US3476659A - Electrophotographic imaging and copying process - Google Patents

Electrophotographic imaging and copying process Download PDF

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Publication number
US3476659A
US3476659A US566845A US3476659DA US3476659A US 3476659 A US3476659 A US 3476659A US 566845 A US566845 A US 566845A US 3476659D A US3476659D A US 3476659DA US 3476659 A US3476659 A US 3476659A
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US
United States
Prior art keywords
layer
photoconductive
image
electrolysis
light sensitive
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
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US566845A
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English (en)
Inventor
Masamichi Sato
Satoru Honjo
Masaaki Takimoto
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Fujifilm Holdings Corp
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Fuji Photo Film Co Ltd
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Publication of US3476659A publication Critical patent/US3476659A/en
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
    • B41M—PRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
    • B41M5/00—Duplicating or marking methods; Sheet materials for use therein
    • B41M5/20—Duplicating or marking methods; Sheet materials for use therein using electric current
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03G—ELECTROGRAPHY; ELECTROPHOTOGRAPHY; MAGNETOGRAPHY
    • G03G17/00—Electrographic processes using patterns other than charge patterns, e.g. an electric conductivity pattern; Processes involving a migration, e.g. photoelectrophoresis, photoelectrosolography; Processes involving a selective transfer, e.g. electrophoto-adhesive processes; Apparatus essentially involving a single such process
    • G03G17/02—Electrographic processes using patterns other than charge patterns, e.g. an electric conductivity pattern; Processes involving a migration, e.g. photoelectrophoresis, photoelectrosolography; Processes involving a selective transfer, e.g. electrophoto-adhesive processes; Apparatus essentially involving a single such process with electrolytic development
    • 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
    • G03G5/02—Charge-receiving layers
    • G03G5/04—Photoconductive layers; Charge-generation layers or charge-transporting layers; Additives therefor; Binders therefor
    • G03G5/08—Photoconductive layers; Charge-generation layers or charge-transporting layers; Additives therefor; Binders therefor characterised by the photoconductive material being inorganic
    • G03G5/087—Photoconductive layers; Charge-generation layers or charge-transporting layers; Additives therefor; Binders therefor characterised by the photoconductive material being inorganic and being incorporated in an organic bonding material
    • 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
    • G03G5/12—Recording members for multicolour processes
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03G—ELECTROGRAPHY; ELECTROPHOTOGRAPHY; MAGNETOGRAPHY
    • G03G9/00—Developers
    • G03G9/06—Developers the developer being electrolytic

