US3565618A - Photographic colloid transfer facilitated by enzyme treatment - Google Patents

Photographic colloid transfer facilitated by enzyme treatment Download PDF

Info

Publication number
US3565618A
US3565618A US562863A US3565618DA US3565618A US 3565618 A US3565618 A US 3565618A US 562863 A US562863 A US 562863A US 3565618D A US3565618D A US 3565618DA US 3565618 A US3565618 A US 3565618A
Authority
US
United States
Prior art keywords
emulsion
enzyme
solution
colloid
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
US562863A
Other languages
English (en)
Inventor
Claude M Marechal
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
Application filed by Eastman Kodak Co filed Critical Eastman Kodak Co
Application granted granted Critical
Publication of US3565618A publication Critical patent/US3565618A/en
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

Links

Images

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
    • G03C11/00—Auxiliary processes in photography
    • G03C11/12—Stripping or transferring intact photographic layers
    • 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
    • G03C5/00—Photographic processes or agents therefor; Regeneration of such processing agents
    • G03C5/26—Processes using silver-salt-containing photosensitive materials or agents therefor
    • G03C5/29—Development processes or agents therefor
    • G03C5/315—Tanning development
    • 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
    • G03C5/00—Photographic processes or agents therefor; Regeneration of such processing agents
    • G03C5/26—Processes using silver-salt-containing photosensitive materials or agents therefor
    • G03C5/40—Chemically transforming developed images

