US3276871A - Printing matrix made by a colloid transfer process - Google Patents

Printing matrix made by a colloid transfer process Download PDF

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Publication number
US3276871A
US3276871A US440671A US44067165A US3276871A US 3276871 A US3276871 A US 3276871A US 440671 A US440671 A US 440671A US 44067165 A US44067165 A US 44067165A US 3276871 A US3276871 A US 3276871A
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Prior art keywords
layer
silver halide
gelatino
halide emulsion
gelatin
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US440671A
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English (en)
Inventor
Thomas I Abbott
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Eastman Kodak Co
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Eastman Kodak Co
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Publication date
Priority to DE19631447892 priority Critical patent/DE1447892A1/de
Priority to FR933765A priority patent/FR1357254A/fr
Priority to GB19001/63A priority patent/GB1023143A/en
Application filed by Eastman Kodak Co filed Critical Eastman Kodak Co
Priority to US440671A priority patent/US3276871A/en
Priority to BE677279D priority patent/BE677279A/xx
Application granted granted Critical
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    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/06—Silver salts

Definitions

  • the present invention concerns photography, and more particularly, photosensitive plates suitable for preparing printing matrixes and processes for preparing such.
  • photosensitive printing or duplicating elements there are several photosensitive printing or duplicating elements known in the art.
  • the printed image is obtained by dissolving a dye in alcohol.
  • this process has many of the characteristics common to spirit duplicating systems in that feathering often results.
  • the most desirable dye for use with this process is the purple commonly seen in copies of this type, this method is not always suitable for reproductions.
  • the spirit duplicating system can only be used with a line copy since there are no intermediate levels of reproduction such as might be obtained in the printing art using a halftone screen or a continuous tone printing plate.
  • a frangible polymer layer is coated over a dye layer, which is then contacted against a moist adhesive photographic image.
  • the frangible layer adheres to the adhesive areas of the photographic element exposing an area of the spirit duplicating medium which then is used for producing an image using alcohol, which dissolves the dye.
  • the present invention concerns a photosensitive element comprising a support, at least one layer coated over the support comprising an organic solventsoluble polymer substrate containing an inert pigment and a tanning developing agent, and coated thereover a photographic gelatino-silver halide emulsion.
  • FIGURE 1 and FIGURE 2 of the drawings are fragmentary sectional views illustrating photosensitive printing elements of the invention.
  • FIGURE 3 of the drawings illustrates in section and schematically three typical stages of the process of the invention for utilizing a photosensitive element such as illustrated by FIGURE 2 to prepare a printing matrix.
  • polymer layer 11 containing a pigment and a tanning developing agent is coated on support 10. Overcoated on polymer layer 11 is photosensitive unhardened gelatino-silver halide layer 12.
  • Polymer layer 11 serves as a reservoir for pigment material to be utilized in mechanically reproducing images with photosensitive elements of the invention.
  • Polymer layer 11 also serves as a reservoir for tanning developer which can be activated by immersing the element in an aqueous alkaline medium.
  • FIGURE 2 is a drawing of another typical photosensitive element of the invention.
  • On support 13 is coated cellulose ether layer 14.
  • Over cellulose ether layer 14 is coated cellulose ether-gelatin layer 15. Both layer 14 and layer 15 serve as reservoirs for pigment and tanning developing agents.
  • Over layer 15 is coated photosensitive unhardened gelatino-silver halide layer 16.
  • FIGURE 3 of the drawings schematically illustrates the processing of the element of FIGURE 2 in accordance with the invention.
  • Stage 1 of the process photosensitive unhardened gelatino-silver halide layer 16 is exposed by light through subject 17 to produce a latent image in layer 16.
  • the resulting exposed element is developed in an aqueous alkaline solution which activates the tanning developing agent in layers 14 and 15 to develop silver halide in the exposed portions of layer 16 to form hardened or tanned gelatino-silver resist image layer 18 as shown in Stage 2 which defines a negative-image area.
  • Unexposed and undeveloped area 19 of layer 16 is thereafter readily stripped out by removing excess water from the surface thereof and pressing in contact therewith, while undeveloped area 19 is still moist, an absorbent grease-free or hydrophilic surface such as receiving sheet 20.
  • unexposed :and undeveloped silver halide 19 is removed or stripped out, leaving hardened gelatino-silver resist image 18 as shown in Stage 3.
  • cellulose ether-gelatin layer 15 is exposed to the surface to form a positive image area.
  • the resulting element can then be utilized as :a matrix to print positive copies of subject 17 by first supplying a suitable organic solvent for the cellulose ether and pressing successive receiving sheets against the element and transferring a portion of the pigment in layers 14 and 15 to such receiving sheet.
