignee
Eastman Kodak Co
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Priority to BE519520D priority Critical patent/BE519520A/xx
Application filed by Eastman Kodak Co filed Critical Eastman Kodak Co
Priority to US285856A priority patent/US2740717A/en
Priority to GB12182/53A priority patent/GB745445A/en
Application granted granted Critical
Publication of US2740717A publication Critical patent/US2740717A/en
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

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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
    • G03C8/24—Photosensitive materials characterised by the image-receiving section
    • G03C8/26—Image-receiving layers
    • G03C8/28—Image-receiving layers containing development nuclei or compounds forming such nuclei
    • 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

  • This invention relates to photography and particularly to a photographic transfer process for use in the reproduction of line or printed material or continuous tone images.
  • a further object is to provide a direct positive transfer process in which the formation of stain in the receiving sheet is avoided.
  • a still further object is to provide a transfer process in which the developing agent is not permitted to permeate and stain the non-image portions of the receiving sheet.
  • Fig. l is a cross-sectional view of our material at successive stages in the process.
  • Fig. 2 is a sectional view of a roll fihn employing our process.
  • a hardened colloid-silver halide emulsion e. g. a gelatin emulsion, coated on film, paper or other support.
  • the emulsion contains a substantially non-diffusing developing agent which may be either of the tanning or non-tanning type.
  • the sensitive layer is exposed to an object or image, usually a line or halftone image although a continuous tone image may also be used to form the record in the sensitive layer. Exposure may be made directly on the emulsion of the sensitive element or by reflex printing.
  • the exposed element is then developed by immersion in a dilute alkaline solution such as dilute sodium carbonate or sodium hydroxide, which may contain well-known fog restrainers such as soluble bromide, antifoggants, etc., and while wet with this solution is pressed into contact with a receiving sheet of paper or other material in the presence of a silver halide solvent and a precipitating agent. It is convenient in most cases to incorporate both the silver halide solvent and the precipitating agent in the receiving sheet although either or both may be incorporated in a separate solution used to treat the negative material after development. After being in contact for about 5 seconds to a minute or more the negative material is then stripped away and a positive image is found in the transfer sheet with which it was in contact, the positive image representing the unexposed portions of the negative.
  • a dilute alkaline solution such as dilute sodium carbonate or sodium hydroxide, which may contain well-known fog restrainers such as soluble bromide, antifoggants, etc.
  • Suitable silver halide solvents which may be used according to our invention are as follows: Ammonium hydroxide Ammonium chloride Ammonium sulfate Ammonium nitrate Sodium thiosulfate Sodium sulfite Thiocyanates of alkali metals Suitable precipitating agents which may be used according to our invention are as follows:
  • Sodium sulfide or selenide Zinc sulfide Amino guanidine sulfate Amino guanidine carbonate Arsenous oxide Sodium stannite Thiourea and its derivatives
  • Organic sulfiding agents e. g. mercaptans Xanthates
  • the precipitating agent should not produce a strong tint in the paper in its oxidized or reduced forms.
  • the agent itself should preferably. be white, as zinc sulfide, or slightly colored, as manganese sulfide. It should be present in sufficient quantity to supply stoichiometric amounts for reductionor precipitation of silver ion, and not merely in the low amounts usually used to promote physical development or catalytic deposition.
  • the developing agent is retained in the silver halide layer throughout development and transfer and serves only to develop the exposed silver halide to metallic silver when the exposed.
  • emulsion is immersed in the alkaline solution.
  • the silver halide solvent permeates the developed layer and dissolves the silver halide in the unexposed and undeveloped regions of the layer.
  • This solution diffuses to the receiving sheet or layer, and when it comes into contact with the precipitating agent, the silver halide complex is reduced or converted to an insoluble form and is retained on the receiving sheet. No development occurs in the receiving sheet nor is there any developing agent present in the receiving sheet to cause stain or discoloration in the layer containing the positive image.
  • the emulsion layer should have a hardness at least as great as that obtained with gelatin containing 0.25 ounce of formaldehyde (40 percent solution diluted 1 to 3 with water) or 0.7 gram of dry formaldehyde per pound of gelatin when freshly coated, or 0.1 ounce of the solution per pound of gelatin aged 3' to 6 months.
