US3654865A - Method for forming dye image using an electrophotographic developer containing a gelatin toner - Google Patents

Method for forming dye image using an electrophotographic developer containing a gelatin toner Download PDF

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Publication number
US3654865A
US3654865A US9077A US3654865DA US3654865A US 3654865 A US3654865 A US 3654865A US 9077 A US9077 A US 9077A US 3654865D A US3654865D A US 3654865DA US 3654865 A US3654865 A US 3654865A
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US
United States
Prior art keywords
gelatin
image
dye
acid
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
US9077A
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English (en)
Inventor
Yasuo Tamai
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Fujifilm Holdings Corp
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Fuji Photo Film Co Ltd
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Application filed by Fuji Photo Film Co Ltd filed Critical Fuji Photo Film Co Ltd
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Publication of US3654865A publication Critical patent/US3654865A/en
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    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03G—ELECTROGRAPHY; ELECTROPHOTOGRAPHY; MAGNETOGRAPHY
    • G03G13/00—Electrographic processes using a charge pattern
    • G03G13/01—Electrographic processes using a charge pattern for multicoloured copies
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03G—ELECTROGRAPHY; ELECTROPHOTOGRAPHY; MAGNETOGRAPHY
    • G03G13/00—Electrographic processes using a charge pattern
    • G03G13/26—Electrographic processes using a charge pattern for the production of printing plates for non-xerographic printing processes
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03G—ELECTROGRAPHY; ELECTROPHOTOGRAPHY; MAGNETOGRAPHY
    • G03G5/00—Recording members for original recording by exposure, e.g. to light, to heat, to electrons; Manufacture thereof; Selection of materials therefor
    • G03G5/10—Bases for charge-receiving or other layers
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03G—ELECTROGRAPHY; ELECTROPHOTOGRAPHY; MAGNETOGRAPHY
    • G03G8/00—Layers covering the final reproduction, e.g. for protecting, for writing thereon
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03G—ELECTROGRAPHY; ELECTROPHOTOGRAPHY; MAGNETOGRAPHY
    • G03G9/00—Developers
    • G03G9/08—Developers with toner particles
    • G03G9/12—Developers with toner particles in liquid developer mixtures
    • G03G9/13—Developers with toner particles in liquid developer mixtures characterised by polymer components