Definitions

  • This invention relates to photography and particularly to a transfer process of printing a photographic image.
  • FIG. 1 illustrates, in enlarged cross-sectional view, a processed photographic element carrying an unhardened emulsion layer containing a silver image.
  • FIG. 2 shows an enlarged cross-sectional view emphasizing the sharply defined area affected by the enzyme treatment.
  • FIG. 3 shows in enlarged cross-sectional view the method of transferring a stratum of the processed emulsion layer to a receiving support.
  • FIG. 4 shows in enlarged cross-sectional view the appearance of the transferred emulsion stratum on the receiving support.
  • a substantially unhardened, dried processed gelatin emulsion layer is Wetted with a proteinase solution.
  • a proteinase solution When the emulsion is dipped into the proteinase solution, the emulsion is superficially degraded and the hydrolysis front progresses in depth with a remarkable and surprising regularity.
  • the emulsion is then brought (by rolling, squeegeeing, etc.) into intimate contact with a suitable receiving support, such as paper, cloth, wood or similar absorptive material. After stripping the receiving support from the emulsion layer, a thin stratum of degraded emulsion is found transferred to the receiving support.
  • the process can be repeated for successive transfers.
  • the appearance of the processed photographic element is simulated in enlarged cross-sectional view in FIG. 1 wherein layer 10 is the emulsion support of a proper base (paper, film or other material) carrying an unhardened emulsion layer 11 containing the image (silver, dye, etc.) 12.
  • the effect of the proteinase treatment on the emulsion is emphasized in FIG. 2 wherein the support 10 is now carrying essentially unaffected emulsion layer 13 containing the image area 14.
  • the layer affected by the proteinase is layer .15 containing image area 16.
  • the method of transferring stratum 15 containing image area 16 to a receiving support is shown in FIG.
  • layer 10 is the emulsion support carrying the residual unhardened emulsion layer 13 and residual image 14 which are left on support 10 after stripping off the stratum of emulsion 15 containing the image 16, 15 and 16 adhering to the receiving support 17.
  • the appearance of the transferred emulsion stratum on the receiving support is shown in enlarged cross-sectional view in FIG. 4 wherein layer 17 is the receiving support carrying emulsion stratum 15 containing the image 16.
  • several prints' are obtained simultaneously by accomplishing transfer onto a stack of several sheets of very thin porous paper.
  • the sandwich formed by the receiving sheets and the matrix sheet is kept at a higher temperature than room temperature, e.g., 40 C. in order to increase the hydrolysis speed.
  • room temperature e.g. 40 C.
  • the hydrolysis materials migrate through the paper sheets and carry along the silver grains or the dyes of the matrix. A single operation is sulficient for obtaining multiple prints.
  • EXAMPLE 1 A daylight incorporated coupler type reversal color film was exposed and processed, except that the emulsion was not hardened. The completely processed and dried element was treated for 15 seconds in a solution containing 4 g. of trypsin per liter. Several successive strata (four or five) of each of the emulsion layers which constitute the color film could be transferred to successive unsized 88 g. paper sheets to obtain as many prints of each of the three separation images. Between two successive transfer operations, the matrix was dipped in the enzyme solution.
  • EXAMPLE 3 A film with a high contrast silver halide emulsion coated on a thin base, was exposed and developed in a nonhardening developer of the following composition:
  • N-methyl-para-aminophenol sulfate 1 Sodium sulfite (desiccated) 75 Hydroquinone 9 Sodium carbonate (desiccated) Potassium bromide 5 Water to make 1 liter.
  • the emulsion was subjected to gelatin softening treatment by a solution of 10 g. urea in 1 liter of water. It was dried and then dipped for 5 seconds in the following enzyme solution:
  • Example 4 The procedure of Example 3 was repeated, except that enzyme solutions containing a softening agent and having one of the following compositions (A) to (D) were used:
  • Baths (A) to (D) contain urea as a softening agent.
  • This softening agent may be used also in a distinct bath as in Example 3; in this case, treatment is first carried out with the softening bath and then with the enzyme bath which itself may contain a softening agent.
  • Softening baths used as a pretreatment are made up of solutions containing 10 g. of urea per liter or 20 g. of potassium thiocyanate per liter. Of course, the bath or baths to be used will depend on the hardening of the emulsion employed and is a matter of choice.
  • substantially unhardened emulsion means an emulsion having a melting point of about 40 C. in hot Water.
  • gelatin emulsions may also be defined as emulsions which are not harder than would be the case with gelatin containing 0.25 ounce of formaldehyde (40%, diluted 1 to 3 with water) per 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.