  • the concentration of developing agent in the emulsion is not criticalbut may be from about 25 grams to 500 grams of developing agent per kilogram of silver nitrate converted to silver halide in making the emulsion.
  • Example An emulsion suitable for use in our process was made by preparing solutions of (A) 25 grams of gelatin in 1 liter of water at 40 C., (B) 100 grams silver nitrate in 500 cc. water at C., and (C) 35 grams of sodium chloride in 500 cc. of water. Solutions B and C were simultaneously run into solution A at a uniform rate while stirring the latter over a period of about 10 minutes; solution B preferably not being allowed to run in faster than C. Thereafter, 150 grams of gelatin in 1500 cc. of
  • This emulsion was exposed to a line image and then placed in a 3% sodium carbonate solution for about 15 seconds to develop a negative image.
  • the excess alkaline solution was removed from the surface of the emulsion by squeegee and the emulsion layer of the exposed and developed element was then rolled into contact with a receiving sheet of common uncoated paper stock which had been bathed in a solution containing 4% of ammonia, and 3% of amino guanidine sulfate. After being in contact for 5 or 10 seconds the sheets were pulled apart and a positive image was obtained in the receiving sheet. Under certain conditions it is possible to make more than one transfer.
  • a support 10 of paper or other suitable material has on it a gelatino silver halide emulsion containing a non-diffusing developing agent, the exposed portions of this layer being represented at 11 and the unexposed portions at 12.
  • a silver image 13 is formed in the exposed portions of the layer as shown in the second stage of the drawing, the unexposed portions 12 being unaffected.
  • the layer bearing the negative image is then rolled into contact with a reducing agent whereupon a positive image 15 is formed in the receiving support.
  • the receiving paper containing ammonium chloride and zinc sulfide may be squeegeed into contact with a negative layer which has been moistened with sodium hydroxide, or the aqueous sodium hydroxide may be spread between the two dry layers.
  • the alkaline solution diffuses into the emulsion layer, promoting development by the developing agent present in the emulsion. Diffusion of the alkaline solution into the receiving sheet or layer will release NH4OH or NH: from NH4C1 by the well-known reaction.
  • This ammonia solution then serves as the silver halide solvent, diffusing to the emulsion layer, dissolving undeveloped silver halide from unexposed areas, and transporting it back to the receivingsurface where it is insolubilized by the precipitant.
  • the sensitive layer and the receiving sheet may be combined in the form of a roll film for use in ordinary roll film cameras.
  • the interleaving or backing paper of the roll film would be replaced by a special receiving sheet to which the positive image would be transferred during processing.
  • the film spool might carry a single web, bearing on one side the light-sensitive silver halide emulsion and on the reverse side the receiving surface for the positive image.
  • the receiving or interleaving sheet would be impermeable to actinic light; in the second case, between the silver halide emulsion and the receiving layer there would be a light impermeable layer to prevent exposure during handling of the roll film in use.
  • the special receiving sheet fulfills the functions of the conventional backing paper to protect the light-sensitive silver halide emulsion from exposure during handling outside the camera, serves as a leader for threading through the camera or the processing equipment and also serves as the receiving sheet for the positive image. It is in a suitable position relative to the emulsion so that conventional camera exposure is not impeded.
  • the receiving sheet is also of such a nature in the dry state that it is inert to the photographic emulsion with which it comes in contact during storage prior to use.
  • a roll film constructed in this Way is shown in Figure 2 of the drawing.v
  • 16 represents the usual transparentor opaque film support and 17 represents the silver halide emulsion: layer containing a developing agent.
  • the interleaving or backing paper 18 is shown as an opaque duplex paper having thereon the receiving layer 19 for the positive image formed by transfer.
  • the backing paper 18 may, of course, be constructed in various ways as by having a light impervious intermediate layer or backing layer and. may have a white reflecting layer between the support and the receiving layer 19 for purposes of viewing the positive image.
  • the spool In processing the exposed roll film material, the spool is removed from the camera in the normal way and transferred to a simple processing tank which can be made light-tight and which has two or more spools for winding the exposed film through the processing bath.
