US2843485A - Transfer process of photographic printing - Google Patents

Transfer process of photographic printing Download PDF

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Publication number
US2843485A
US2843485A US430074A US43007454A US2843485A US 2843485 A US2843485 A US 2843485A US 430074 A US430074 A US 430074A US 43007454 A US43007454 A US 43007454A US 2843485 A US2843485 A US 2843485A
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US
United States
Prior art keywords
layer
gelatin
emulsion
emulsion layer
image
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
US430074A
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English (en)
Inventor
Henry C Yutzy
Herbert B Cowden
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 BE538152D priority Critical patent/BE538152A/xx
Priority claimed from US285855A external-priority patent/US2725298A/en
Priority to GB12183/53A priority patent/GB746186A/en
Application filed by Eastman Kodak Co filed Critical Eastman Kodak Co
Priority to US430074A priority patent/US2843485A/en
Priority claimed from US430424A external-priority patent/US2831766A/en
Priority to GB14211/55A priority patent/GB804283A/en
Priority to FR1132420D priority patent/FR1132420A/fr
Application granted granted Critical
Publication of US2843485A publication Critical patent/US2843485A/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
    • G03C1/00—Photosensitive materials
    • G03C1/005—Silver halide emulsions; Preparation thereof; Physical treatment thereof; Incorporation of additives therein
    • G03C1/04—Silver halide emulsions; Preparation thereof; Physical treatment thereof; Incorporation of additives therein with macromolecular additives; with layer-forming substances
    • G03C1/043—Polyalkylene oxides; Polyalkylene sulfides; Polyalkylene selenides; Polyalkylene tellurides