  • a suitable organic solvent for the cellulose ether can be utilized, .for example, on a multilith press without ink to prepare copies.
  • the tanning developing agents that can be suitably incorporated in the photosensitive elements of the invention can be of a wide variety.
  • the subject developing agents are typically substantially Water-insoluble developing agents which tan the gelatin carrier for the silver halide upon development in an alkaline solution.
  • tanning developing agents specially useful because of their non-wandering characteristics, high rate of development, high tanning efliciency and solubility in the preferred range, are those having a solubility of from about .005 to 1.0 gram per 100 cc. of a phosphate citric acid bulfer solution of pH 5.0 prepared from a 1.5% solution of sodium dihydrogen phosphate and sufficient citric acid to bring the pH to 5.0.
  • Dihydroxy diphenyl tanning developers are particularly useful.
  • Illustrative suitable tanning developing agents include 3,4-dihydroxy diphenyl, 2,5-dihydroxy diphenyl, 5,6,7,8- tetrahydronaphthohydroquinone, 2,3-dihydroxy diphenyl, methyl pyrocatechol, methyl gentisate, gentisaldehyde, 4- tertiary butyl catechol, 3-methoxy catechol, 4-hexylpyrogallol, 2-phenoxy hydroquinone, and the like.
  • Yackel U.S. Patent No. 2,592,368 dated April 8,1952, and Yackel, U.S. Patent No. 2,685,51O dated August 3, 1954, with respect to suitable tanning developing agents and their incorporation and use in photographic layers.
  • tanning developing agents having low solubility e.g. 4-phenyl catechol
  • the tanning developing agent is dispersed in the polymeric sublayers of the present elements to produce matrixes useful for printing sharp images. This disposition of the developing agents provides a harder resist than can be obtained when the developing agents are used in the gelatino-silver halide emulsion overcoat layer, and further, it is useful in the elimination of an otherwise necessary drying step between strip out and printing.
  • Sufficient developing agent is incorporated in the subject elements to develop the silver halide in the overcoat layeron exposure thereof.
  • the photosensitive layer, the overcoat layer, on the .subject photosensitive element comprises an unhardened gelatino-silver halide emulsion.
  • Silver chloride emulsions are particularly useful, although other silver halide emulsions such as silver bromide, silver chloroiodide, silver chlorobromide, silver chlorobromoiodide and silver bromoiodide emulsions can also be suitably utilized.
  • the gelatino-silver halide emulsion layer is not harder than a gelatin layer containing about 0.7 gram of formaldehyde per pound of gelatin freshly coated.
  • the gelatin substrate of the photosensitive layer is coated so as to have a coverage of about 5Q to 150 mg.
  • gelatin coverage in the photosensitive layer is controlled between such limits to facilitate complete removal of unexposed and undeveloped gelatinosilver halide emulsion during the stripping-out step described above to expose the pigment dispersed in the polymeric substrate below.
  • the pigment utilized in the elements of the invention as built-in ink materials includes a wide variety of coloring materials. Suitable coloring materials are carbon black, ultra-marine blue, Nigrosine dyes, copper phthalocyanine dye, and the like. . The pigment is utilized .only in the subcoatings and not in the photosensitive overcoat layer, this resulting in the printing of particularly sharp images with matrixes prepared in accordance with the invention. Also, the present photoelements are more sensi tive to light than photoelements having the pigment dispersed in silver halide, emulsion layers.
  • the pigment may be a magnetic pigment either in whole or in part.
  • a mixture of carbon black and a magnetic pigment may be used.
  • magnetite Fe O may be used at a coverage of 1.542 g./ft.
  • Magnetite is also described as a ferrosoferric oxide.
  • Other ferro-magnetic iron oxides may. be used, including gamma ferric oxide (Fe O and other magnetic particles which possess the ability to become permanently magnetized, i.e. particles having a high-magnetic susceptibility.
  • the ferro-magnetic particles useful in this invention can be those having a high magnetic permeability. Magnetic particles of nickel, cobalt, and iron are useful for this purpose.
  • a particularly useful material is carbonyl iron, containing iron obtained in particles having a diameter as small as 3 microns from iron carbonyl. However, larger particles can be used depending upon the fineness of detail desired in the image.
  • Carbonyl Iron, Type G sold by the. General Aniline and Film Corporation, is our preferred material. It is about 98 percent pure and has a weight-average diameter of about 8 microns, and is spherically formed.
  • the quantity of pigment and/or magnetic material which is used is not critical but depends upon the desired effect.
  • the magnetic particles will be of particular interest so that the printed image can be sensed .or read by automated equipment, such as in banking applications where the magnetic image is used on checks and related records. It may be desirable to incorporate a small amount of pigment in these magnetic adaptations to provide additional density to the image areas.
  • the pigment may be used solely for the purpose of supplying density and to obtain a sharp image.
