US3042514A - Diffusion-transfer reversal process - Google Patents

Diffusion-transfer reversal process Download PDF

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Publication number
US3042514A
US3042514A US831953A US83195359A US3042514A US 3042514 A US3042514 A US 3042514A US 831953 A US831953 A US 831953A US 83195359 A US83195359 A US 83195359A US 3042514 A US3042514 A US 3042514A
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US
United States
Prior art keywords
image
coating
light sensitive
exposed
layer
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
US831953A
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English (en)
Inventor
Curt B Roth
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.)
GAF Chemicals Corp
Original Assignee
General Aniline and Film Corp
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 BE593815D priority Critical patent/BE593815A/xx
Application filed by General Aniline and Film Corp filed Critical General Aniline and Film Corp
Priority to US831953A priority patent/US3042514A/en
Priority to GB26910/60A priority patent/GB914035A/en
Priority to DEG30228A priority patent/DE1131091B/de
Application granted granted Critical
Publication of US3042514A publication Critical patent/US3042514A/en
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

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Classifications

    • 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

Definitions

  • Patented July 3, 19%2 This invention relates to a novel photographic process. More particularly, this invention relates to a novel ditfu sion-transfer reversal process wherein ordinary tap water is used as the processing liquid.
  • the diffusion-transfer reversal process comprises exposing a photographic element comprising a base having thereon a coating of a light sensitive silver halide emulsion and developing the exposed coating with a developer containing a silver halide solvent while the coating is in contact with a specially-prepared layer which is not light sensitive.
  • the solvent in the developer dissolves the unexposed silver halide which is transferred image-wise to the specally-prepared layer toform thereon a positive image by reaction of the dissolved silver-halide with substances present in the layer.
  • the DTR process as heretofore practiced is relatively slow, complicated and diflicult to control.
  • the novel process of this invention comprises exposing a photosensitive film comprising a base having as a photosenistive layer a known print-out emulsion and then pressing the exposed film against an image receiving layer in the presence of moisture.
  • the moisture may be supplied by means of ordinary tap water or deionized water.
  • the pressing of the two layers may take place at room temperature.
  • a contact time of from 120 seconds, preferably about 2 to 5 seconds is sufficient to accomplish the transfer of the image.
  • the two very slightly moist layers are then separated and dried.
  • this process can be practiced as a dry process.
  • Heat alone may be utilized to accomplish the transfer of the image.
  • a reagent can be added to the coating which loses moisture on heating. Such reagent is disclosed in German Patent No. 888,045 and in Schm und T011, 11, 62 (1958).
  • the increased temperature may be such as to speed up the diffusion to such an extent that a more rolling of the contacting layers between hot rollers will be sufficient to transfer the image.
  • this process can be practiced as a semi-dry process.
  • the moisture necessary to accomplish the transfer may be supplied in the form of steam.
  • Print-out emulsions are well known in the art. These emulsions are described in various publications. Special reference is here made to pages 245-257 of a book by T. T. Baker entitled, Photographic Emulsion Technique 1948, published by American Photographic Publishing Company. These emulsions are also described in a book entitled, Photographic Facts and Formulas (1947), pages 188200, by E. 1. Wall and in a book entitled, Chimie Photographique (1957), pages 299401, by Pierre Glafkides.
  • emulsions all contain a soluble silver salt such as silver nitrate, for example, a halide, such as ammonium chloride, sodium chloride, etc, capable of reacting with the soluble silver salt to form silver halide, the amount of soluble silver salt in the composition being in excess of that which will react with the halide to form silver halide so that a certain amount of the soluble silver salt is present in the emulsion after exposure.
  • a soluble silver salt such as silver nitrate
  • a halide such as ammonium chloride, sodium chloride, etc
  • secondary adjuncts such as surfactants, ultraviolet absorbers and the like.
  • the print-out emulsion may be coated on any desired base used in the photographic art.
  • suitable bases are the cellulose esters such as cellulose acetate, cellulose nitrate, for example, the vinyl resins such as vinyl acetate, paper, metals and others.
  • colloidal Ag colloidal sulfur, Na S, Z-mercaptobenzothia- Zole, phenyl-mercapto-tetrazole
  • colloidal silica such as silica aerogel, Santogel, fullers earth, diatomaceous earth, kieselguhr, wood flour, infusorial earth, bentonite, filter aids such as Celite, Super-Floss and finely-powdered glass, talc, mica and the like.
