US3152898A - Photographic material for spirit duplicating - Google Patents

Photographic material for spirit duplicating Download PDF

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Publication number
US3152898A
US3152898A US45919A US4591960A US3152898A US 3152898 A US3152898 A US 3152898A US 45919 A US45919 A US 45919A US 4591960 A US4591960 A US 4591960A US 3152898 A US3152898 A US 3152898A
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US
United States
Prior art keywords
layer
insoluble
dye
blue
water
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
US45919A
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English (en)
Inventor
Hepher Martin
Przezdziecki Wojciech Maria
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Eastman Kodak Co
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Eastman Kodak Co
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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
    • 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
    • G03F7/26—Processing photosensitive materials; Apparatus therefor
    • G03F7/34—Imagewise removal by selective transfer, e.g. peeling away
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10S101/00—Printing
    • Y10S101/29—Printing involving a color-forming phenomenon

Definitions

  • the image is formed in reverse on a master by transfer from a carbontype sheet coated with a composition containing a high proportion of a spirit soluble dye such as Crystal Violet,.
  • our photographic element consists of a sheet of paper similar to that used for normal photographic sensitizing that is coated with a layer of.
  • Waterinsoluble alcohol-soluble dye in a suitable water-insoluble binder over which is coated a thin layer of unhardened silver halide emulsion with an incorporated tanning developing agent.
  • the silver halide emulsion layer of the material is exposed to a positive image by contact printing or by projection printing. Then the incorporated tanning developing agent in the exposed silver halide emulsion layer is activated by immersing the material in an alkaline .solution. In those areas where the silver halide has been-exposed, the gelatin is tanned or hardened as a silver image is developed, while the gelatin in the areas of the emul- "sion that were not exposed remain unhardened.
  • the unhardened areas of the gelatin silver halide emulsion are then stripped off by squeegeeing this layer of the element into contact with a plain sheet of paper and after 20 or 30 seconds stripping off the paper with the unhardened emulsion, thus exposing in these areas the resin dye layer of the printing matrix.
  • the gelatin stencil image on the matrix is then dried, then the matrix is placed on the cylinder of a spirit duplicator and positive images transferred'to receiving or copy paper by the usual method.
  • the strongly colored dye used in the resin layer of the photographic element described above for port of the photographic element.
  • Patented Get. is, 1964 making a printing matrix can be replaced by a dye intermediate or color-forming compound that does not absorb light in the region of sensitivity of the silver halide in the photographic emulsion layer.
  • This element can be exposed as described above or more advantageously by reflex printing in which the image side of the original document to be copied is held in firm contact with the light-sensitive silver halide emulsion layer of the photo graphic element while the light-sensitive emulsion layer is exposed by passing the exposing light through the sup-
  • the printing matrix is then prepared by developer activation, stripping and drying as described above.
  • the dye intermediate or colorforming component is then transferred to the receiving sheet and converted into the strongly colored dye by reacting the dye intermediate with a suitable coupler or reagent either in the transfer solvent or in the receiving sheet.
  • any suitable support may be used for making the photographic element of our invention.
  • the support may be paper, a plastic such as cellulose acetate, cellulose nitrate, polyethylene terephthalate, polystyrene, polycarbonate, etc., glass, metal, etc.
  • the support used must not be opaque to the exposing light but must transmit this light sufilciently well to facilitate exposure of the light-sensitive silver halide emulsion layer by this method.
  • Plain paper or paper of the kind usually used in the production of commercial. photographic papers which usually bear a gelatinous subbing layer are used advantageously.
