EP0056096A2 - Process for multi-color electrolytic printing - Google Patents

Process for multi-color electrolytic printing Download PDF

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Publication number
EP0056096A2
EP0056096A2 EP81109158A EP81109158A EP0056096A2 EP 0056096 A2 EP0056096 A2 EP 0056096A2 EP 81109158 A EP81109158 A EP 81109158A EP 81109158 A EP81109158 A EP 81109158A EP 0056096 A2 EP0056096 A2 EP 0056096A2
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EP
European Patent Office
Prior art keywords
leuco
dye
substrate
dyes
printing
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.)
Withdrawn
Application number
EP81109158A
Other languages
German (de)
French (fr)
Other versions
EP0056096A3 (en
Inventor
William Emmett Bernier
Hi Dong Chai
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.)
International Business Machines Corp
Original Assignee
International Business Machines Corp
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 International Business Machines Corp filed Critical International Business Machines Corp
Publication of EP0056096A2 publication Critical patent/EP0056096A2/en
Publication of EP0056096A3 publication Critical patent/EP0056096A3/en
Withdrawn legal-status Critical Current

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Classifications

    • BPERFORMING OPERATIONS; TRANSPORTING
    • B41PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
    • B41MPRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
    • B41M5/00Duplicating or marking methods; Sheet materials for use therein
    • B41M5/20Duplicating or marking methods; Sheet materials for use therein using electric current

Definitions

  • the present invention is concerned with a process for multi-colored electrolytic printing.
  • Electrolytic printing per se is fairly well known in the art.
  • the basic concept involves production of images by application of electric current to selected portions of a substrate, such as paper, which has been impregnated with a material which changes color upon the application of electric potential.
  • the following references deal with some aspects of electrolytic printing:
  • Object of the invention is a process for multi-color printing using a mixture of dyes and a plurality of electrical stimuli.
  • the object of the invention is achieved by a process which is characterized in that to selected portions of a substrate which comprises a plurality of leuco dyes, each having a different sensitivity to threshold potential and pulse width of current required to convert it to its colored form, a plurality of electrical stimuli is applied, one for each leuco dye, with each of the plurality of electrical stimuli converting one leuco dye to its colored form.
  • electrolytic printing with a plurality of colors is achieved.
  • a substrate such as paper is impregnated with a plurality of dyes in the leuco form thereof.
  • the dyes in their leuco forms are selected so that they differ in the electrical stimulus required to convert. each dye from the leuco form to the colored form.
  • the dyes differ in the threshold potential and pulse width of the applied current required to convert them from the leuco form to the colored form.
  • a plurality of electrical stimuli, one for each leuco dye, is applied at an electrode to selected portions of the substrate. Each stimulus converts one leuco dye to its colored form.
  • multi-color electrolytic printing is achieved by careful dye selection and control of the potentials and pulse widths in the electrode.
  • Each leuco dye has a characteristic threshold potential at which it reacts to form the parent dye. Independent of this voltage, as long as the threshold value is surpassed, the leuco dye reacts with a characteristic electrical pulse width (i.e. kinetic rate) under a specified set of printing conditions to form the parent dye.
  • a characteristic electrical pulse width i.e. kinetic rate
  • the leuco dye reacts with a characteristic electrical pulse width (i.e. kinetic rate) under a specified set of printing conditions to form the parent dye.
  • a characteristic electrical pulse width i.e. kinetic rate
  • Black printing can be generated by developing all three colors simultaneously, as shown in the table, using high voltage and long pulse widths.
  • a fourth dye can be added to the system to give black.
  • the process of the present invention is also useful to develop intermediate variations of color between two dyes, by discharge of the higher threshold potential and careful modulation of the pulse width.
  • the process of the present invention is applicable to many mixtures of suitable leuco dyes. It is to be understood that when the expression “plurality of colors" is used, black is to be considered a color. That is to say, the present invention is useful for printing with black and another color simultaneously.
  • the substrate comprises three different leuco dyes, one for each of the primary colors of cyan, magenta and yellow. Selection of dyes from the three primary colors makes possible printing throughout the entire spectrum of colors.
  • the process of the present invention is also useful to produce intermediate shades or combinations of printed colors on a substrate by using intermediate levels of voltage and pulse width.
  • the following show selective generation of multiple colors in single pass electrolytic printing systems.
  • a paper substrate is coated sequentially with two leucodye solutions.
  • the first coating solution contains 0.2 % benzoylleucomethylene blue (leucodye) in acetone.
  • the second solution is aqueous and contains 0.35 % Potassium iodide (leucodye) in addition to an electrolyte buffer mixture - 4.5 % ammonium bromide, 5 % potassium bromide, 1.4 % potassium dihydrogen phosphate, and 1 % urea.
  • the second solution is adjusted to pH 7.
  • the printing behavior is listed in the table below.
  • a paper substrate is coated sequentially with an aqueous solution containing two leuco dyes followed by three coatings of aqueous electrolyte solution.
  • the first solution contains 1 % potassium iodide (leuco dye), 1 % o-sulfobenzoylleucomethylene blue (leuco dye), 0.1 % ascorbic acid, 1 % oxalic acid, and adjusted to pH 2.3.
  • the electrolyte solution contains 9 % ammonium bromide, 10 % potassium bromide, 1.4 % potassium dihydrogen phosphate, and adjusted to pH 7.
  • the printing behavior is listed in the table below.