  • photolytic silver Upon exposure of the light sensitive layer, photolytic silver is formed in the exposed areas. This photolytic silver does not diffuse. The unexposed areas contain still the soluble silver salts such as silver nitrate, silver citrate and/or silver and ammonia complexes, depending upon the composition of the print-out type emulsion used. Upon contact of the exposed layer with the image receiving layer in the presence of water, the water soluble silver salts dissolve and diffuse into the image-receiving layer to form the image.
  • soluble silver salts such as silver nitrate, silver citrate and/or silver and ammonia complexes
  • the silver halide is no essential ingredient and does not take part in the DTR step.
  • the development and transfer of the prior art processes takes about 60 seconds whereas in my process 3 seconds or less is sufficient. My process may be carried out in the presence of room light whereas the prior art processes must be carried out in darkness.
  • Example I A light sensitive coating was prepared by adding to a commercial print-out emulsion as obtained from production (50.0 g.) a 20% aqueous formaldehyde solution (1.0 ml.), and coating the above mixture at 40 C. onto a subbed cellulose triacetate film base.
  • the coating was placed behind a photographic negative in a printing frame.
  • the printing frame was placed 41 cm. from a Medium Beam Reflector Photo Lamp. Be-
  • the light intensity at the plane, where the printing frame stood during exposure was set at 200 footcandles.
  • the intensity of the lamp output was controlled by means of a voltage regulator.
  • the light intensity was measured before each exposure with a Weston Foot-Candle Meter, model L-61.
  • the coatings were then stripped apart 5 seconds after they had emerged together from the roller system.
  • Example II The light sensitive coating was prepared by coating the following mixture (40 C.) on baryta subbed paper base: Commercial print-out emulsion g 50 MnSO .4l-I O (50% aqueous solution) m1 1 (2) The image-receiving coating was prepared by coating the following mixture (40 C.) on baryta subbed paper base:
  • the coatings were then stripped apart 5 seconds after they had emerged together from the roller system.
  • the image-receiving layer was then dipped into 5% aqueous NaOH for 30 seconds, and then washed 1 minute with runnin 20 C. tap water.
  • Example 111 (l) The light sensitive coating was prepared by coating the following mixture (40 C.) on transparent film base:
  • Example IV The light sensitive coating used was the same as that described in Example III, step 1.
  • the image-receiving coating was prepared by pulling strips of baryta subbed paper base through a solution consisting of 30 mg. of 2-mercaptobenzothiazole per liter of distilled methanol; these strips were dried thoroughly before using.
  • the coatings were then stripped apart 5 to 10 seconds after they had emerged together from the bath.
  • Example V The light sensitive coating used was the same as that described in Example III, step 1.
  • the image-receiving coating was prepared by pulling strips of baryta subbed paper base through a solution consisting of 30 mg. of phenyl-mercapto-tetrazole per liter of distilled methanol; these strips were dried thoroughly before using.
  • the coatings were then stripped apart 5 to 10 seconds after they had emerged together from the roller system.
  • Example VI The light sensitive coating was the same as in Example III, step 1.
  • the image-receiving layer was prepared by coating the following mixture (40 C.) on baryta subbed paper base:
  • the coatings were then stripped apart to 20 seconds after they had emerged together from the roller system.
  • Example VII The light sensitive layer used was the same as that described in Example III, step 1.
  • the image-receiving layer was prepared by coating the following mixture (40 C.) on baryta subbed paper base:
  • the coatings were then stripped apart 0 to 20 seconds after they had emerged together from the roller system.
  • Example VIII The light sensitive coating used is the same as that described in Example III, step 1.
  • the image-receiving layer consisted of colloidal 6 zinc sulfide in gelatin (see U.S.P. 2,843,485, Yutzy and Cowden, Example I) prepared in the following manner:
  • Example IX The light sensitive coating used is the same as that described in Example III, step 1.
  • the image-receiving layer was prepared by coating the following mixture (40 C.) on baryta subbed paper base:
  • Example X 1 The light sensitive coating used is the same as that described in Example III, step 1.
  • the image-receiving coating was prepare-d by pulling strips of baryta subbed paper base through a slurry of 2.0 grams of zinc oxide in 200 ml. of deionized waterv (mixing at 60 volts in a metal cup on a Waring Blendor). (3) The light sensitive coating was exposed through a photographic positive for 5 minutes in the same setup as described in Example I, step 2.
  • Example X1 The light sensitive coating was the same as that described in Example III, step 1.
  • the image-receiving layer was prepared by pulling strips of baryta subbed paper base through a mixture of 2 grams of TiO in 200 ml. of deionized water (mixing at 60 volts in a metal cup on a Waring Blendor).
  • the coatings were then stripped apart 0 to 20 seconds after they had emerged together from the roller system.
  • Example XII 1 The light sensitive coating was the same as that used in Example III, step 1.
  • the image-receiving layer was prepared by coating Lhe following mixture (40 C.) on baryta subbed paper ase:
  • Colloidal zinc sulfide (see Example VIII, step 2) ml 50 Ascorbic acid g 1 10% aqueous K-Cr-Alum ml 0.5 TiO ..g 0.5