Definitions

  • a color printing process which comprises the steps of (1) processing with an acid an electrophotographic sensitive layer of a photoconductor mainly consisting of photoconductive zinc oxide, the layer having a gelatin image prepared by forming an electrostatic latent image on the layer and then converting the latent image into the gelatin layer by processing with an electrophotographic developer containing fine particles of gelatin, whereby the zinc oxide contained in the electrophotographic sensitive layer is removed, (2) bringing the gelatin layer into contact with a solution of a dye in a solvent mainly consisting of water to provide the dye to the gelatin image, (3) rinsing the layer with acid water to remove the excessive solution of the dye wetting the gelatin image, whereby the dye is once insolubilized, and (4) bringing the dyed gelatin image into contact with a layer capable of being readily dyed by the dye to transfer the dye onto the layer.
  • the other method is the dye transfer process whereby the tanning development is accomplished by means of a silver halide emulsion and the gelatin relief obtained consequently is utilized for transfer. These methods have both been popularized such as in Technicolor system.
  • the former method is suitable for mass production.
  • the image to be obtained thereby sufiers from insufficiency of durability.
  • the latter method can give images of good quality having extremely high durability.
  • This dye transfer process rather approaches to printing. For this reason, this process proves to be more economical when it is used for obtaining a larger number of duplicates from one original.
  • it is not suitable for purposes of making a small number of duplicates, for the cost per duplicate will be considerably higher in this case. The reason is that the preparation of gelatin relief to be used as the original plate consumes time and calls for skill.
  • An object of the present invention is to provide a method for obtaining color prints inexpensively and easily. Another object of the invention is to provide improvements in the dye transfer process utilizing the gelatin relief which is produced by means of electrophotography.
  • a still further object of the invention consists in providing a method for obtaining a clear color image having high image density by the dye transfer process which makes use of gelatin relief produced by means of either electrography or electrostatic recording method.
  • the present invention is directed to a color printing process, which comprises (1) processing with an acid an electrophotographic sensitive layer of a photoconductor mainly consisting of photoconductive zinc oxide, said layer having a gelatin image prepared by forming an electrostatic latent image on the layer and then converting said latent image into the gelatin layer by processing with an electrophotographic developer containing fine particles of gelatin, whereby the zinc oxide in said layer is removed, steps of: (2) bringing said gelatin image into contact with solution of a dye in a solvent mainly consisting of water to provide said dye to the gelatin image, (3) rinsing said layer with acid water to remove the excessive dye solution wetting said gelatin image, whereby the dye is once insolubilized, and (4) bringing said dyed gelatin image into contact with a layer capable of being readily dyed with the dye to transfer said dye onto said layer.
  • the aforementioned color printing process of the present invention comprises the following steps of treatment, for example,
  • the electrophotographic sensitive layer containing therein zinc oxide is electrically charged in the dark and then exposed to light projected through an image, whereby an electrostatic latent image is formed thereon.
  • the sensitive layer now carrying thereon the electrostatic latent image is treated with the electrophotographic developer containing therein gelatin toner (such as electrophotographic liquid developer containing gelatin toner in a carrier liquid) so as to develop the image.
  • the electrophotographic developer containing therein gelatin toner such as electrophotographic liquid developer containing gelatin toner in a carrier liquid
  • the gelatin image thus obtained is fixed and hardened by a suitable method.
  • the zinc oxide and other photoconductive element soluble in acid which are present in the electrophotographic sensitive layer are removed by treating with an acid.
  • the aqueous solution of a water-soluble dye is brought into contact with the gelatin image so as to provide the dye to the image.
  • a sheet possessed of a surface layer capable of readily receiving the aforementioned dye is brought into contact with the gelatin image. At this time, thedye transfers it self onto the dye-receiving layer to produce a final color image on the sheet.
  • the color printing process of the present invention mentioned above is characterized by incorporation of such step of treatment as shown in (IV), namely, the step for removing acid-soluble photoconductive elements (such as zinc oxide) contained in the electrophotographic sensitive layer by means of an acid.
  • step (IV) If the only aforementioned step of (IV) is omitted from the whole course of steps (I) through (VH), the final color image to be obtained will suffer from low optical density and insufficient clearness of image.
  • the water-soluble dye to be used in the dye transfer process is either an acid dye or a mordant dye.
  • an acidic dye In an acid solution an acidic dye generally has its solubility decreased.
  • the excessive dye solution adhering to the gelatin relief is removed and the dye in the gelatin image is fixed when the dye solution is brought into contact with the gelatin relief to cause the dye to be adsorbed and subsequently the gelatin relief is washed with acid water.
  • the electrophotographic sensitive layer having photoconductive zinc oxide as the principal photoconductive element (generally having more than 70 parts by weight of zinc oxide contained in 100 parts by weight by photoconductive elements as a whole) such as is used by the present invention
  • zinc oxide is contained in a considerably large quantity, substantially all zinc oxide particles exist in mutually contacting state or a state approaching thereto in the photosensitive layer. Therefore, zinc oxide can be removed easily even while there exists the insulative resin for combination in the photosensitive layer. It does not matter whether such zinc oxide particles as are unremovable exist isolated in the resin and remain therein after the treatment with acid. The reason is that such zinc oxide particles cannot exert any obstructive activity either in the step of absorption of dye by the gelatin image or in the step of washing with acidic solution.
  • the electrophotographic sensitive material to be used for the present invention uses zinc oxide as the principal photoconductive element and forms on a base a sensitive layer consisting of such photoconductive element and in insulative resin.
  • the base is desired to be resistant to water and to acid.