  • the exposed roll film is placed in position on one of the cranks and unrolled sufiiciently so that the interleaving leader or receiving sheet can be threaded through the tank to the take-up roll.
  • the film is then wound through the processing; solution under conditions such that the emulsion. is developed and: the emulsion and receiving sheet,
  • the silver halide emulsion of the roll film may contain a non-diffusing developing agent as described earlier and the receiving sheet may contain a precipitating agent such as zinc sulfide.
  • a single processing bath of alkaline hypo or alkaline sulfite then sufiices for development of the exposed emulsion.
  • the roll film material may also employ an emulsion free of developing agent in which case it is processed by the solvent transfer method.
  • the silver halide emulsion in this case is of the conventional type and should be coated somewhat thinner than normal.
  • the receiving paper bears on the receiving surface suitable nuclei to promote physical development, for instance, colloidal silver, colloidal gold, silver sulfide, and the like.
  • the processing solution in this case is a conventional blackand'white developer containing a suitable quantity, say 20 grams per liter of sodium thiosulfate. It may be desirable to increase the pH above the normal ranges of developer solutions by the addition of alkali, to add suitable antifoggants such as benzotriazole, or to employ other means to control development rate, all of which are wellknown in the art. Alternatively, it may be desirable to employ two-solution treatment in which case the first tank would contain a conventional black-and-white developer modified as indicated if necessary and the second tank would contain a suitable solution of hypo, possibly at reduced pH.
  • a process for producing direct positive photographic images by transfer of a silver compound from a lightsensitive layer to a light-insensitive layer which comprises exposing to an object or image a photographic emulsion layer of hardened colloid containing silver halide and a silver halide developing agent which is substantially nondiffusing in said colloid, treating said emulsion with an alkaline solution to initiate and promote development by the developing agent incorporated in said emulsion, and, while said emulsion layer is wet with said solution, pressing it into contact with a light-insensitive receiving support while there is at least on the surface of said support a silver halide solvent and a silver precipitating agent.
  • a process for producing direct positive photographic images by transfer of a silver compound from a lightsensitive layer to a light-insensitive layer which comprises exposing to an object or image a photographic emulsion layer of hardened colloid containing silver halide and a silver halide developing agent which is substantially non-diffusing in said colloid, and treating said emulsion with an alkaline solution to initiate and promote development by the developing agent incorporated in said emulsion and simultaneously, while said emulsion layer is wet with said solution, pressing it into contact with a lightiusensitive receiving support while there is at least on the surface of said support a silver halide solvent and a silver precipitating agent.
  • a process for producing direct positive photographic images by transfer of a silver compound from a lightsensitive layer to a light-insensitive layer which comprises exposing to an object or image a photographic emulsion layer of hardened gelatin containing silver halide and a silver halide developing agent which is substantially nondifi'using in said gelatin, treating said emulsion with sodium carbonate solution to cause development of a silver image in said emulsion, and then, while said emulsion layer is wet with said solution, pressing said emulsion layer into contact with a light-insensitive receiving support having at least a surface coating of a silver halide solvent and a silver precipitating agent.
  • a process for producing direct positive photographic images by transfer of a silver compound from a lightsensitive layer to a light-insensitive layer which comprises exposing to an object or image a photographic emulsion layer of hardened gelatin containing silver halide and 3,4-dihydroxy diphenyl as a silver halide developing agent which is substantially non-diffusing in said gelatin, immersing said emulsion in a sodium carbonate solution to cause development of a silver image in said emulsion layer, and then, while said emulsion layer is wet with said solution, pressing said emulsion layer into contact with a light-sensitive paper stock having a coating of an ammonium compound and amino guanidine sulfate at least on its surface, thereby forming a positive image on said paper stock.
  • a light-insensitive receiving sheet for transfer of a silver compound image from an exposed silver halide emulsion by diffusion comprising a paper stock containing an ammonium compound and amino guanidine sulfate.

