US3622468A - High-speed electrolytic printing including image intensification - Google Patents

High-speed electrolytic printing including image intensification Download PDF

Info

Publication number
US3622468A
US3622468A US878815A US3622468DA US3622468A US 3622468 A US3622468 A US 3622468A US 878815 A US878815 A US 878815A US 3622468D A US3622468D A US 3622468DA US 3622468 A US3622468 A US 3622468A
Authority
US
United States
Prior art keywords
recording sheet
solution
metal
additional
ions
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
US878815A
Other languages
English (en)
Inventor
Dennis R Turner
Catherine Wolowodiuk
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
AT&T Corp
Original Assignee
Bell Telephone Laboratories Inc
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Bell Telephone Laboratories Inc filed Critical Bell Telephone Laboratories Inc
Application granted granted Critical
Publication of US3622468A publication Critical patent/US3622468A/en
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

Links

Images

Classifications

    • 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
    • B41M5/205—Duplicating or marking methods; Sheet materials for use therein using electric current and an eroding electrode
    • 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

Definitions

  • the latent image is subsequently intensified and made visible by the deposition of additional metal on the metal image particles from a solution. Because of the small amount of catalyst such as silver needed on the sheet to develop the image, the erosion of the anodes is relatively slow. The production of one SlXl 1 inch sheet of printed matter every 2 seconds is well within the capabilities of the process,
  • a number of printing processes depend upon the fact that finely divided particles of any metallic substance appear black.
  • silver ions are transferred electrolytically from a silver anode electrode into an electrolyte moistened paper and reduced by reducing agents in the paper to form finely divided silver particles which produce the visual image.
  • the anode electrode is a silver bar which is in contact with the paper over its entire width.
  • the cathode electrode which is in the form of a spiral wrapped around a rotating drum is pressed against it from the other side. A conducting path is thus formed which repeatedly moves across the paper as the drum rotates generating a series of lines.
  • electroless plating technique is one way of producing a conductive coating on an insulating body, for instance to serve as a conductive base for subsequent electrode plating. It consists of the immersion of a suitable treated body in a solution which contains, among other things, ions of the required metal and a reducing agent. The reduction of metal is catalyzed at the treated surface of the body and a metal film is deposited thereon without the application of an external current. The process then becomes autocatalytic and the plating is allowed to continue until the desired thickness is reached. Bright copper platings, for instance, whose conductivity is as high as the conductivity of electroplated films are regularly produced in this manner.
  • FIG. I is a schematic representation of an exemplary printing apparatus.
  • FIG. 2 is a schematic representation of a second exemplary printing apparatus.
  • An electrolyte must be chosen which is chemically appropriate to the choice of anode material.
  • the electrochemical reaction at the anode must produce solution of metal ions at a low electrode potential.
  • replating can also be minimized by suitable electrode arrangement.
  • any of the soluble nitrates such as potassium or sodium nitrate, are suitable.
  • This can be done by the incorporation in the electrolyte of a reducing agent such as formaldehyde or paraformaldehyde (a polymeric form of formaldehyde with no objectional odor).
  • a reducing agent such as formaldehyde or paraformaldehyde (a polymeric form of formaldehyde with no objectional odor).
  • Silver ions may also be reduced to metallic silver with light.
  • a sufficient quantity of the selected reducing agent can be incorporated in the electrolyte to serve as a reducing agent for the subsequent electroless process.
  • the electroless plating solution contains a source of metal ions, a complexing agent to control the reaction rate and an acid or base, if needed to adjust the pH of the solution.
  • An exemplary plating solution employs copper sulfate as a source of metal ions, Rochelle salt (potassium sodium tartrate) as a complexing agent and some potassium hydroxide.
  • Another complexing agent which has been used extensively in this solution is a soluble salt of ethylene diamine tetra-acetic acid. This plating solution should be kept separate from the reducing agent until the plating is desired to prevent its deterioration.
  • FIG. 1 shows an exemplary printer.
  • the recording sheet 11 is unrolled from its source 12 and passes around roller 13 through solution A,14.
  • the moisten sheet is then held against the writing head 15 which contains an array of electrode pairs.