  • particularly suitable are cellulose triacetate film, polyethylene terephthalate film, polycarbonate film and the like.
  • a low electric resistance layer is formed ordinarily between the sensitive layer as mentioned above and the base.
  • the acid to be used in the aforementioned step of (IV) is desired to have a concentration exceeding 5 percent by weight, though variable with the kind of acid.
  • the upper limit of the concentration of the acid is determined by the kind of acid, the acidproofness of the base and the low electric resistance layer of the electrophotographic sensitive material to be used, and the acidproofness of the gelatin image. Generally, consideration must be paid to the fact that while the dissolving power of a given acid against zinc oxide increases with the concentration of that acid, the dissolving power of the acid against zinc oxide declines as the acid concentration rises extremely high.
  • the concentration of the acetic acid is suitable in the range of from 8 to 50 percent by weight.
  • acidic dyes and mordant dyes are suitable.
  • specific examples of such dyes are as follows.
  • Cyan dyes acid blue 45, acid green 16, acid green 1, acid blue 1, acid blue 9, and acid blue 54.
  • Magenta dyes acid red 80, acid red 34, acid red 1, acid violet 19, and acid violet 7.
  • Yellow dyes acid yellow 23, acid yellow 1 1, acid yellow 12, and acid yellow 34.
  • the image to be obtained by the present invention has very high quality, high resistance to light, and excellent color quality. Since this image has no surface reflection compared with the image obtainable electrophotographically by using toners of different colors, it reproduces colors with depth.
  • the image which is obtained once can produce images by dye transfer so far as the image is replenished with dye.
  • the image can produce many prints.
  • the present invention is advantageous for the electrophotographic sensitive layer using zinc oxide as the photoconductive element. It is similarly advantageous for the photoconductive layer combining zinc oxide with other photoconductive elements.
  • the photoconductive elements which are thus used in combination with zinc oxide include Cds, CdSe, Cd(S, Se), ZnS, ZnSe, and TiO Some of these photoconductive elements can be removed, together with zinc oxide, from the sensitive layer by means of acid, and others, if suffered to remain in the sensitive layer, do not impede the step of dye transfer.
  • EXAMPLE 1 Five grams of photographic gelatin was added to g. of distilled water. The gelatin became impregnated with water 30 minutes later. This was heated to 60 C to give rise to a clear water solution of gelatin.
  • Acetone Cotton seed oil Varnish prepared by cooking rosinmodified phenolformaldehyde resin with linseed oil Toluene 3 ml. 36 ml.
  • the resin component of this varnish was insoluble in acetone and soluble in the carrier liquid.
  • the sediment could be dissolved substantially completely by agitation to give rise to a viscous gelatin dispersion having a yellowish white color.
  • the liquid was a concentrated dope of liquid developer and could be preserved for a long time.
  • Kerosene was added for the purpose of lowering the rate at which the liquid developing agent evaporates.
  • the gelatin toner within the liquid developing agent was found to have positive electric charge.
  • This electrophotographic sensitive sheet was exposed to corona discharge in a dark place to have its surface negatively charged uniformly. Then a color slide selected as to the original was mounted on an enlarger, with a red filter set on the slide. The negatively charged sensitive sheet was exposed to light projected through the original.
  • the sensitive plate which had undergone the exposure was wetted with kerosene and immediately soaked in the liquid developer mentioned above.
  • a stainless steel tray was used as the container, so that the tray could play the part of developing electrode when the surface of latent image was brought close to the tray bottom.
  • the sheet wax removed from the bath washed with iso-paraffin (Isoper E made by Esso Standard Oil Co.), and then dried.
  • the sheet which had undergone the developing treatment was soaked in 1 percent methanol solution of formaldehyde, allowed to stand at rest overnight at room temperature, and then treated so as to harden the gelatin image.
  • the sensitive sheet carrying the gelatin image was soaked.
  • the solution was agitated occasionally. Two minutes later, it was observed that zinc oxide was removed from the surface of the sensitive layer and the entire surface assumed a metallic gloss because of the aluminum layer formed below the sensitive layer.
  • the sheet was washed sufficiently in distilled water. Finally, the sheet was soaked in methanol, removed from methanol, and dried in a forced current of hot air.
  • the three gelatin reliefs were soaked for 2 minutes in the aqueous solution of acid blue 54, acid violet 7, and acid yellow 23 respectively, removed from the solutions, and washed in a bath incorporating therein acetic acid.
  • the excessive dye solution adhering to the sheet was removed by this treatment. However, it is completely recognized the phenomenon so that the dye absorbed in the gelatin image portion may melt out into the cleaning bath.
  • EXAMPLE 2 The procedure of Example 1 was followed, except 20 parts by weight of epoxy ester of dehydrated castor oil fatty acid serving as the insulative binding agent for the photoconductive zinc oxide was substituted by 20 parts by weight of copolymer of vinyl chloride with vinyl acetate to form the sensitive layer. In this blending, a suitable quantity of acetone was used in the place of toluene.
  • the sheet was soaked in an acetic acid cleaning bath. When it was washed therein, it was found that the dye continued to be aluted from the gelatin image portion.
  • EXAMPLE 3 In the procedure of Example 1, 14 percent nitric acid was used in place of the aqueous solution of acetic acid for the removal of zinc oxide. By following the same procedure as in Example 1, there were obtained gelatin reliefs. In the present process, the aluminum layer vacuum deposited on the sheet withstood nitric acid of the aforementioned concentration. These gelatin reliefs were employed for color printing in the same way of dye transfer as in Example 1, to produce satisfactory results.
  • Example 4 The procedure of Example 1 was followed, except 1.5N hydrochloric acid was used for the removal of zinc oxide in the place of acetic acid. Thus were obtained gelatin reliefs.
  • EXAMPLE 6 In the procedure of Example 1, the development of image was carried out by employing a cascade developer containing therein gelatin toner having the average particle size of 12 instead of using the liquid developer containing therein gelatin toner.
  • the toner had positive polarity.
  • gelatin was fixed by exposing the sheet surface to a forced current of steam. Thereafter, the
  • said electrophotographic sensitive layer is formed on a film comprising a material selected from the group consisting of cellulose triacetate, polyethylene terephthalate and polycarbonate.