  • EXAMPLE 5 It is possible to carry out development in a hardening developer containing an enzyme; for example an emulsion of the type described in Example 4 can be processed in a developer of the following composition:
  • Hydroquinone 10 Sodium sulfite (desiccated) 2 Sodium carbonate (desiccated) 20 Trypsin (20,000 units) 5 Distilled water 1000 ml.
  • Examples 6 and 7 give compositions of developers that may be used in place of the one described in Examples 3 and 4.
  • EXAMPLE 8 A print was prepared which contained a color image in a mordanted gelatin layer, by the imbibition printing process.
  • the print was soaked with a A solution of trypsin, at 25 C., then the emulsion side was applied into contact with a stack of sheets of 12 g./m. paper, intended for the making of tea bags, also soaked with enzyme.
  • the sandwich was drained between two rubber rollers and kept at 40 C. on a heating plate. Two minutes later, four prints were obtained.
  • This process provides multiple prints from any of a variety of 'known gelatin and gelatin derivative emulsions which are used in standard, commercial, X-ray, graphic arts black and white negative, color, negative, black and white positive, and color positive film.
  • the number of transfers possible is dependent upon the time the enzyme acts on the colloid, the particuler enzyme chosen, as well as the hardening characteristics, temperature, thickness, etc., of the emulsion.
  • the system is utilized for a stratum transfer, i.e., a thin layer of the total surface of the photographic element is carried off into a receiving support, the system works well with emulsions which have portions of the surface area hardened and portions unhardened. The hardened areas are substantially unaffected while the unhardened areas are transferred readily to a receiving support.
  • Proteinases which are very effective in the invention are pepsine, trypsin, papaine, in solution in relatively pure state or admixed with other enzymes, etc. as in pancreatine, which is a mixture of lipase, amylase and trypsin and also in commercially available proteinase compositions, e.g. Rhozyme (registered trademark of Rohm and Haas Co.) which is known as a saccharifying enzyme. Enzymes of this type are also useful in my invention.
  • enzymes which hydrolyze proteins include: peptidase, erepsin, arginase, carbamase, nuclease, etc.
  • the selection of the specific enzymes in each case is mainly dependent upon the pH at which the operation is to be conducted. For example, pepsin is active in low pH medium whereas trypsin acts optimally at slightly alkaline pH values.
  • the bath is generally kept at 22 C. although for the specific enzymes mentioned, the hydrolysis may start at about 18. At about 55 C. the enzymes are most active but the activity drops off sharply at 70 C.
  • the concentration of the enzyme can vary from only a few milligrams to several grams per liter of bath.
  • the enzyme solution can contain any of a number of conventional photographic addenda and can serve as a simultaneous processing bath and enzyme bath, providing the pH, etc., of the processing bath do not inhibit enzyme action. If the pH does inhibit the enzyme action, an after bath adjusting the enzyme soaked film to the proper pH can be effective.
  • the enzyme solution can also be applied to the film in various ways, for example dipping the film in a bath as mentioned above, spraying the solution on the film, applying the solution from a processing pod wherein the enzyme is normally associated in a thickened (e.g., with carboxymethylcellulose) aqueous solution.
  • the enzyme solution has to be in contact with the colloid only for a short time, for example, when employing an enzyme bath, usually only a 2-10 second period (preferably 4-5 seconds) is required. Most effective transfers can be accomplished in -20 seconds later.
  • the process and materials of the present invention have a host of apparent uses in experimental photography such as in determining the penetration of light, in determining the penetration of various processing baths, study of hardening diffusion of the sensitizing dyes, posltion of coatrng defects, study of interimage effects, etc.
  • Commercial applications are just as numerous, e.g., illustrating punch cards, black and white and color copying processes, coating extra thin layers, ersonalizing conventional household and business items, etc.
  • This invention finds particular advantage in the solvent transfer system wherein previously no practical, inexpensive method existed for making multiple prints.
  • proteinase is selected from the group consisting of pepsin, trypsin, papaine and saccharifying enzymes.
  • a method for the reproduction of photographic images by a colloid stratum transfer process from a relatively dry, processed, image-bearing photographic eemperent, the image-forming material of which is suspended in a proteinaceous colloid emulsion vehicle comprising:
  • a method of claim 12 in which the proteinase is selected from the group consisting of pepsin, trypsin, papaine and saccharifying enzymes.
  • 20. A method of claim 19 wherein the proteinase solu- 17.