  • the resin dye layer coated over the support should advantageously possess the following characteristics.
  • C It should be preferably alcohol soluble but substantially insoluble in water or alkali.
  • a polyvinyl acetate which has not been hydrolyzed or sufiiciently hydrolyzed to make it water soluble is a preferred resin for making our photographic elements.
  • Other resins which can be used include zein, alcohol-soluble nylon plastic, polyvinyl butal, polyvinyl formal, polyethylacrylate, polymethylmethacrylate, etc.
  • polyvinyl phthalate can be used advantageously for this purpose.
  • a thin layer of an alkali-swellable or alkali-soluble colloid such as polyvinyl phthaiate may be coated between the resin layer and the light-sensitive silver halide emulsion layer.
  • the photographic elements of our invention that are designed for contact or projection printing contain dye in the resin layer. This dye should advantageously fulfill the following conditions.
  • the photographic elements of our invention that are designed for reflex printing contain a colorless dyeforming material.
  • the one or two component systems used should advantageously have the following characteristics.
  • the spectral absorption of the color-forming component used beneath the emulsion that is in the resin layer must be low in the actinic region (green).
  • At least one component has to be freely soluble in alcohol but completely insoluble in water.
  • the component present in the sub-layer or resin layer should be stable at the pH of the emulsion.
  • the dye produced should be stable to light and atmosphere.
  • colorless material useful for making this type of photographic element is bis(para-dimethylaminophenyl)rnethane which is incorporated in the resin layer. This material is oxidized during the transfer operation to produce a deep blue dye.
  • the transfer solvent used for this purpose contains cupric chloride and phosphotungstic acid in methyl alcohol in order to facilitate oxidation of the colorless dye former and produce the dye.
  • organic dyestufi derivatives that can be used for the present process are the leuco bases and the lactones of triphenylmethane-dyes.
  • leuco bases For example, Leuco Malachite Green and Malachite Green lactone.
  • the leuco compound is oxidized during the transfer operation to the carbinol base of Malachite Green which in the presence of an acid changes to the dye proper.
  • the lactone on the other hand gives a corresponding dye in the presence of an acid or other acetic inorganic compound.
  • the dyes produced from triphenylmethane lactones by adsorption onto attapulgite, for example, are not completely stable at atmospheric conditions. For this reason up to 50 percent of an oxidizable dye-forming material such as benzoyl leuco methylene blue should be addedto the dye-forming layer.
  • an oxidizable dye-forming material such as benzoyl leuco methylene blue
  • the lactone takes part in the adsorption reaction immediately upon making contact with the acidic substance and turns to a dark blue.
  • the benzoyl leuco methylene base when in contact with the acidic substances oxidizes after the passage of some time and turns to a dark blue color reinforcing the color formed from the lactone which is apt to fade after being exposed to light and air.
  • colorless x-anthene derivatives such as those mentioned in British Patent 712,216 are alcohol soluble compounds which give readily a red dye When contacted with inorganic clays.
  • the derivative is xanthene 9, orthobenzoic acid, 3,6-diethylamino-9-para-nitroanilino lactam.
  • the photographic element with the emulsion layer containing incorporated developing agent is developed by immersion in a development activator such as those described in Yutzy et al., US. Patents 2,716,059 and 2,739,890. If the emulsion of the element does not contain incorporated developing agent, the exposed element is developed in a. solution containing developing agent and activator. Following development, the wet photographic element is squeegeed into contact with a receiving sheet which may be a piece of ordinary paper, a translucent copy paper, or a paper containing thiourea and sodium formaldehyde bisulfite as described in U.S.
  • a receiving sheet which may be a piece of ordinary paper, a translucent copy paper, or a paper containing thiourea and sodium formaldehyde bisulfite as described in U.S.