  • the sheet then passes around roller 16 through solution 8,17, between a heated roller 18 and a drive roller 19 and into a mechanism 111 in which the sheet is dried and processed to final form 112 and collected in a receptacle 113.
  • composition of solution A,l4 and 8,17 may be any one of several combinations of the three basic solutions; that is the electrolyte, the reducing agent and the plating solution.
  • the electrolyte and reducing agent may be introduced as solution A while the plating solution is introduced as solution B.
  • the electrolyte and plating solution can be introduced as solution A and the reducing agent as solution B as long as the plating solution does not interfere chemically with the electrolytic writing process.
  • some of the constituents of solution A as described above can be incorporated in the recording sheet in either wet or dry form. If all of the constituents of solution A are incorporated in the recording sheet solution A,l4 and the corresponding roller 13 can be eliminated.
  • these ions must be reduced to metallic form so that they can precipitate as metal particles and serve as the catalyst for the subsequent electroless intensification.
  • These ions can be reduced by a reducing agent present in solution A or by some process such as the exposure to light from a light source 114. If silver ions are used in the writing process and copper ions are used in the intensification process, the reduction of the silver ions by exposure to radiation can take place even in the presence of the copper ions. Since silver is more noble than copper, conditions can be chosen which will allow this selective reduction.
  • the plating reaction In order to produce a visible image rapidly and form the fine metallic grains which are required for a black image instead of the shiny metal plating usually derived from the electroless plating process, the plating reaction must be caused to take place rapidly. This can be accomplished by heating the recording sheet after it emerges from solution B,l7. One way this can be accomplished is by passing the sheet over the heated roller 18.
  • FIG. 2 shows another exemplary printer.
  • the recording sheet 21 is not passed through the solutions 24 and 27, but metered portions of these solutions are carried on to the recording sheet 21 by the rough or porous surface of the rollers 23 and 26.
  • the degree of roughness or porosity can be used to meter the solutions.
  • the constitution of the solutions I EXAMPLE One chemical system which has proven successful is presented below:
  • a process for the production of a record on a porous recording sheet at least partially impre nated with an electrolytic solution comprising the electro ytic introduction of metallic ions into the said recording sheet from an anode electrode as the said recording sheet is moved relative to the said anode electrode, the reduction of the said ions, and the precipitation of the resulting metal as metallic particles, characterized in that the recording sheet is brought into contact with at least one additional solution and that additional metal is subsequently deposited at the sites of the said metallic particles from the said at least one additional solution by a chemical reaction catalyzed by the said metallic particles whereby the said record is intensified.
  • said electrolytic solution and said at least one additional solution comprise paraforrnaldehyde as a first portion and copper sulfate and a member of the group consisting of potassium sodium tartrate and a soluble salt of ethylene diamine tetra-acetic acid as a second portion and in which said first portion and said second portion are kept separate from one another until said deposition is desired.
  • Apparatus for the production of a record on a porous recording sheet at least partially impregnated with an electrolytic solution comprising, feeding means for the storage and dispensing of the said recording sheet, writing means for the electrolytic introduction of first metal ions into said recording sheet, transportation means for the introduction of relative motion between the said recording sheet and said printing means, said first metal ions being reduced and deposited as first metal particles characterized in the subsequent inclusion of wetting means for the introduction into said recording sheet of at least one additional solution said solution containing additional metal ions, a portion of said additional metal ions being subsequently catalytically reduced at the sites of said first metal particles and precipitated, thereby intensifying said record.
  • Apparatus of claim 9 in which the said electrolytic solution and the said at least one additional solution comprise paraformaldehyde as a first portion and copper sulfate and potassium sodium tartrate as a second portion and in which the said first portion and the said second portion are kept separate from one another until the said deposition is desired.
  • Apparatus of claim 10 including, subsequent to said wetting means, thermal means for maintaining the temperature of said recording sheet in the range 50 to 80 C.