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  • Physics & Mathematics (AREA)
  • General Physics & Mathematics (AREA)
  • Photoreceptors In Electrophotography (AREA)
  • Printing Plates And Materials Therefor (AREA)
US9077A 1969-02-05 1970-02-05 Method for forming dye image using an electrophotographic developer containing a gelatin toner Expired - Lifetime US3654865A (en)

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Application Number Priority Date Filing Date Title
JP851869 1969-02-05

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US3654865A true US3654865A (en) 1972-04-11

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US (1) US3654865A (enrdf_load_stackoverflow)
BE (1) BE745534A (enrdf_load_stackoverflow)
CA (1) CA924951A (enrdf_load_stackoverflow)
FR (1) FR2032748A5 (enrdf_load_stackoverflow)
GB (1) GB1257296A (enrdf_load_stackoverflow)
NL (1) NL7001563A (enrdf_load_stackoverflow)

Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3864125A (en) * 1969-02-10 1975-02-04 Xerox Corp Electrophotographic method of making an imaging master
US4040828A (en) * 1975-01-06 1977-08-09 Xerox Corporation Multicolor imaging method and imaged member employing combinations of transparent toner and colorant
US4124471A (en) * 1977-08-22 1978-11-07 Diamond Shamrock Corporation Controlling silica sol particle size
US5004664A (en) * 1989-02-27 1991-04-02 Xerox Corporation Toner and developer compositions containing biodegradable semicrystalline polyesters
US5080292A (en) * 1988-03-03 1992-01-14 Sadao Nishibori Method for pulverizing gelatin, and paint, coating layer, film and finished cloth
US5171494A (en) * 1986-08-06 1992-12-15 Ein (America) Inc. Method of producing a paint which on application imparts a surface with a tanned skin or leather-like appearance
US5225536A (en) * 1989-08-16 1993-07-06 Sadao Nishibori Particles of gelatin and amino acid to be blended in resins
US20050079243A1 (en) * 2002-11-14 2005-04-14 Charles Lin Pet food compositions comprising electrostatically charged gelatin

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2297691A (en) * 1939-04-04 1942-10-06 Chester F Carlson Electrophotography
US2952536A (en) * 1958-04-21 1960-09-13 Haloid Xerox Inc Method of preparing a lithographic printing plate
US3001872A (en) * 1957-03-18 1961-09-26 Xerox Corp Preparing planographic plates and solution therefor
US3428453A (en) * 1964-03-19 1969-02-18 Xerox Corp Image forming process utilizing xerography

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2297691A (en) * 1939-04-04 1942-10-06 Chester F Carlson Electrophotography
US3001872A (en) * 1957-03-18 1961-09-26 Xerox Corp Preparing planographic plates and solution therefor
US2952536A (en) * 1958-04-21 1960-09-13 Haloid Xerox Inc Method of preparing a lithographic printing plate
US3428453A (en) * 1964-03-19 1969-02-18 Xerox Corp Image forming process utilizing xerography

Cited By (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3864125A (en) * 1969-02-10 1975-02-04 Xerox Corp Electrophotographic method of making an imaging master
US4040828A (en) * 1975-01-06 1977-08-09 Xerox Corporation Multicolor imaging method and imaged member employing combinations of transparent toner and colorant
US4124471A (en) * 1977-08-22 1978-11-07 Diamond Shamrock Corporation Controlling silica sol particle size
US5171494A (en) * 1986-08-06 1992-12-15 Ein (America) Inc. Method of producing a paint which on application imparts a surface with a tanned skin or leather-like appearance
US5080292A (en) * 1988-03-03 1992-01-14 Sadao Nishibori Method for pulverizing gelatin, and paint, coating layer, film and finished cloth
US5004664A (en) * 1989-02-27 1991-04-02 Xerox Corporation Toner and developer compositions containing biodegradable semicrystalline polyesters
US5225536A (en) * 1989-08-16 1993-07-06 Sadao Nishibori Particles of gelatin and amino acid to be blended in resins
US20050079243A1 (en) * 2002-11-14 2005-04-14 Charles Lin Pet food compositions comprising electrostatically charged gelatin
US7351437B2 (en) * 2002-11-14 2008-04-01 Del Monte Corporation Pet food compositions comprising electrostatically charged gelatin

Also Published As

Publication number Publication date
FR2032748A5 (enrdf_load_stackoverflow) 1970-11-27
CA924951A (en) 1973-04-24
DE2005267B2 (de) 1975-04-17
NL7001563A (enrdf_load_stackoverflow) 1970-08-07
GB1257296A (enrdf_load_stackoverflow) 1971-12-15
BE745534A (fr) 1970-07-16
DE2005267A1 (de) 1970-08-20

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