  • Patent 2,865,745 then the receiving sheet is separated from the photographic element so as to remove the unexposed and unhardened gelatin from the photographi element and lays bare the spirit soluble resin layer containing the dye or dye-forming compound.
  • Any suitable solvent may be used in the spirit duplicating process which will dissolve the dye or dye-forming compound and preferably be capable of dissolving the resin layer.
  • Methyl alcohol or the mixtures of methyl alcohol and other organic solvents such as acetone, toluene, etc., can be used to advantage in making multiple copies of our photographioally produced printing matrix on a spirit duplicating machine.
  • Other materials may be added to the spirit solvent for specific purposes. For example, phosphotungstic acid, citric acid, and oxidizing agents such as cupric chloride, etc.
  • any paper such as that used for receiving sheets on spirit duplicating process can be used for receiving the dye image from our printing matrix.
  • Plain paper may be used to advantage as a receiving material excepting in those cases where special conditions are required.
  • the laetones of triphenylmethane dyes are used as a colorless dye former in the resin layer, the corresponding dye is formed in the presence of an acid or acidic inorganic compound.
  • This may be present in the spirit duplicating solvent or may be present on the surface of the receiving sheet.
  • the receiving sheet may contain inorganic compounds such as attapulgite, kaolin, bentonite, etc.
  • Example I as described in YutZy et al., U.S. Patent 2,596,756, Example 1.
  • a sheet of baryta paper was coated with a mixture of 90 cc. of 3 percent polyvinyl acetate in methyl alcohol, 10 cc. of 3 percent polvinyl phthalate in. 70/30 methyl alcohol/ acetone and 1 g. of Brilliant Oil Blue EMA dye. Over this was coated a thin layer of the gelatin silver chloride emulsion of Example 1. After drying, it was exposed and processed as in Example 1. Similarly twenty copies were obtained from this printing matrix by -a spirit duplicating process.
  • Example III A sheet of baryta paper was coated with a mixture of g. of polyvinyl acetate, 2 g. of Michlers Hydrol and 100 cc. of methyl alcohol. After drying, this layer was coated with a gelatin silver chloride emulsion layer prepared as in Example 1. After drying, this layer was exposed, processed and dried as in Example I. The dried matrix was then used to prepare copies by a spirit duplicating process in which the solvent had the following composition:
  • FIGS. 1, 2, and 3 will serve to further describe the process fior making printing matrices from our photographic element and using them to produce spirit copies.
  • our photographic element comprising support it over which is coated layer 11 containing polyvinyl acetate and Brilliant Oil Blue BMA dye over which is coated layer 12 consisting of a substantially unhardened gelatin silver chloride emulsion layer that is being exposed to the image in the original record 13 by light from light source 14.
  • FIG. 2 shows how the exposed photographic element of FIG. 1, which has been developed, is converted into a printing matrix by stripping oil the unexposed, undeveloped gelatin areas of layer 12 with receiving layer 15 which was squeegeed in contact with layer 12 and then stripped off.
  • FIG. 3 shows how a Brilliant Oil Blue BMA dye image has been transferred from the exposed areas of resin dye layer 11 to the receiving sheet 16 by a spirit duplicating process to produce the spirit copy.
  • the photographic element of our invention is valuable for use in preparing multiple copies of printed documents. It provides a simple and rapid process by which an original document may be copied by contact printing, projection printing or reflex printing and by which this photographic exposure may be converted into a printing matrix for producing multiple spirit copies using com- 5 monly available spirit duplicating equipment.
  • Our photographic element makes it possible to eliminate the involved and complicated wet processing that is required by prior art materials available for producing spirit duplicating matrices.
  • Our photographic elements are not only adapted to make the spirit duplicating matrices rapidly and simply but are adapted to be used in lighted office areas on equipment that is generally readily available.
  • a photographic element designed for preparing a printing matrix for spirit duplicating processes comprising:
  • a water-insoluble, alkali-insoluble organic resin binder selected from the class consisting of a polyvinyl acetate, zein, an alcohol-soluble nylon plastic, polyvinyl butal, polyvinyl formal, polyethylacrylate, and polymethylmethacrylate, and
  • a water-insoluble, organic solvent-soluble member selected from the class consisting of 6- (2,4 dinitro 6'-N-ethylsulfonamidebenzeneazo) N-flgy-dihydroxypropyl-Z-methyltetrahydroquinoline, Brilliant Oil Blue EMA, Solvent Blue 16, Grasol Blue R, Celanthrene Sky Blue B, the Carbinol base of Victoria Blue, Michlers hydrol, a lactone of a triphenylmethane dye, a
  • a photographic element of claim 1 containing between the water-insoluble, alkali-insoluble layer and the thin light-sensitive substantially unhardened organic colloid silver halide emulsion layer, a thin water-insoluble layer consisting of polyvinyl phthalate.
  • a photographic reproduction process utilizing a photographic element designed for preparing a printing matrix for spirit duplication processes comprising:
  • a water-insoluble, alkali-insoluble organic resin blender selected from the class consisting of a polyvinyl acetate, zein, an alcohol-soluble nylon plastic, polyvinyl butal, polyvinyl formal, polyethylacrylate, and polymethylmethacrylate, and
  • a water-insoluble, vorganic solvent-soluble member selected from the class consisting of 6- (2',4' dinitro 6'-N-ethylsulfonamidebenzeneazo) N 5,'y-dihydroxypropy1-2-methyltetrahydroquinoline, Brilliant Oil Blue BMA, Solvent Blue 16, Grasol Blue R, Celanthrene Sky Blue B, the Carbinol base of Victoria Blue, Michlers hydrol, a lactone of a triphenylmethane dye, a leuco base of a triphenylmethane dye, a lower alkyl ether of a triphenylmethane dye, and Xanthene 9, orthobenzoic acid, 3,6-diethylamino- 9-p-nitroanilino lactam, and coated over said Water-insoluble layer,
  • a photographic element designed for preparing a printing matrix for spirit duplicating processes comprising a support, a water-insoluble, alkali-insoluble resin layer coated over the support, said layer comprising polyvinyl acetate and Brilliant Oil Blue BMA dye and a thin light-sensitive substantially unhardened gelatin silver halide emulsion layer incorporating 3,4-dihydroxy diphenyl coated over said resin layer.
  • a photographic element designed for preparing a printing matrix for spirit duplicating processes comprising a support, a Water-insoluble, alkali-insoluble resin layer coated over the support, said layer comprising polyvinyl acetate, polyvinyl phthalate and Brilliant Oil Blue BMA dye and a thin light-sensitive substantially unhardened gelatin silver halide emulsion layer incorporating 3,4-dihydroXy diphenyl coated over said resin layer.
  • a photographic element designed for preparing a printing matrix for spirit duplicating processes comprising a support, a water-insoluble, alkali-insoluble resin layer coated over the support, said layer comprising polyvinyl acetate and Brilliant Oil Blue BMA dye and a thin light-sensitive substantially unhardened gelatin silver halide emulsion layer incorporating 3,4-dihydroxy diphenyl coated over said resin layer.
  • a photographic element designed for preparing a printing matrix for spirit duplicating processes comprising a support, a Water-insoluble, alkali-insoluble resin layer coated over the support, said layer comprising polyvinyl acetate, polyvinylphthalate and the carbinol base of Victoria Blue and a thin light-sensitive substantially unhardened gelatin silver halide emulsion layer incorporating 3,4-dihydroxy diphenyl coated over said resin layer.
  • a photographic element designed for preparing a printing matrix for spirit duplicating processes comprising a support, a water-insoluble, alkali-insoluble resin layer coated over the support, said layer comprising polyvinyl acetate and the carbinol base of Victoria Blue, a thin subbing layer of polyvinyl phthalate coated over said resin layer and a thin light-sensitive substantially unhardened gelatin silver halide emulsion layer incorporating 3,4-dihydroxy diphenyl coated over said resin layer.
  • a photographic element designed for preparing a printing matrix for spirit duplicating processes comprising a support, a water-insoluble, alkali-insoluble resin layer coated over the support, said layer comprising polyvinyl acetate and his (para-dimethylamino-phenyl)methane and a thin light-sensitive substantially unhardened gelatin silver halide emulsion layer incorporating 3,4-dihydroxy diphenyl coated over said resin layer.