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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)
US285856A 1952-05-03 1952-05-03 Photographic transfer process Expired - Lifetime US2740717A (en)

Priority Applications (3)

Application Number Priority Date Filing Date Title
BE519520D BE519520A (en)van) 1952-05-03
US285856A US2740717A (en) 1952-05-03 1952-05-03 Photographic transfer process
GB12182/53A GB745445A (en) 1952-05-03 1953-05-01 Improvements in materials for and processes of photographic reproduction

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
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BE (1) BE519520A (en)van)
GB (1) GB745445A (en)van)

Cited By (24)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2834676A (en) * 1955-07-19 1958-05-13 Sperry Rand Corp Photographic diffusion transfer process for producing multiple direct positive copies
US2937086A (en) * 1955-07-26 1960-05-17 Eastman Kodak Co Multilayer reversal color material
US2971840A (en) * 1955-02-07 1961-02-14 Agfa Ag Process for the production of nonlaterally reversed positive copies by heat development
US2972532A (en) * 1956-07-05 1961-02-21 Polaroid Corp Photographic process
US2992102A (en) * 1955-03-29 1961-07-11 Polaroid Corp Photographic processes and products
US3003871A (en) * 1955-09-29 1961-10-10 Polaroid Corp Photographic apparatus and process for treating light-sensitive material
US3021212A (en) * 1959-08-14 1962-02-13 Eastman Kodak Co Developers for photographic reversal processes
US3063837A (en) * 1958-11-07 1962-11-13 Agfa Ag Photographic diffusion transfer process for planographic printing
US3091530A (en) * 1959-12-21 1963-05-28 Polaroid Corp Photographic products, processes and compositions
US3108001A (en) * 1959-08-17 1963-10-22 Polaroid Corp Novel photographic products, processes, and compositions
US3113910A (en) * 1959-08-20 1963-12-10 Eastman Kodak Co Process for electro-development of photographic images
US3132577A (en) * 1961-08-21 1964-05-12 Eastman Kodak Co Method and apparatus for removing wrinkles from film backing strips
US3157500A (en) * 1962-09-11 1964-11-17 Eastman Kodak Co Photographic products containing magnetic particles and processes therefor
US3177792A (en) * 1960-04-06 1965-04-13 Itek Corp Photographic print processing apparatus
US3253916A (en) * 1962-09-12 1966-05-31 Polaroid Corp Photographic product and process
US3278958A (en) * 1955-03-31 1966-10-18 Dick Co Ab Method of imaging a photolithographic plate and elements for use in the preparation of same
US3406064A (en) * 1965-02-02 1968-10-15 Polaroid Corp Diffusion transfer with 4-methylphenylhydroquinone in the emulsion and n,n-diethylhydroxylamine in the processing fluid
US3510301A (en) * 1965-11-17 1970-05-05 Lumoprint Zindler Kg Silver salt diffusion transfer method
US3510302A (en) * 1966-02-10 1970-05-05 Walter Limberger Transfer method for silver salt diffusion and liquid agent for use in this method
DE1772603A1 (de) * 1967-06-08 1971-05-19 Agfa Gevaert Ag Photographisches Material und Verfahren
US4186005A (en) * 1972-05-01 1980-01-29 Polaroid Corporation Photographic products and processes employing roll film with acid backing layer
US4775614A (en) * 1985-10-28 1988-10-04 Agfa-Gevaert N.V. Method for fixing a photographic silver halide emulsion layer material
US4830949A (en) * 1988-04-29 1989-05-16 Agfa-Gevaert N.V. Method for processing a photographic silver halide emulsion material
US4888267A (en) * 1987-05-06 1989-12-19 Agfa-Gevaert N.V. Method for processing a photographic material

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
BE586258A (en)van) * 1959-01-07
JP2992373B2 (ja) * 1991-06-21 1999-12-20 日本ピストンリング株式会社 シンクロナイザーリング

Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2196133A (en) * 1936-09-28 1940-04-02 Robert Laing Bruce Gall Photography
US2388894A (en) * 1943-09-02 1945-11-13 Eastman Kodak Co Method of developing photographic emulsions
US2409959A (en) * 1944-05-17 1946-10-22 Polaroid Corp Method of forming images of dichroic materials
US2500421A (en) * 1944-11-03 1950-03-14 Polaroid Corp Photographic silver halide transfer process
US2563387A (en) * 1951-08-07 Photographic image receiving sheet
US2565377A (en) * 1950-06-13 1951-08-21 Polaroid Corp Hinged photographic film unit containing a liquid
US2592368A (en) * 1947-11-04 1952-04-08 Eastman Kodak Co Gelatine silver halide emulsion layer containing a dihydroxy diphenyl tanning developing agent
US2647056A (en) * 1948-02-12 1953-07-28 Polaroid Corp One step photographic transfer process