  • Example XIII (1) The light sensitive layer was the same as that described in Example III, step 1.
  • the image-receiving layer was prepared by pulling strips of baryta subbed paper base through a solution consisting of Silica powder (Floated Powder, 240 mesh, Fisher,
  • the coatings were then stripped apart 5 seconds after they had emerged together from the roller system.
  • Example XIV (1) The light sensitive layer was the same asin Example III, step 1.
  • the image-receiving layer was prepared by pulling strips of baryta subbed paper base through a mix- .ture of 0.1% aqueous Zn(NO .6H O solution ml 100 0.1% aqueous Na S solution ml 23 Deionized water ml 1 57 Ascorbic acid g 1.0
  • the coatings were stripped apart from 0 to 20 seconds after they had emerged together from the roller system.
  • Example XVI 1 The light sensitive coating was the same as that described in Example IH, step 11.
  • the image-receiving coating was prepared by coating the following mixture (at 40 C.) on baryta subbed paper base:
  • a suspension of colloidal silver in gelatin (with 9 g. of colloidal silver per kg. of suspension and particle sizes of 20-30 millimicrons diameters) g 6% surface gel ml 3 5 aqueous K-Cr-Alum ml 1 Ascorbic acid g 1 8% Saponin ml 0.3
  • the exposed light sensitive coating was rolled into contact with the dampened image-receiving coating through a bath containing tap water for a period of 2 seconds.
  • the coatings were then stripped apart 5 seconds after they had emerged together from the roller system.
  • Example XVII 1 The light sensitive coating was prepared as follows:
  • the above mixture was coated on subbed film base and paper.
  • the image-receiving coating was prepared by coating the following mixture at 40 C. on subbed film base and paper:
  • the apparatus used in pressing together the light sensitive layer and the image-receiving layer may be of very simple construction.
  • one of the layers may be wetted with water and the two layers pressed together by running over them with a rubber roller.
  • the two layers are then separated and dried.
  • the image appears on the image-receiving layer.
  • the two layers may also be placed into a Constat or Ozalid Photo Copy Processor machine. This machine is nothing more than a rubber roller system mounted in a tray. In operation, the tray is cfilled with water and the handle turned which causes the two rollers to rotate at the same speed resulting in the two layers being pressed together.
  • a process of forming a positive silver image in an image receiving layer which comprises imagewise exposing a silver salt print-out emulsion layer containing a water-soluble silver salt so as to form metallic silver in the exposed areas of said print-out layer and then contacting said exposed silver salt emulsion layer under pressure with said image receiving layer in the presence of pure water, whereby said water-soluble silver salt in the unexposed portions of the emulsion is dissolved in said pure water, transferred to the receiving layer and converted into metallic silver in the presence of a nucleating agent for promoting image formation which is located in said image receiving layer, thereby transforming the dissolved silver salt which is transferred and deposited in said receiving layer into a visible image.
  • a process according to claim 1 wherein said nucleating agent for promoting image formation comprises physical development nuclei.
  • a process of forming a positive silver image in an image receiving layer comprising a baryta subbed paper having a coating comprising phenyl-mercapto-tetrazcle thereon, which comprises exposing imagewise, a silver chloride print-out emulsion layer containing an excess of silver nitrate so as to form metallic silver in the exposed areas of said print-out layer and then contacting said exposed silver chloride print-out emulsion under pressure with said image receiving layer in the presence of pure water which is used as the sole processing agent, thereby dissolving the silver nitrate in the unexposed portions of the print-out emulsion and transferring it to the receiving layers where said dissolved water-soluble silver salt is deposited as metallic silver in visible form.
  • the imagereceiving layer comprises baryta subbed paper having a coating thereon comprising MnSO 10.
  • the imagereceiving layer comprises baryta subbed paper having a coating thereon comprising ascorbic acid.
  • the imagereceiving layer comprises baryta subbed paper having a coating thereon comprising phenyl-mercapto-tetrazole.
  • the imagereceiving layer comprises baryta subbed paper having a coating thereon comprising ZnO.
  • a process as recited in claim 1 wherein the imagereceiving layer comprises baryta subbed paper having a coating thereon comprising Mn(OAc) 14. A process as recited in claim 1 wherein the imagereceiving layer comprises baryta subbed paper having a coating thereon comprising TiO 15. A process as recited in claim 1 wherein the imagereceiving layer comprises baryta subbed paper having a coating thereon comprising Na S.
  • the imagereceiving layer comprises baryta subbed paper having a coating thereon comprising Zn(NO 17).
  • the imagereceiving layer comprises baryta subbed paper having a coating thereon comprising ZnS.
  • the imagereceiving layer comprises baryta subbed paper having a coating thereon comprising Silica in finely dispersed form.
  • the imagereceiving layer comprises baryta subbed paper having a coating thereon comprising colloidal silver.