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  • Color Printing (AREA)
  • Electronic Switches (AREA)

Abstract

The invention relates to a process for multi-color electrolytic printing.
This process is achieved by applying to selected portions of a substrate a plurality of electric currents of controlled voltage and controlled pulsewidth, said substrate comprising a plurality of leuco dyes each having a different sensitivity to the threshold potential and pulse width of current required to convert the leuco dye to the colored form thereof.

Description

  • The present invention is concerned with a process for multi-colored electrolytic printing.
  • Electrolytic printing per se is fairly well known in the art. The basic concept involves production of images by application of electric current to selected portions of a substrate, such as paper, which has been impregnated with a material which changes color upon the application of electric potential. The following references deal with some aspects of electrolytic printing:
    • (a) Fujitsu Scientific & Technical Journal, Sept. 1976, page 131, Article by T. Kitakohji;
    • (b) United States patent 3 713 996 to Letter (Bausch & Lomb)
    • (c) United States patent 3 816 838 to Higaki et al (Kanzaki Paper Mfg. Co.)
    • (d) United States patent 3-864 684 to Shimuzu (Mitsubishi Paper Mills)
    • (e) United States patent 3 772 159 to Sakata et al (Jujo Paper Co.).

    None of the listed prior art references describes or suggests the critical features of the present invention.
  • Object of the invention is a process for multi-color printing using a mixture of dyes and a plurality of electrical stimuli.
  • The object of the invention is achieved by a process which is characterized in that to selected portions of a substrate which comprises a plurality of leuco dyes, each having a different sensitivity to threshold potential and pulse width of current required to convert it to its colored form, a plurality of electrical stimuli is applied, one for each leuco dye, with each of the plurality of electrical stimuli converting one leuco dye to its colored form.
  • According to the present invention, electrolytic printing with a plurality of colors is achieved. A substrate such as paper is impregnated with a plurality of dyes in the leuco form thereof. The dyes in their leuco forms are selected so that they differ in the electrical stimulus required to convert. each dye from the leuco form to the colored form. In particular, the dyes differ in the threshold potential and pulse width of the applied current required to convert them from the leuco form to the colored form. A plurality of electrical stimuli, one for each leuco dye, is applied at an electrode to selected portions of the substrate. Each stimulus converts one leuco dye to its colored form. Thus, multi-color electrolytic printing is achieved by careful dye selection and control of the potentials and pulse widths in the electrode.
  • Each leuco dye has a characteristic threshold potential at which it reacts to form the parent dye. Independent of this voltage, as long as the threshold value is surpassed, the leuco dye reacts with a characteristic electrical pulse width (i.e. kinetic rate) under a specified set of printing conditions to form the parent dye. Thus, for example, when a three-color system of leuco dyes is chosen so that the dye with the lowest threshold potential is activated by a long electrical pulse width, another dye with an intermediate threshold potential is activated by a somewhat shorter pulse width, and a third dye has a high threshold potential but needs only a short pulse width, three colors and black can be printed at one electrode and color facsimile printing is achieved.
  • To illustrate the above concept, the following table gives a general example, listing arbitrary solution threshold potentials and printing pulse widths.
    Figure imgb0001
  • Black printing can be generated by developing all three colors simultaneously, as shown in the table, using high voltage and long pulse widths. In another variation of the invention, a fourth dye can be added to the system to give black. The process of the present invention is also useful to develop intermediate variations of color between two dyes, by discharge of the higher threshold potential and careful modulation of the pulse width.
  • The process of the present invention is applicable to many mixtures of suitable leuco dyes. It is to be understood that when the expression "plurality of colors" is used, black is to be considered a color. That is to say, the present invention is useful for printing with black and another color simultaneously. In one particularly useful variation of the present invention, the substrate comprises three different leuco dyes, one for each of the primary colors of cyan, magenta and yellow. Selection of dyes from the three primary colors makes possible printing throughout the entire spectrum of colors.
  • The process of the present invention is also useful to produce intermediate shades or combinations of printed colors on a substrate by using intermediate levels of voltage and pulse width.
  • The following examples are given solely for the purposes of illustration and are not to be considered limitations on the invention, many variations of which are possible without departing from the spirit and scope thereof.
  • The following show selective generation of multiple colors in single pass electrolytic printing systems.
  • Example One:
  • A paper substrate is coated sequentially with two leucodye solutions. The first coating solution contains 0.2 % benzoylleucomethylene blue (leucodye) in acetone. The second solution is aqueous and contains 0.35 % Potassium iodide (leucodye) in addition to an electrolyte buffer mixture - 4.5 % ammonium bromide, 5 % potassium bromide, 1.4 % potassium dihydrogen phosphate, and 1 % urea. The second solution is adjusted to pH 7. The printing behavior is listed in the table below.
    Figure imgb0002
  • Example Two:
  • A paper substrate is coated sequentially with an aqueous solution containing two leuco dyes followed by three coatings of aqueous electrolyte solution. The first solution contains 1 % potassium iodide (leuco dye), 1 % o-sulfobenzoylleucomethylene blue (leuco dye), 0.1 % ascorbic acid, 1 % oxalic acid, and adjusted to pH 2.3. The electrolyte solution contains 9 % ammonium bromide, 10 % potassium bromide, 1.4 % potassium dihydrogen phosphate, and adjusted to pH 7. The printing behavior is listed in the table below.
    Figure imgb0003