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  • Physics & Mathematics (AREA)
  • General Physics & Mathematics (AREA)
  • Silver Salt Photography Or Processing Solution Therefor (AREA)
  • Color Printing (AREA)
  • Photosensitive Polymer And Photoresist Processing (AREA)
US45919A 1958-10-08 1960-07-28 Photographic material for spirit duplicating Expired - Lifetime US3152898A (en)

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
GB32060/58A GB931397A (en) 1958-10-08 1958-10-08 Photographic process and materials for spirit duplicating

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US3152898A true US3152898A (en) 1964-10-13

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US45919A Expired - Lifetime US3152898A (en) 1958-10-08 1960-07-28 Photographic material for spirit duplicating

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US (1) US3152898A (en(2012))
BE (1) BE583385A (en(2012))
DE (1) DE1095663B (en(2012))
FR (1) FR1247963A (en(2012))
GB (1) GB931397A (en(2012))

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3241965A (en) * 1959-12-11 1966-03-22 Ritzerfeld Wilhelm Method of preparing and using hectographic masters
US3252412A (en) * 1955-05-11 1966-05-24 Gevaert Photo Prod Nv Process for producing hectographic prints
US3276871A (en) * 1962-05-14 1966-10-04 Eastman Kodak Co Printing matrix made by a colloid transfer process

Citations (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2131747A (en) * 1937-10-13 1938-10-04 Eastman Kodak Co Antihalation backing for photographic film
US2172801A (en) * 1936-06-05 1939-09-12 Du Pont Film Mfg Corp Surface-treating film
GB555103A (en) * 1941-07-22 1943-08-04 Genevoise Instr Physique Improvements in or relating to optical and electrical means for determining the position of an object
US2461485A (en) * 1945-06-21 1949-02-08 Gen Aniline & Film Corp Xanthylium dye salts as filter and antihalation dyes in photographic materials
US2702243A (en) * 1950-06-17 1955-02-15 Azoplate Corp Light-sensitive photographic element and process of producing printing plates
US2898852A (en) * 1957-06-10 1959-08-11 Eastman Kodak Co Photomechanical spirit duplicating process
GB821507A (en) * 1956-02-25 1959-10-07 Agfa Ag A process for the production of photomechanical printing formes
US2937085A (en) * 1954-01-11 1960-05-17 Ditto Inc Composite photosensitive plate, and method of making printing plate therefrom
US3012885A (en) * 1956-12-03 1961-12-12 Eastman Kodak Co Pressure image transfer process

Patent Citations (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2172801A (en) * 1936-06-05 1939-09-12 Du Pont Film Mfg Corp Surface-treating film
US2131747A (en) * 1937-10-13 1938-10-04 Eastman Kodak Co Antihalation backing for photographic film
GB555103A (en) * 1941-07-22 1943-08-04 Genevoise Instr Physique Improvements in or relating to optical and electrical means for determining the position of an object
US2461485A (en) * 1945-06-21 1949-02-08 Gen Aniline & Film Corp Xanthylium dye salts as filter and antihalation dyes in photographic materials
US2702243A (en) * 1950-06-17 1955-02-15 Azoplate Corp Light-sensitive photographic element and process of producing printing plates
US2937085A (en) * 1954-01-11 1960-05-17 Ditto Inc Composite photosensitive plate, and method of making printing plate therefrom
GB821507A (en) * 1956-02-25 1959-10-07 Agfa Ag A process for the production of photomechanical printing formes
US3012885A (en) * 1956-12-03 1961-12-12 Eastman Kodak Co Pressure image transfer process
US2898852A (en) * 1957-06-10 1959-08-11 Eastman Kodak Co Photomechanical spirit duplicating process

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3252412A (en) * 1955-05-11 1966-05-24 Gevaert Photo Prod Nv Process for producing hectographic prints
US3241965A (en) * 1959-12-11 1966-03-22 Ritzerfeld Wilhelm Method of preparing and using hectographic masters
US3276871A (en) * 1962-05-14 1966-10-04 Eastman Kodak Co Printing matrix made by a colloid transfer process

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Publication number Publication date
BE583385A (en(2012))
FR1247963A (fr) 1960-12-09
DE1095663B (de) 1960-12-22
GB931397A (en) 1963-07-17

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