Definitions

  • This invention is concerned with an improvement in electrolytic development applicable to photography, reproduction, printing facsimiles, etc. and other such processes utilizing electrolysis.
  • the coated plate is subjected to image exposure, usually negative image exposure, and the plate is immediately subjected to electrolysis in an aqueous solution containing a dye forming ionic material, such as quaternary anhydro base, nickel chloride or silver nitrate, while using the zinc oxide layer as a cathode.
  • a dye forming ionic material such as quaternary anhydro base, nickel chloride or silver nitrate
  • a paper or plastic film having a thin metal layer provided by vapor deposition or lamination, used as a base plate or suppo'rt, is hard to handle as compared with usual papers, since'the metal layer tends to be injured.
  • Aluminum has been found to be suitable for use as a thin metal layer in such elements, but in any case the surface condition on which a light sensitive layer is to be provided has a remarkable influence upon the finished image. That is, if the surface of a metal layer is coarse, a similarly coarse pattern appears in the image formed by electrolysis. Therefore, the finishing of the surface should be carried out with great care, which further increases the importance of the first above described disadvantage.
  • the light sensitive layer have a light sensitivity over the whole range of wave lengths of visible rays. If so, the appearance of the light sensitive layer is naturally gray to black or at least is not pure white. Although any spectral characteristic is permitted, if three resolving negatives are specially provided, such complicated procedure is now out of the question. If the back-ground is of pure white, it is done at the sacrifice of the light sensitivity to maintain the appearance nearly white.
  • two or three sensitizing dyes are added so as to impart the panchromatic property thereto, since the intrinsic absorption range of zinc oxide is in the near ultraviolet portion. In this case, the amount of the dyes is maintained as low as possible because of the reason mentioned above. Thus, possible increase of light sensitivity is hereby given up and the utilization of colored photoconductive material is similiarly restricted.
  • a photoconductive layer containing zinc oxide being chemically active and having photocatalytic action under radiation of light, tends to decompose organic compounds. Therefore, images formed thereon by electrolysis discolor in the course of long storage, and this is accelerated by zinc oxide.
  • a photoconductive layer is so composed that at least its surface is of low adhesiveness and an electrolytic product formed by electrolysis can be readily stripped from the photoconductive layer, so that the image consisting of the electrolytic product is transferred to a record receiving element.
  • This transfer should be substantially complete to such an extent that the photoconductive layer can be reused after the transfer. If this is done, the light sensitive material can be used repeatedly. The cost per one print can be overlooked, even if the cost required for the production of the light sensitive material is high.
  • the foregoing problems (1) and (2) can be solved by a single effort. It will be understood that problems 4) and (5) are also solved. Moreover, it is found that the remaining problem (3) is somewhat improved by the presence of the surface layer of our invention.
  • 1 is a support, such as, paper, plastic film and a metal plate
  • 2 is an electrically conducting layer such as an aluminum vapor deposition layer or high conductive metal film
  • a subbing layer is provided between 1 and 2 for the purpose of strengthening the adhesion thereof as occasion demands
  • 3 is a photoconductive insulating layer, for example consisting of a uniform mixture of zinc oxide and a binder
  • 4 is a thin low-adhesion layer, the surface of which, for example, consists of a silicone-type surface releasing agent.
  • this layer if necessary, may be incorporated a material miscible with a silicone type surface releasing agent, such as, nitro-cellulose, polyvinyl acetate, carboxymethyl cellulose, and polyvinyl alcohol.
  • Silicone oils and waxes may be used for the low adhesive layer in accordance with the use.
  • the surface layer is not present as a clear, independent layer, but may be uniformly mingled with a photoconductive layer so as to give a low adhesion surface.
  • a photoconductive layer so as to give a low adhesion surface.
  • the whole body of a light sensitive material may be so composed. The important point lies in that the surface has a low adhesiveness.
  • the low adhesion surface means a surface having a low alfinity to a number of strongly viscous and adhesive materials, even if pressed strongly against each other, and a good stripping property therefrom. It has been well known that paraffin-type compounds exhibit low adhesiveness. Therefore, polyethylene has such property. Fluorine resins have the same property. A layer consisting of a silicone type surface releasing agent that has been marketed of late exhibits more excellent properties than those described above or has no affinity to very viscous and adhesive materials. The characteristic of the low adhesion layer is represented by the force required to strip a strongly viscous and adhesive material, to be the standard, from the layer onto which the adhesive material is pressed in a predetermined manner.
  • the force required for stripping a strongly adhesive tape pressed at a rate of about 30 cm./min. onto the low adhesion layer is preferably 100 g./cm. or less.
  • Silicone type surface releasing agents are on the market in forms of aqueous emulsions and organic solvent solutions and it is found that any of them may be employed in our invention. In particular, the use of the former raises no fear of attacking the photoconductive layer,
  • the photoconductive layer often uses a binder miscible with organic solvents and immiscible with water.
  • the coated surface is not uniformly wetted.
  • an organic solvent solution on the other hand, a uniform thin layer is readily formed but the binder in a photoconductive layer is often dissolved therein. In such cases a special coating procedure should be devised.
  • the thickness of the surface layer should be as thin as possible. A thick layer hinders the passage of electric current, resulting in reduction of the practical sensitivity and operating speed in our invention. It has been made clear by our experiments that the electrolysis takes place without trouble at a thickness up to several microns, a preferred range being less than 2 microns.
  • Example 1 parts of photoconductive zinc oxide, 25 parts of a copolymer of styrene and butadiene Pliolite S-7 (manufactured by Goodyear Tire & Rubber Co.) and 75 parts of toluene were charged to a ball mill of porcelain and mixed for a long time to give a uniform dispersion.