Landscapes

  • Chemically Coating (AREA)
  • Fax Reproducing Arrangements (AREA)
  • Electrolytic Production Of Metals (AREA)
  • Manufacture Or Reproduction Of Printing Formes (AREA)
US878815A 1969-11-21 1969-11-21 High-speed electrolytic printing including image intensification Expired - Lifetime US3622468A (en)

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
US87881569A 1969-11-21 1969-11-21

Publications (1)

Publication Number Publication Date
US3622468A true US3622468A (en) 1971-11-23

Family

ID=25372902

Family Applications (1)

Application Number Title Priority Date Filing Date
US878815A Expired - Lifetime US3622468A (en) 1969-11-21 1969-11-21 High-speed electrolytic printing including image intensification

Country Status (7)

Country Link
US (1) US3622468A (fr)
JP (1) JPS4934160B1 (fr)
BE (1) BE759043A (fr)
DE (1) DE2057271A1 (fr)
FR (1) FR2069542A5 (fr)
GB (1) GB1309279A (fr)
NL (1) NL7016753A (fr)

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3786515A (en) * 1972-06-19 1974-01-15 Horizons Inc Latent image recording method and electric recording apparatus
US4046074A (en) * 1976-02-02 1977-09-06 International Business Machines Corporation Non-impact printing system
US4150387A (en) * 1976-10-27 1979-04-17 Mita Industrial Company Ltd. Alternating current electrostatic recording process
EP0023754A1 (fr) * 1979-06-04 1981-02-11 Xerox Corporation Appareil et procédé pour l'enregistrement électrostatique

Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US670510A (en) * 1898-06-18 1901-03-26 Electrical Inkless Printing Syndicate Ltd Process of printing and product thereof.
US2063992A (en) * 1932-06-10 1936-12-15 Westinghouse Electric & Mfg Co Facsimile reception
US2453484A (en) * 1946-05-31 1948-11-09 Rca Corp Electrolytic signal recording
US2636848A (en) * 1948-07-19 1953-04-28 Rca Corp High-speed electrolytic marking
US2874072A (en) * 1956-09-17 1959-02-17 Gen Electric Autocatalytic copper plating process and solution
US3245826A (en) * 1963-06-12 1966-04-12 Clevite Corp Magnetic recording medium and method of manufacture
US3477847A (en) * 1965-07-16 1969-11-11 Eastman Kodak Co Process for autoelectrolytic reproduction of documents

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US670510A (en) * 1898-06-18 1901-03-26 Electrical Inkless Printing Syndicate Ltd Process of printing and product thereof.
US2063992A (en) * 1932-06-10 1936-12-15 Westinghouse Electric & Mfg Co Facsimile reception
US2453484A (en) * 1946-05-31 1948-11-09 Rca Corp Electrolytic signal recording
US2636848A (en) * 1948-07-19 1953-04-28 Rca Corp High-speed electrolytic marking
US2874072A (en) * 1956-09-17 1959-02-17 Gen Electric Autocatalytic copper plating process and solution
US3245826A (en) * 1963-06-12 1966-04-12 Clevite Corp Magnetic recording medium and method of manufacture
US3477847A (en) * 1965-07-16 1969-11-11 Eastman Kodak Co Process for autoelectrolytic reproduction of documents

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3786515A (en) * 1972-06-19 1974-01-15 Horizons Inc Latent image recording method and electric recording apparatus
US4046074A (en) * 1976-02-02 1977-09-06 International Business Machines Corporation Non-impact printing system
US4150387A (en) * 1976-10-27 1979-04-17 Mita Industrial Company Ltd. Alternating current electrostatic recording process
EP0023754A1 (fr) * 1979-06-04 1981-02-11 Xerox Corporation Appareil et procédé pour l'enregistrement électrostatique

Also Published As

Publication number Publication date
GB1309279A (en) 1973-03-07
NL7016753A (fr) 1971-05-25
BE759043A (fr) 1971-04-30
FR2069542A5 (fr) 1971-09-03
DE2057271A1 (de) 1972-05-25
JPS4934160B1 (fr) 1974-09-12

Similar Documents

Publication Publication Date Title
CA1087599A (fr) Procede de depot d'un metal sur un substrat
AU748566C (en) Method of providing conductive tracks on a printed circuit and apparatus for use in carrying out the method
US3668003A (en) Printed circuits
NL8302344A (nl) Werkwijze voor het elektrisch bekleden van niet-metallieke oppervlakken.
US5206102A (en) Photoelectrochemical imaging system
GB1490229A (en) Method of forming a hydrophobic surface
US3622468A (en) High-speed electrolytic printing including image intensification
JPH08501348A (ja) 不伝導性表面を金属被覆する方法、及び当該方法におけるヒドロキシメチルスルフィン酸の使用法
JPH0274344A (ja) 印刷版の製造方法
US2063992A (en) Facsimile reception
JPH10511743A (ja) メッキ設備
EP0774889A1 (fr) Fabrication photoélectrochimique de circuits électroniques
US3544319A (en) Production of printing plates
US3152969A (en) Photoconductolithography employing hydrophobic images
US3072541A (en) Developer
US3418217A (en) Electrolytic image formation
Turner et al. Electroless copper plating as an image amplifier for electrolytic printing
US3432406A (en) Photoconductographic material and process of preparation
Lee et al. Economical selective metallization of insulating surfaces
Mittal Jim Y. Lee and CQ Cui¹ Department of Chemical Engineering National University of Singapore
DE2323507A1 (de) Verfahren zur herstellung metallischer muster
GB2083077A (en) Selective electro-plating method
US3402109A (en) Electrolytic recording medium
US3713169A (en) Electrode configuration for electrolytic printing
WO2004031454A2 (fr) Nouvelle conception de cathode a utiliser dans une cellule d'electrodeposition