Definitions

  • This invention relates to photography and particularly to a transfer process of printing a photographic image.
  • the colloid layer has dispersed therein an agent forpromoting image formation, comprising physical development nuclei or a chemical precipitant for dissolved silver ions, so that the dissolved silver salts transported to the colloid layer from the silver halide emulsion layer during solvent development, are deposited and retained in a visible formin the colloid layer.
  • the image thus obtained in the colloid layer may be transferred layerwise to an absorbent support and successive transfers of the colloid layer containing the image may be made on successive absorbent supports to produce dupli- 'Z c ate images.
  • FIG. 1 illustrates sectional views of the photographic elements at various stages in our preferred process
  • Fig. 2 is a sectional view of a modified form of the sensitive element used according to our invention.
  • the silver halide emulsion used in the sensitive element of our invention may be an ordinary unsensitized gelatino silver halide emulsion,- or an optically sensitized or chemically sensitized emulsion, in which the gelatin is substantially unhardened or hardened in such away that it does not harden the colloid layer coated over it, as explained more fully hereinafter.
  • the emulsion may contain a substantially non-difiiusing developing agent of the tanning type as disclosed in Yackel U. S. Patent 2,592,368, or a non-tanning, substantially non-dilfusing developing agent as described in U. S. Patent- 2,716,059;
  • the colloid layer coated over the emulsion layer is a layer of water-susceptible or water-permeable colloid, such as gelatin or polyvinyl alcohol, containing an agent promoting image formation and capable of yielding with silver ion a dark-color silver substance, when the dissolved silver salts from the emulsion layer come in con tact with it.
  • This agent in the colloid layer may comprise either physical development nuclei or a chemical precipitantfor dissolved silver ions, the following being suitable agents:
  • the developing solution maybe the usual and customary type of photographic developing solution containing hydroquinone, N-methyl-p-aminophcnol sulfate, p-phenylene diamine, etc., or any mixture of these, as the developing agent andcontaining the usual ingredients such as alkali, potassium bromide and sodium sulfite. If the developing agent is incorporated in the emulsion layer the solution used to effect development may be a simple alkaline solution such as a sodium carbonate or sodium hydroxide solution.
  • the developing solution must also contain a silver halide solvent such as sodium thios'ulfate, sodium sulfite, ammonium hydroxide, ammonium sulfate, ammonium nitrate, ammonium chloride or a thiocyanate of an alkali metal. If the silver halide solvent is contained in the sensitive element as shown in Examples 3 and 4 hereinafter, the developing solution need not, of course, contain a silver halide solvent.
  • a silver halide solvent such as sodium thios'ulfate, sodium sulfite, ammonium hydroxide, ammonium sulfate, ammonium nitrate, ammonium chloride or a thiocyanate of an alkali metal.
  • any of the following compounds will serve for this purpose:
  • Example 1 B was poured into A at room temperature with rapid stirring. The mixture was quickly poured into 110 g. 20 percent gelatin (containing 10 cc. 7.5 percent aqueous saponin) at 40 C. The whole was held at 40 C. for coating.
  • This composite element was exposed to a positive original and the silver halide emulsion layer developed to a negative in a developing solution of the following composition:
  • the sheet was removed from the developer solution, squeegeed to remove excess developer and pressed into contact with a sheet of absorbent paper, for example, an ordinary bond typewriter paper. After a few seconds the photographic sheet was stripped from the receiving paper, which was found to carry a positive image representing a stratum of the total positive image formed in the overcoated nucleating layer.
  • the original photographic layer carrying the negative and the remainder of the nucleating layer with the positive image was rewet in the developer solution, squeegeed and rolled into contact with a second sheet of receiving paper, then stripped as before leaving another portion of the image on the second receiving sheet. This operation could be repeated several times.
  • Example 2 An ordinary photographic paper stock was coated with a high contrast contact speed gelatino-silver chloride emulsion hardened with 4.9 cc. of 20 percent formalde hyde solution per kilogram of emulsion. On this emulsion layer there was coated a layer of polyvinyl alcohol containing cadmium sulfide prepared as follows:
  • This composite element after exposure to a positive image and development in the developer of Example 1 was squeegeed to remove excess developer and rolled into contact with an absorbent receiving sheet.
  • the positive image formed in the polyvinyl alcohol layer was transferred to the receiving support, yielding a direct positive image.
  • the advantage of this element is that conventional photographic emulsions with conventional hardening agents such as formaldehyde may be used. Such gelatin hardeners have little hardening action on polyvinyl alcohol so that the polyvinyl alcohol layer retains the proper physical characteristics for a transfer to the receiving sheet.
  • Example 3 A photographic paper support free from formaldehyde or other gelatin hardeners bearing instead of the usual baryta coat a similar layer made with barium sulfite instead of barium sulfate was coated with the emulsion layer of Example 1 containing 12 g. of 3,4-dihydroxy diphenyl per kilogram of emulsion and also the nucleating layer of Example 1.
  • the nucleating layer could also be coated on a separate sheet and squeegeed into contact with the emulsion layer just prior to the development process.
  • the barium sulfite layer was made as follows:
  • the wet BaSO from above (310 g.) was dispersed in 264 cc. of water containing 45 cc. of 7.5% aqueous saponin. The mixture was heated to 40 C. and 206 g. 10% gelatin was added. This was held at 40 C. for coating.
  • solvent systems may be substituted for the barium sulfite such as calcium or strontium sulfite.
  • Other examples of solvents are slightly soluble or non-wandering ammonium salts or amines.
  • Long-chain amines may be included in the undercoat by coating high molecular resins in the layer as complexes with the amines, the complexes being broken up by the action of the alkali in the developer.
  • a separate receiving sheet bearing the nucleating layer may be used in conjunction with a conventional silver halide paper, by incorporating the insoluble or nonwandering solvent in the nucleating layer or under the nucleating layer on the receiving sheet.
  • the silver halide emulsion may contain a substantially non-diifusing developing agent as described in Example 3, the chemical energy required for forma tion of the positive image being obtained from suitable reagents in a second layer either overcoated on the emulsion layer or coated on a second transfer sheet.
  • Example 1 In the process of Example 1 in which both emulsion and nucleating layer were unhardened it has been found that there is some tendency for the fracture to occur at the paper base during transfer to the receiving sheet, resulting in unwanted transfer of all of the layers. This can be prevented by incorporating in the baryta layer or in a layer beneath the sensitive emulsion layer a completely exposed silver halide emulsion having therein an issoluble tanning developing agent. During development the completely exposed or fogged bottom layer is rapidly developed and tanned at the same time thus hardening the bottom layer and causing it to adhere more strongly to the paper support.
  • This layer may contaian the usual baryta or it may contain barium sulfite as described in Example 3. The black density developed in the barium sulfite layer does not affect the transfer results.
  • the following example illustrates a coating made in this way.
  • Example 4 A paper support was coated with a suspension of barium sulfite, silver chloride emulsion, and 4-phenyl catechol as a tanning developing agent. This layer was thoroughly flashed to white light before subsequent coating. Over this layer there was coated a gelatino-silver chloride emulsion also containing 4-phenyl catechol. Over the emulsion there was coated a gelatin layer containing zinc sulfide.
  • a support has coated thereon a silver halide emulsion layer 11 having exposed portions 12 and unexposed portions 13, an unhardened colloid layer 14 containing a nucleating agent which is coated over the emulsion layer 11.
  • an unhardened colloid layer 14 containing a nucleating agent which is coated over the emulsion layer 11.
  • a silver image 15 is formed in layer 11 and a silver or silver compound image 16 is formed in the nucleating layer by solvent transfer.
  • this element is rolled into contact with a receiving sheet 17 a portion 18 of the nucleating layer carrying the image is transferred to the sheet 17 as shown in the final stage of Fig. 1.
  • Fig. 2 illustrates the modification of our material in which a support 20 is coated with a layer 21 containing an insoluble sulfite, an emulsion layer 22 and a nucleating layer 23.
  • substantially unhardened gelatin emulsion layer we mean a layer that is not harder than would be the case with gelatin contining 0..25 ounce of formaldehyde (40 percent, diluted 1 to 3 with water) or pound of gelatin when freshly coated, or 0.1 ounce of the formaldehyde solution per pound of gelatin for a sample aged 3 to 6 months.
  • a light-sensitive photographic element comprising a support having thereon at least two layers including a substantially unhardened gelatino-silver halide emulsion layer having a dihydroxy diphenyl developing agent incorporated therein, and a layer of unsensitized, substantially unhardened gelatin containing a chemical precipitant for dissolved silver ions coated directly on said emulsion layer and attached to said emulsion layer to permit transfer of dissolved, undeveloped silver ions from said emulsion layer to said gelatin layer containing said chemical precipitant for dissolved silver ions, upon exposure and development of said emulsion layer in a solvent developer, and to form a reversed photographic image in said stratum containing said chemical precipitant for dissolved silver ions, and to permit transfer of a stratum of said gelatin layer containing said reversed photographic image to a dry, absorbent surface, said gelatin layers being not harder than a gelatin layer containing /4 ounce of formaldehyde per pound of gelatin.
  • the support is a paper support, and a layer of gelatin containing an alkaline earth metal sulfite is located between said support and said emulsion.