  • the thus treated cylinder was allowed to stand in a furnace at C. for 20 minutes to cure the surface layer thereof.
  • the zinc oxide layer was used as cathode and a direct current of 4 v. was applied.
  • a silver image was obtained as a positive image.
  • the image was transferred completely to a marketed cellulose tape by pressing it lightly to the surface of the photoconductive layer. Thirty different images could be obtained from the same photoconductive layer by repeating the similar steps while bringing the light sensitive material into a dark adaptation state. There was little difference in the image quality of the first image and thirtieth image, and the light sensitive layer could be used more.
  • the surface layer has no influence upon the passage of electrolytic current in spite of the fact that it is of an insulating material.
  • the adhesion of the low adhesion layer and photoconductive layer is good enough to resist to repeated uses.
  • the generation of pinholes was not observed before the tenth treatment.
  • the good adhesion of the low adhesive layer and the photoconductive layer is likely due to the fact that there is no elfective force between the photoconductive layer and the low adhesive layer, since an adhesive tape has no affinity to the low adhesion layer. It is natural that the formation of pinholes can be suppressed by performing the stripping of an adhesive tape with great care.
  • thermoplastic film is superior to an adhesive tape, since the adhesive layer of the latter contains often a plasticizer or solvent for dyes, whereby an image is blotted in the course of a long storage.
  • Example -2 The following dyes were added to the mixture of Example 1 for dye-sensitization to impart a light sensitivity over the. whole visible range and. applied to thesame support as in Example 1, followed by drying.
  • Yellow thiuronium compound obtained by reacting bis(chloromethyl)- 4,4-bis(6-methylbenzthiazyl-2-)-azobenzene and N,N,N', N'-tetramethylthiourea was used as the yellow dye, and thiuronium salt of Anthragen Red Violet RHC obtained by the reaction thereof with N,N,N',N'-tetramethylthiourea, as the magenta dye.
  • the methods for the synthesis of these dyes are described in Japanese patent publication No. 15,444/1963.
  • Any support can be adapted therefor.
  • the contrast and the density of an image transferred can be controlled. For example, when a sufficient density of an image is not obtained by one electrolytic development, the image is once transferred, and the same image is put on after the second exposure and development. The control of contrasts will be performed similarly.
  • the present invention is applicable to other recording methods accompanied by electrolysis.
  • One of them for example, comprises providing a material consisting of an electrically conductive thin layer covered with an insulating coating, breaking the insulating coating by means of a pen pressure or discharge in accordance with an image, subjecting this, as a master, to electrolysis in a suitable electrolytic bath, whereby to deposit a metal, dye or metal hydroxide on the conductive portions from the electrolytic bath, and transferring the thus deposited material to a transfer material by suitable means.
  • a number of reproductions are thereby obtained, but it is very important in this method also that the transfer is satisfactorily carried out.
  • the following procedure is preferred.
  • a master obtained once by suitable means is coated thinly and uniformly with a silicone oil, fluorinated hydrocarbon oil or silicone surface releasing agent.
  • the resulting layer acts as a surface releasing agent without hindering of the passage of electric currendt, resulting in a similarly remarkable improvement.
  • Example 3 As the surface releasing agent of Example 2 required much time for curing, a solution of polymethylsiloxane having a viscosity of cp. at normal temperature in toluene was applied to an original plate by spraying in place of the surface releasing agent of Example 2. This method appeared to be similarly effective for our aims.
  • An electrically conductive pattern than can be adapted for electrolytic development may be obtained by many other methods.
  • a light sensitive layer whose electric resistance is remarkably lowered by applying pressure thereto or a recording material comprising an electrically conductive thin layer continuously provided with such a pressure sensitive layer, that is, to be transferred to some other support by pressure a master will be readily obtained by a pen pressure.
  • a permanent electrically conductive pattern may be obtained by providing a photoconductive layer utilizing a photoconductive material to be reduced electrolytically, for example, zinc oxide and/ or indium oxide and subjecting the photoconductive layer to electrolysis in aqueous solution of alkali metal halide, whereby to reduce the compounds in the photoconductive layer.
  • a photoconductive material to be reduced electrolytically, for example, zinc oxide and/ or indium oxide
  • a still further application of our invention consists in making facsimiles.
  • Our invention gives records not accompanied by discolorations or changes in color with the passage of time in a method wherein electric signals transmitted in accordance with information modulate the voltage of a needle-like electrode to color an electric current color forming paper.
  • an electrolytic color forming solution is flowed thereon and the recording is carried out by a needle-like electrode, dyes and other electrolytic products are deposited on the low adhesion layer once.
  • the drum is then immersed in water with revolving to wash electrically conductive salts and color forming components off, and
  • the drum can be reused, if necessary, by washing with water again.
  • a recording method involving electrolytic deposition of material on a photoconductive element which comprises providing a low adhesion layer on the surfac'e'of said photoconductive element, electrolytically depositing a material on the low adhesion layer of the photoconductive element, after exposure, and then transferring the deposited material from the low adhesion surface to the surface of a record receiving element.
  • said low adhesion layer comprises a silicone surface releasing agent.
  • a recording element for electrolytic recording comprising an electroconductive layer, operative as an electrode during the electrolysis and a photoconductive layer,
  • a recording element for electrolytic recording comprising a support, an electroconductive layer, operative as an electrode during the electrolysis, on said support, a photoconductive layer on said electroconductive layer and a low adhesion layer on said photoconductive layer.