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  • Chemical & Material Sciences (AREA)
  • Inorganic Chemistry (AREA)
  • Physics & Mathematics (AREA)
  • General Physics & Mathematics (AREA)
  • Photosensitive Polymer And Photoresist Processing (AREA)
  • Color Printing (AREA)
  • Silver Salt Photography Or Processing Solution Therefor (AREA)
  • Non-Silver Salt Photosensitive Materials And Non-Silver Salt Photography (AREA)
US831953A 1959-08-06 1959-08-06 Diffusion-transfer reversal process Expired - Lifetime US3042514A (en)

Priority Applications (4)

Application Number Priority Date Filing Date Title
BE593815D BE593815A (en)) 1959-08-06
US831953A US3042514A (en) 1959-08-06 1959-08-06 Diffusion-transfer reversal process
GB26910/60A GB914035A (en) 1959-08-06 1960-08-03 Process of forming a positive silver image
DEG30228A DE1131091B (de) 1959-08-06 1960-08-04 Verfahren zur Herstellung von Bildern nach dem Diffusionsuebertragungsverfahren

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US831953A US3042514A (en) 1959-08-06 1959-08-06 Diffusion-transfer reversal process

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US3042514A true US3042514A (en) 1962-07-03

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Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3248219A (en) * 1960-09-06 1966-04-26 Cons Electrodynamics Corp Photographic element for dry processing
US3257205A (en) * 1960-10-12 1966-06-21 Gevaert Photo Prod Nv Method for heat development
US3334584A (en) * 1962-09-24 1967-08-08 William C Toland Production of lithographic printing plates
US3379532A (en) * 1963-07-05 1968-04-23 Zindler Lumoprint Kg Image receiving sheet with a double pvahygroscopic salt layer coating
US3450535A (en) * 1962-01-25 1969-06-17 Lumoprint Zindler Kg Diffusion transfer receiving layer with high soda content
US3532497A (en) * 1963-08-05 1970-10-06 Eastman Kodak Co Nuclei for use in solvent transfer systems
US4036650A (en) * 1974-08-27 1977-07-19 Canon Kabushiki Kaisha Heat developable photosensitive material containing compounds of sulfur

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE1285311B (de) * 1965-05-08 1968-12-12 Agfa Gevaert Ag Verfahren zur Herstellung von Bildern nach dem Silbersalzdiffusionsverfahren

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB695905A (en) * 1950-04-15 1953-08-19 Bayer Ag Direct production of positive photographic images
US2846309A (en) * 1952-07-17 1958-08-05 Polaroid Corp Photographic products
CA566522A (en) * 1958-11-25 Polaroid Corporation Photographic process

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CA566522A (en) * 1958-11-25 Polaroid Corporation Photographic process
GB695905A (en) * 1950-04-15 1953-08-19 Bayer Ag Direct production of positive photographic images
US2846309A (en) * 1952-07-17 1958-08-05 Polaroid Corp Photographic products

Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3248219A (en) * 1960-09-06 1966-04-26 Cons Electrodynamics Corp Photographic element for dry processing
US3257205A (en) * 1960-10-12 1966-06-21 Gevaert Photo Prod Nv Method for heat development
US3450535A (en) * 1962-01-25 1969-06-17 Lumoprint Zindler Kg Diffusion transfer receiving layer with high soda content
US3334584A (en) * 1962-09-24 1967-08-08 William C Toland Production of lithographic printing plates
US3379532A (en) * 1963-07-05 1968-04-23 Zindler Lumoprint Kg Image receiving sheet with a double pvahygroscopic salt layer coating
US3532497A (en) * 1963-08-05 1970-10-06 Eastman Kodak Co Nuclei for use in solvent transfer systems
US4036650A (en) * 1974-08-27 1977-07-19 Canon Kabushiki Kaisha Heat developable photosensitive material containing compounds of sulfur

Also Published As

Publication number Publication date
BE593815A (en))
DE1131091B (de) 1962-06-07
GB914035A (en) 1962-12-28

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