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  • Physics & Mathematics (AREA)
  • Chemical & Material Sciences (AREA)
  • General Physics & Mathematics (AREA)
  • Spectroscopy & Molecular Physics (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Paints Or Removers (AREA)
  • Color Printing (AREA)
  • Silver Salt Photography Or Processing Solution Therefor (AREA)
US430074A 1952-05-03 1954-05-17 Transfer process of photographic printing Expired - Lifetime US2843485A (en)

Priority Applications (5)

Application Number Priority Date Filing Date Title
BE538152D BE538152A (en)van) 1952-05-03
GB12183/53A GB746186A (en) 1952-05-03 1953-05-01 Improvements in processes of photographic reproduction and in light-sensitive materials therefor
US430074A US2843485A (en) 1952-05-03 1954-05-17 Transfer process of photographic printing
GB14211/55A GB804283A (en) 1952-05-03 1955-05-17 Improved coating compositions comprising gelatin, particularly for photography
FR1132420D FR1132420A (fr) 1952-05-03 1955-05-17 Procédé de couchage de compositions contenant de la gélatine et nouveaux produits mis en oeuvre

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
US285855A US2725298A (en) 1952-05-03 1952-05-03 Transfer process of photographic printing
US430424A US2831766A (en) 1954-05-17 1954-05-17 Gelatin coating compositions
US430074A US2843485A (en) 1952-05-03 1954-05-17 Transfer process of photographic printing