Patent Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2563387A (en) * 1951-08-07 Photographic image receiving sheet
US2196133A (en) * 1936-09-28 1940-04-02 Robert Laing Bruce Gall Photography
US2388894A (en) * 1943-09-02 1945-11-13 Eastman Kodak Co Method of developing photographic emulsions
US2409959A (en) * 1944-05-17 1946-10-22 Polaroid Corp Method of forming images of dichroic materials
US2500421A (en) * 1944-11-03 1950-03-14 Polaroid Corp Photographic silver halide transfer process
US2592368A (en) * 1947-11-04 1952-04-08 Eastman Kodak Co Gelatine silver halide emulsion layer containing a dihydroxy diphenyl tanning developing agent
US2647056A (en) * 1948-02-12 1953-07-28 Polaroid Corp One step photographic transfer process
US2565377A (en) * 1950-06-13 1951-08-21 Polaroid Corp Hinged photographic film unit containing a liquid

Cited By (24)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2971840A (en) * 1955-02-07 1961-02-14 Agfa Ag Process for the production of nonlaterally reversed positive copies by heat development
US2992102A (en) * 1955-03-29 1961-07-11 Polaroid Corp Photographic processes and products
US3278958A (en) * 1955-03-31 1966-10-18 Dick Co Ab Method of imaging a photolithographic plate and elements for use in the preparation of same
US2834676A (en) * 1955-07-19 1958-05-13 Sperry Rand Corp Photographic diffusion transfer process for producing multiple direct positive copies
US2937086A (en) * 1955-07-26 1960-05-17 Eastman Kodak Co Multilayer reversal color material
US3003871A (en) * 1955-09-29 1961-10-10 Polaroid Corp Photographic apparatus and process for treating light-sensitive material
US2972532A (en) * 1956-07-05 1961-02-21 Polaroid Corp Photographic process
US3063837A (en) * 1958-11-07 1962-11-13 Agfa Ag Photographic diffusion transfer process for planographic printing
US3021212A (en) * 1959-08-14 1962-02-13 Eastman Kodak Co Developers for photographic reversal processes
US3108001A (en) * 1959-08-17 1963-10-22 Polaroid Corp Novel photographic products, processes, and compositions
US3113910A (en) * 1959-08-20 1963-12-10 Eastman Kodak Co Process for electro-development of photographic images
US3091530A (en) * 1959-12-21 1963-05-28 Polaroid Corp Photographic products, processes and compositions
US3177792A (en) * 1960-04-06 1965-04-13 Itek Corp Photographic print processing apparatus
US3132577A (en) * 1961-08-21 1964-05-12 Eastman Kodak Co Method and apparatus for removing wrinkles from film backing strips
US3157500A (en) * 1962-09-11 1964-11-17 Eastman Kodak Co Photographic products containing magnetic particles and processes therefor
US3253916A (en) * 1962-09-12 1966-05-31 Polaroid Corp Photographic product and process
US3406064A (en) * 1965-02-02 1968-10-15 Polaroid Corp Diffusion transfer with 4-methylphenylhydroquinone in the emulsion and n,n-diethylhydroxylamine in the processing fluid
US3510301A (en) * 1965-11-17 1970-05-05 Lumoprint Zindler Kg Silver salt diffusion transfer method
US3510302A (en) * 1966-02-10 1970-05-05 Walter Limberger Transfer method for silver salt diffusion and liquid agent for use in this method
DE1772603A1 (de) * 1967-06-08 1971-05-19 Agfa Gevaert Ag Photographisches Material und Verfahren
US4186005A (en) * 1972-05-01 1980-01-29 Polaroid Corporation Photographic products and processes employing roll film with acid backing layer
US4775614A (en) * 1985-10-28 1988-10-04 Agfa-Gevaert N.V. Method for fixing a photographic silver halide emulsion layer material
US4888267A (en) * 1987-05-06 1989-12-19 Agfa-Gevaert N.V. Method for processing a photographic material
US4830949A (en) * 1988-04-29 1989-05-16 Agfa-Gevaert N.V. Method for processing a photographic silver halide emulsion material

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BE519520A (en)van)
GB745445A (en) 1956-02-29

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