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  • Physics & Mathematics (AREA)
  • General Physics & Mathematics (AREA)
  • Chemical & Material Sciences (AREA)
  • Inorganic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • Molecular Biology (AREA)
  • Photoreceptors In Electrophotography (AREA)
  • Printing Plates And Materials Therefor (AREA)
  • Thermal Transfer Or Thermal Recording In General (AREA)
US566845A 1965-07-21 1966-07-21 Electrophotographic imaging and copying process Expired - Lifetime US3476659A (en)

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JP4383765 1965-07-21

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BE (1) BE684406A (enrdf_load_html_response)
DE (1) DE1522601C3 (enrdf_load_html_response)
GB (1) GB1159394A (enrdf_load_html_response)

Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE2415334A1 (de) * 1973-03-30 1974-10-03 Eastman Kodak Co Loesungsmittel-loeslicher blockcopolyester, verfahren zu seiner herstellung und verwendung desselben
US4404276A (en) * 1982-06-14 1983-09-13 Eastman Kodak Company Polymer compositions containing crosslinked silicone polycarbinol and having a low coefficient of friction
US4473676A (en) * 1982-06-14 1984-09-25 Eastman Kodak Company Polymer compositions having a low coefficient of friction
US4600673A (en) * 1983-08-04 1986-07-15 Minnesota Mining And Manufacturing Company Silicone release coatings for efficient toner transfer
USRE32514E (en) * 1982-06-14 1987-10-06 Eastman Kodak Company Polymer compositions having a low coefficient of friction
US5262259A (en) * 1990-01-03 1993-11-16 Minnesota Mining And Manufacturing Company Toner developed electrostatic imaging process for outdoor signs
US6342324B1 (en) 2000-02-16 2002-01-29 Imation Corp. Release layers and compositions for forming the same

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS552237A (en) * 1978-06-21 1980-01-09 Ricoh Co Ltd Photoreceptor for electrophotography

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3165458A (en) * 1961-09-22 1965-01-12 Minnesota Mining & Mfg Electrolytic recording sheets
GB1006115A (en) * 1960-07-28 1965-09-29 Eastman Kodak Co An improved method of producing electro-photographic records
US3242858A (en) * 1960-07-28 1966-03-29 Eastman Kodak Co Photoconductography employing absorbed metal ions
US3363556A (en) * 1962-03-22 1968-01-16 Minnesota Mining & Mfg Electrophotographic imaging and copying process

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB1006115A (en) * 1960-07-28 1965-09-29 Eastman Kodak Co An improved method of producing electro-photographic records
US3242858A (en) * 1960-07-28 1966-03-29 Eastman Kodak Co Photoconductography employing absorbed metal ions
US3165458A (en) * 1961-09-22 1965-01-12 Minnesota Mining & Mfg Electrolytic recording sheets
US3363556A (en) * 1962-03-22 1968-01-16 Minnesota Mining & Mfg Electrophotographic imaging and copying process

Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE2415334A1 (de) * 1973-03-30 1974-10-03 Eastman Kodak Co Loesungsmittel-loeslicher blockcopolyester, verfahren zu seiner herstellung und verwendung desselben
US4404276A (en) * 1982-06-14 1983-09-13 Eastman Kodak Company Polymer compositions containing crosslinked silicone polycarbinol and having a low coefficient of friction
US4473676A (en) * 1982-06-14 1984-09-25 Eastman Kodak Company Polymer compositions having a low coefficient of friction
USRE32514E (en) * 1982-06-14 1987-10-06 Eastman Kodak Company Polymer compositions having a low coefficient of friction
US4600673A (en) * 1983-08-04 1986-07-15 Minnesota Mining And Manufacturing Company Silicone release coatings for efficient toner transfer
US5262259A (en) * 1990-01-03 1993-11-16 Minnesota Mining And Manufacturing Company Toner developed electrostatic imaging process for outdoor signs
US6342324B1 (en) 2000-02-16 2002-01-29 Imation Corp. Release layers and compositions for forming the same

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BE684406A (enrdf_load_html_response) 1967-01-03
DE1522601B2 (de) 1973-11-08
GB1159394A (en) 1969-07-23
DE1522601C3 (de) 1974-06-06
DE1522601A1 (de) 1969-09-18

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