Publications (1)

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US2843485A true US2843485A (en) 1958-07-15

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US430074A Expired - Lifetime US2843485A (en) 1952-05-03 1954-05-17 Transfer process of photographic printing

Country Status (4)

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US (1) US2843485A (en)van)
BE (1) BE538152A (en)van)
FR (1) FR1132420A (en)van)
GB (2) GB746186A (en)van)

Cited By (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3148060A (en) * 1962-10-16 1964-09-08 Eastman Kodak Co Colloid transfer process and activator solution therefor
US3248219A (en) * 1960-09-06 1966-04-26 Cons Electrodynamics Corp Photographic element for dry processing
US3335005A (en) * 1961-04-13 1967-08-08 Gevaert Photo Prod Nv Silver complex diffusion transfer process
US3364024A (en) * 1963-06-24 1968-01-16 Eastman Kodak Co Photographic process
US3464822A (en) * 1965-09-13 1969-09-02 Du Pont Process for making electrically conductive images
US3511656A (en) * 1955-03-31 1970-05-12 Dick Co Ab Single sheet lithographic dtr master and method of use
US3547641A (en) * 1966-06-20 1970-12-15 Du Pont Planographic offset printing masters
DE1772677A1 (de) * 1967-06-19 1971-05-27 Agfa Gevaert Ag Verwendung eines fotografischen Materials in einem Verfahren zur Herstellung von Flachdruckplatten
US3645731A (en) * 1969-02-08 1972-02-29 Agfa Gevaert Ag Silver salt diffusion alkaline bath of trisodium phosphate and a polyalcohol
US4033770A (en) * 1974-04-11 1977-07-05 Agfa-Gevaert N.V. Production of adhesive transfers by diffusion transfer
US4407932A (en) * 1981-03-12 1983-10-04 Minnesota Mining & Manufacturing Co. Fade-resistant and abrasion resistant photographic reproduction, method of preparing, and photographic product therefor

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB1053568A (en)van) * 1964-08-20

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
NL59365C (en)van) * 1939-11-02
US2543181A (en) * 1947-01-15 1951-02-27 Polaroid Corp Photographic product comprising a rupturable container carrying a photographic processing 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 (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
NL59365C (en)van) * 1939-11-02
US2543181A (en) * 1947-01-15 1951-02-27 Polaroid Corp Photographic product comprising a rupturable container carrying a photographic processing 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

Cited By (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3511656A (en) * 1955-03-31 1970-05-12 Dick Co Ab Single sheet lithographic dtr master and method of use
US3248219A (en) * 1960-09-06 1966-04-26 Cons Electrodynamics Corp Photographic element for dry processing
US3335005A (en) * 1961-04-13 1967-08-08 Gevaert Photo Prod Nv Silver complex diffusion transfer process
US3148060A (en) * 1962-10-16 1964-09-08 Eastman Kodak Co Colloid transfer process and activator solution therefor
US3364024A (en) * 1963-06-24 1968-01-16 Eastman Kodak Co Photographic process
US3464822A (en) * 1965-09-13 1969-09-02 Du Pont Process for making electrically conductive images
US3547641A (en) * 1966-06-20 1970-12-15 Du Pont Planographic offset printing masters
DE1772677A1 (de) * 1967-06-19 1971-05-27 Agfa Gevaert Ag Verwendung eines fotografischen Materials in einem Verfahren zur Herstellung von Flachdruckplatten
US3645731A (en) * 1969-02-08 1972-02-29 Agfa Gevaert Ag Silver salt diffusion alkaline bath of trisodium phosphate and a polyalcohol
US4033770A (en) * 1974-04-11 1977-07-05 Agfa-Gevaert N.V. Production of adhesive transfers by diffusion transfer
US4407932A (en) * 1981-03-12 1983-10-04 Minnesota Mining & Manufacturing Co. Fade-resistant and abrasion resistant photographic reproduction, method of preparing, and photographic product therefor

Also Published As

Publication number Publication date
GB804283A (en) 1958-11-12
BE538152A (en)van)
GB746186A (en) 1956-03-14
FR1132420A (fr) 1957-03-11

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