Landscapes

  • Physics & Mathematics (AREA)
  • General Physics & Mathematics (AREA)
  • Silver Salt Photography Or Processing Solution Therefor (AREA)
  • Paper (AREA)
  • Laminated Bodies (AREA)
  • Photosensitive Polymer And Photoresist Processing (AREA)
US562863A 1966-03-02 1966-07-05 Photographic colloid transfer facilitated by enzyme treatment Expired - Lifetime US3565618A (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
FR51627A FR1476797A (fr) 1966-03-02 1966-03-02 Procédé de report de couches de colloïde utilisable notamment en photographie
FR562863 1966-07-05

Publications (1)

Publication Number Publication Date
US3565618A true US3565618A (en) 1971-02-23

Family

ID=26168930

Family Applications (1)

Application Number Title Priority Date Filing Date
US562863A Expired - Lifetime US3565618A (en) 1966-03-02 1966-07-05 Photographic colloid transfer facilitated by enzyme treatment

Country Status (5)

Country Link
US (1) US3565618A (de)
BE (1) BE693709A (de)
DE (1) DE1547778A1 (de)
FR (1) FR1476797A (de)
GB (1) GB1179769A (de)

Cited By (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3909328A (en) * 1973-04-10 1975-09-30 Du Pont Decoration of substrates by thermal transfer of photosensitive, thermoplastic, dye-imaged film
US4207102A (en) * 1974-10-21 1980-06-10 E. I. Du Pont De Nemours And Company Marking transfer sheets and process
US4232108A (en) * 1979-05-01 1980-11-04 E. I. Du Pont De Nemours And Company Marking transfer sheets
US4390614A (en) * 1981-03-16 1983-06-28 Richard M. Peck Color facsimile printing device comprising photosensitive ink in pores
US4420552A (en) * 1981-03-16 1983-12-13 Richard M. Peck Method of producing printed images with a color facsimile printing device
US4567131A (en) * 1983-07-11 1986-01-28 Vickers Plc Lithographic printing plates
US6258520B1 (en) * 2000-04-11 2001-07-10 Eastman Kodak Company Hydrolyzed water-resistant protective overcoat for an imaging element
US6280912B1 (en) * 2000-09-19 2001-08-28 Eastman Kodak Company Protective overcoat for an imaging element comprising an enzyme-treated biopolymer
FR2920553A1 (fr) * 2007-09-05 2009-03-06 Valerie Legembre Matiere a multicouches a base d'image photographique

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE3325762A1 (de) * 1983-07-16 1985-01-24 Agfa-Gevaert Ag, 5090 Leverkusen Fotografisches farbdiffusionsuebertragungsverfahren und hierfuer geeignetes farbfotografisches aufzeichnungsmaterial

Cited By (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3909328A (en) * 1973-04-10 1975-09-30 Du Pont Decoration of substrates by thermal transfer of photosensitive, thermoplastic, dye-imaged film
US4207102A (en) * 1974-10-21 1980-06-10 E. I. Du Pont De Nemours And Company Marking transfer sheets and process
US4232108A (en) * 1979-05-01 1980-11-04 E. I. Du Pont De Nemours And Company Marking transfer sheets
US4390614A (en) * 1981-03-16 1983-06-28 Richard M. Peck Color facsimile printing device comprising photosensitive ink in pores
US4420552A (en) * 1981-03-16 1983-12-13 Richard M. Peck Method of producing printed images with a color facsimile printing device
US4567131A (en) * 1983-07-11 1986-01-28 Vickers Plc Lithographic printing plates
US6258520B1 (en) * 2000-04-11 2001-07-10 Eastman Kodak Company Hydrolyzed water-resistant protective overcoat for an imaging element
US6280912B1 (en) * 2000-09-19 2001-08-28 Eastman Kodak Company Protective overcoat for an imaging element comprising an enzyme-treated biopolymer
US6406838B1 (en) * 2000-09-19 2002-06-18 Eastman Kodak Company Protective overcoat for an imaging element comprising an enzyme-treated biopolymer
FR2920553A1 (fr) * 2007-09-05 2009-03-06 Valerie Legembre Matiere a multicouches a base d'image photographique

Also Published As

Publication number Publication date
FR1476797A (fr) 1967-04-14
BE693709A (de) 1967-07-17
GB1179769A (en) 1970-01-28
DE1547778A1 (de) 1969-12-04

Similar Documents

Publication Publication Date Title
US2596756A (en) Photomechanical copy method
US2352014A (en) Photomechanical printing process and printing material for carrying out the same
US2647056A (en) One step photographic transfer process
US3565618A (en) Photographic colloid transfer facilitated by enzyme treatment
US2596754A (en) Photomechanical copy method
US2725298A (en) Transfer process of photographic printing
US4226927A (en) Photographic speed transfer element with oxidized polyethylene stripping layer
US2692830A (en) Photographic silver halide transfer process
US2388894A (en) Method of developing photographic emulsions
US2013116A (en) Photographic matrix
GB1256971A (de)
US3232756A (en) Colloid transfer process
US2852371A (en) Photographic duplicating process
GB825866A (en) Method of making a lithographic printing plate suitable for lithographic printing and hardening solution therefor
GB878149A (en) Improvements in the preparation of photographic dye images
GB1337071A (en) Reversal colour photographic process
US3960567A (en) Process and composition for producing photolithographic plate for the graphic arts
US1946640A (en) Method of making wash-off relief images
US4012250A (en) Imaging system
US3240600A (en) Colloid transfer process
US1950903A (en) Controlled reduction of photographic images
GB1061728A (en) Photographic methods and materials for making relief images
US1417328A (en) Light film
US3060052A (en) Transfer of xerographic dye images
US2705676A (en) Method of copying negative photographic images by transfer of silver salt to a receiving layer