Claims (5)

1. Process for multi-color electrolytic printing with a plurality of colors, characterized in that to selected portions of a substrate which comprises a plurality of leuco dyes, each having a different sensitivity to threshold potential and pulse width of current required to convert it to its colored form, a plurality of electrical stimuli is applied, one for each leuco dye, with each of the plurality of electrical stimuli converting one leuco dye to its colored form.
2. Process as claimed in claim 1, characterized in that the substrate comprises the leuco form of two dyes of different colors.
3. Process as claimed in claims 1 and 2, characterized in that the substrate comprises the leuco form of a black dye and a leuco form of a dye of another color.
4. Process as claimed in claims t and 2, characterized in that the substrate comprises the leuco form of three dyes, one for each of the primary colors cyan, magenta and yellow.
5. Process as claimed in claim 1, characterized in that intermediate levels of voltage and pulse width are employed to produce intermediate shades or combinations of printed colors on a substrate.
EP81109158A 1981-01-09 1981-10-29 Process for multi-color electrolytic printing Withdrawn EP0056096A3 (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US22361681A 1981-01-09 1981-01-09
US223616 1981-01-09

Publications (2)

Publication Number Publication Date
EP0056096A2 true EP0056096A2 (en) 1982-07-21
EP0056096A3 EP0056096A3 (en) 1983-03-23

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Family Applications (1)

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EP81109158A Withdrawn EP0056096A3 (en) 1981-01-09 1981-10-29 Process for multi-color electrolytic printing

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0058338A2 (en) * 1981-02-05 1982-08-25 International Business Machines Corporation Electrochromic printing media
EP0097220A2 (en) * 1982-06-18 1984-01-04 International Business Machines Corporation The stabilization of leucomethylene blue dyes on a printing substrate

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE817821C (en) * 1948-12-31 1951-10-22 Siemens & Halske A G Writing device for registering measuring devices
DE1020261B (en) * 1953-10-06 1957-11-28 Atlas Werke Ag Electrically sensitive paper
FR1499526A (en) * 1965-10-20 1967-10-27 Allied Chem A method of electrographically producing images by passing an electric current through a sensitive composition and electrographic sheets for use in the method
DE2164387A1 (en) * 1970-12-25 1972-10-05 Jujo Paper Co Ltd Electrical recording medium and method of recording thereon
US3864684A (en) * 1974-03-22 1975-02-04 Mitsubishi Paper Mills Ltd Multicolor electrothermic recording sheet
EP0020974A1 (en) * 1979-05-24 1981-01-07 International Business Machines Corporation Electrochromic printing ink dissolved in water and method for printing with this printing ink

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE817821C (en) * 1948-12-31 1951-10-22 Siemens & Halske A G Writing device for registering measuring devices
DE1020261B (en) * 1953-10-06 1957-11-28 Atlas Werke Ag Electrically sensitive paper
FR1499526A (en) * 1965-10-20 1967-10-27 Allied Chem A method of electrographically producing images by passing an electric current through a sensitive composition and electrographic sheets for use in the method
DE2164387A1 (en) * 1970-12-25 1972-10-05 Jujo Paper Co Ltd Electrical recording medium and method of recording thereon
US3864684A (en) * 1974-03-22 1975-02-04 Mitsubishi Paper Mills Ltd Multicolor electrothermic recording sheet
EP0020974A1 (en) * 1979-05-24 1981-01-07 International Business Machines Corporation Electrochromic printing ink dissolved in water and method for printing with this printing ink

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0058338A2 (en) * 1981-02-05 1982-08-25 International Business Machines Corporation Electrochromic printing media
EP0058338A3 (en) * 1981-02-05 1983-03-23 International Business Machines Corporation Electrochromic printing media
EP0097220A2 (en) * 1982-06-18 1984-01-04 International Business Machines Corporation The stabilization of leucomethylene blue dyes on a printing substrate
EP0097220B1 (en) * 1982-06-18 1988-06-08 International Business Machines Corporation The stabilization of leucomethylene blue dyes on a printing substrate

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Inventor name: CHAI, HI DONG