  • the polymeric substrate beneath the photosensitive layer of the subject photosensitive elements is comprised essentially of an oleophilic polymeric material that can be solubilized with an organic solvent which does not substantially affect the hardened gelatino-silver resist image produced in the present process.
  • the polymeric layer or layers beneath the photosensitive layer serves as a reservoir for the pigment, and which pigment is brought to the surface for transfer to a receiving sheet for producing an image in the presence of an organic solvent which solubilizes the polymeric material having the pigment dispersed therein, and which solvent is applied to the matrix prepared in accordance with the invention at the time of printing.
  • cellulose polymers such as cellulose ethers are particularly suitable for the subjectsublayers.
  • suitable polymeric substrates include polyvinyl chloride acetates, polyvinyl chloride butyrals, polyvinyl chloride acetals, polyvinyl chloride formals, polystyrenes, polymethacrylates, polyacrylates, and related polymeric compositions.
  • Gelatino-silver halide emulsion layers such as the present photosensitive overcoat layers tend to have poor adhesion to oleophilic layers such as cellulose ether layers.
  • oleophilic layers such as cellulose ether layers.
  • a minor proportion of gelatin mixed with the oleophilic polymeric material improves the adherence of the gelatino-silver halide emulsion layer thereto, and particularly the adherence of the hardened or tanned gelatino-silver resist image thereon during the utilization of the subject elements for printing.
  • from about 10% to 40% by weight of gelatin based on the combined weight of the gelatin and the oleophilic polymer are utilized in the layer immediately below the photosensitive gelatino-silver halide layer..
  • more than one layer is utilized beneath the photosensitive layer.
  • a cellulose ether-gelatin layer is positioned immediately below the photosensitive layer, and the cellulose ether layer is positioned beneath the cellulose ether-gelatino layer for purposes of incorporating additional pigment material in the element.
  • aqueous alkaline solutions are utilized to activate the tanning developer in the present elements in accordance with usual practice.
  • Such alkaline solutions desirably have a pH of at least 10, although the alkalinity of the developing solution can be widely varied in accord-. ance with usual practice, the higher alkalinities serving to reduce the processing time.
  • Alkaline materials such as alkali metal carbonates and hydroxides including sodium carbonate, sodium hydroxide, potassium carbonate, p0- tassium hydroxide, and the like, can be suitably employed as alkaline materials in such activating or processing solutions.
  • the printing matrix prepared in accordance with the invention contains on the surface thereof a gelatino-silver resist negative area and an exposed sublayer of polymeric material as a positive image area, the polymeric material serving as a reservoir for the pigment or ink utilized in the printing process. No additional ink or related material need be utilized to make prints with the present printing matrixes.
  • the surface of the matrix is moistened with a solvent for the polymeric substrate containing the pigment. Organic solvents that are at least as waterimmiscible or oleophilic as n-butanol are utilized. If the solvent is too miscible with water, the gelatino-silver resist tends to dissolve.
  • Useful organic solvents include ether alcohols and ether acetates such as 2-(2-butoxyethoxy) ethyl acetate, as well as such solvents as cyclohexanol, N-butyl acetanilide, di(tetrahydrofural) adipate, and the like,
  • a wide variety of photographic supports can be utilized in preparing the photosensitive elements of the invention. I prefer to utilize conventional photographic supports such as could be utilized in conjunction with multilith and related duplicating equipment. Suitable supports include paper, polyethylene film, cellulose acetate film, polystyrene film, cellulose nitrate film, polyvinyl acetal film, polyethylene terephthalate film, and the like.
  • Example 1 A two-layer photosensitive element of the type illustrated by FIG. 1 was prepared on a polyethylene support. A dispersion containing essentially ethyl cellulose, gelatin, finely divided carbon particles and 4-phenyl catechol in tricresyl phosphate was coated on the support at 10.0 cc. per square foot, the resulting dried coating containing:
  • the resulting photosensitive element was then exposed through a line positive for 1.5 seconds with a No. 2 photoflood bulb at 18 inches. The exposed element was then immersed for seconds in a 3% aqueous sodium carbonate bath at 82 F. to develop the image.
  • a sheet of bond receiving paper was rolled in contact with the developed element, and substantially all unexposed and undeveloped silver halide in the photosensitive overcoat layer was transferred to the receiving paper and stripped oil leaving a matrix-containing a hardened or tanned gelatino-silver resist image.
  • the resulting matrix was attached to the blanket of a multilith press, no ink being used.
  • the surface of the matrix was wetted with organic solvent, 2-(2-butoxyethoxy) ethyl acetate, through the ink rollers and plate cylinder of the press. Approximately 3 cc. of the organic solvent was used for making sharp dense prints on sheets (8%" x 11") of printing paper.
  • organic solvent 2-(2-butoxyethoxy) ethyl acetate
  • FIG. 2 A three-layer photosensitive element of the type illustrated by FIG. 2 was prepared on a polyethylene support.
  • the first layer contained essentially ethyl cellulose, finely milled carbon particles, 4-phenyl catechol, and sucrose acetate isobutyrate, and was coated on the support at 15.0 cc. per square foot, the resulting dried coating containing:
  • Example 3 Addenda: Concentration mg./ft. Magnetite 1,252 Ethyl cellulose 262 Sucrose acetate isobutyrate 1,042 4-phenyl catechol 262 Over the first layer was coated a second layer containing essentially powdered magnetite, ethyl cellulose, gelatin, and 4-phenyl catechol, the resulting dried coating containing:
  • the exposed element was developed by immersing the exposed element for seconds in a 3% aqueous sodium carbonate bath at 82 F., and then unexposed and undeveloped silver halide stripped out by rolling a sheet of bond re- The resulting DCving paper in contact with the developed emulsion on the element and peeling oif the receiving sheet.
  • the resulting matrix was afiixed in a multilith press, wetted with the organic solvent, 2-(2-butoxy-ethoxy) ethyl acetate, and a plurality of prints made having printed characters with high magnetic permeability.
  • the present process thus can be utilized to print magnetic characters of the type utilized'for printing such information as account numbers and branch bank numbers on negotiable instruments and the like.
  • the photoelement described herein comprises a photographic support coated with an organic solvent soluble polymer layer containing a pigment of high magnetic permeability overcoated with an organic solvent soluble polymer :layer containing a pigment of high magnetic permeability, gelatin, and a tanning developing agent. Over this latter layer is coated a photographic unhardened gelatino-silver halide emulsion.
  • the present invention thus provides a new and useful photosensitive element particularly adapted for the photomechanical duplication of positive images.
  • organic solvent-soluble oleophilic polymer is a cellulose ether.
  • tanning developing agent is 4-phenyl catechol.
  • a process as described in claim 12 wherein the tanning developing agent is 4-phenyl :catechol.
  • a photosensitive element comprising a support, a polymer-containing layer comprising an organic oleophilic polymer compatible with a silver halide emulsion and soluble in an organic solvent, at least as immiscible in water as n-butanol, containing dispersed therein a gelatin tanning silver halide developing agent and at least one photographically inert pigment, and coated over said polymer-containing layer a photographic unhardened gelatino-silver halide emulsion layer.
  • a photosensitive element comprising a support, a polymer-containing sublayer comprising an organic oleophilic polymer compatible with a silver halide emulsion and soluble in an organic solvent, at least as immiscible in water as n-butanol, and gelatin at a concentration of about 10% to 40% based on the combined weight of the oleophilic polymer and the gelatin, a dihydroxy diphenyl gelatin tanning silver halide developing agent and at least one photographically inert pigment being dispersed in said sublayer, and coated over said polymer-containing sublayer a photographic unhardened gelatino-silver halide emulsion layer at a coverage of about 50 mg. to mg. of gelatin per square foot.
  • a photosensitive element comprising a support, a first sublayer comprising an organic polymer compatible with a silver halide emulsion and soluble in an organic solvent, at least as immiscible in water as n-butanol, containing dispersed therein a dihydroxy diphenyl gelatin tanning silver halide developing agent and at least one photographically inert pigment, a second sublayer coated over said first sublayer comprising gelatin and said organic solvent-soluble oleophilic polymer containing about 10% to 40% by weight of gelatin, based on the combined weight of the gelatin and organic solvent-soluble oleophilic polymer a dihydroxy diphenyl gelatin tanning silver halide developing agent and at least one photographically inert pigment being dispersed in said second sublayer, and coated over said second sublayer a photographic unhardened gelatino-silver halide emulsion layer at a cover- .age of about 50 mg. to 150 mg. of gelatin per square foot.
  • a photosensitive element comprising a support, a sublayer comprising gelatin and ethyl cellulose containing about 10% to 40% by weight of gelatin based on the combined weight of the ethyl cellulose and the gelatin, a dihydroxy diphenyl gelatin tanning silver halide developing agent and at least one pigment selected from the class consisting of magnetic particles and particulate carbon being dispersed in said sublayer, and coated over said sublayer a photographic unhardened gelatino-silver chloride emulsion layer at a coverage of about 50 mg. to 150 mg. of gelatin per square foot.
  • a photosensitive element comprising a support, a first sublayer comprising ethyl cellulose containing dispersed therein a dihydroxy diphenyl gelatin tanning silver halide developing agent and at least one pigment selected from the class consisting of magnetic particles and particulate carbon, a second sublayer coated over said first sublayer comprising gelatin and ethyl cellulose containing about 10% to 40% by weight of gelatin based on the combined weight of the ethyl cellulose and the gelatin, a dihydroxy diphenyl gelatin tanning silver halide developing agent and at least one pigment selected from the class consisting of magnetic particles and particulate carbon being dispersed in said second sublayer, and coated over said second sublayer a photographic unhardened gelatinosilver chloride emulsion layer at a coverage of about 50 mg. to 150 mg. of gelatin per square foot.

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  • Physics & Mathematics (AREA)
  • General Physics & Mathematics (AREA)
  • Photosensitive Polymer And Photoresist Processing (AREA)
  • Silver Salt Photography Or Processing Solution Therefor (AREA)
  • Paints Or Removers (AREA)
US440671A 1962-05-14 1965-03-04 Printing matrix made by a colloid transfer process Expired - Lifetime US3276871A (en)

Priority Applications (5)

Application Number Priority Date Filing Date Title
DE19631447892 DE1447892A1 (de) 1962-05-14 1963-03-27 Photographisches Material sowie Verfahren zur Herstellung von Druckmatrizen aus diesem Material
FR933765A FR1357254A (fr) 1962-05-14 1963-05-06 Nouveau produit photosensible utilisable pour la préparation de clichés d'impression
GB19001/63A GB1023143A (en) 1962-05-14 1963-05-14 Photographic production of printing matrices
US440671A US3276871A (en) 1962-05-14 1965-03-04 Printing matrix made by a colloid transfer process
BE677279D BE677279A (pm) 1962-05-14 1966-03-02

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US19430562A 1962-05-14 1962-05-14
US440671A US3276871A (en) 1962-05-14 1965-03-04 Printing matrix made by a colloid transfer process

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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4369245A (en) * 1980-07-28 1983-01-18 Minnesota Mining And Manufacturing Company Photographic element for tanning development and method for obtaining colored relief image
US4427757A (en) 1982-08-27 1984-01-24 Minnesota Mining And Manufacturing Company Tannable imaging element
US4444866A (en) * 1980-04-28 1984-04-24 Fuji Photo Film Co., Ltd. Photographic light-sensitive material with forced oxidized carbon black

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3637389A (en) * 1969-04-07 1972-01-25 Agfa Gevaert Nv Method of producing photographic images by rapid processing

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2409564A (en) * 1941-05-28 1946-10-15 Noc Mfg Company Di Transfer material
US3146104A (en) * 1959-12-21 1964-08-25 Eastman Kodak Co Silver halide sensitized lithographic printing plate
US3152898A (en) * 1958-10-08 1964-10-13 Eastman Kodak Co Photographic material for spirit duplicating
US3157506A (en) * 1957-11-08 1964-11-17 Eastman Kodak Co Photographic film base subbed with acid-cooked pigskin gelatin

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2409564A (en) * 1941-05-28 1946-10-15 Noc Mfg Company Di Transfer material
US3157506A (en) * 1957-11-08 1964-11-17 Eastman Kodak Co Photographic film base subbed with acid-cooked pigskin gelatin
US3152898A (en) * 1958-10-08 1964-10-13 Eastman Kodak Co Photographic material for spirit duplicating
US3146104A (en) * 1959-12-21 1964-08-25 Eastman Kodak Co Silver halide sensitized lithographic printing plate

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4444866A (en) * 1980-04-28 1984-04-24 Fuji Photo Film Co., Ltd. Photographic light-sensitive material with forced oxidized carbon black
US4369245A (en) * 1980-07-28 1983-01-18 Minnesota Mining And Manufacturing Company Photographic element for tanning development and method for obtaining colored relief image
US4427757A (en) 1982-08-27 1984-01-24 Minnesota Mining And Manufacturing Company Tannable imaging element

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BE677279A (pm) 1966-08-01
GB1023143A (en) 1966-03-23
DE1447892A1 (de) 1969-03-06

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