EP0116313A2 - Matériel imprimable pour l'impression sans frappe et procédé pour le fabriquer - Google Patents

Matériel imprimable pour l'impression sans frappe et procédé pour le fabriquer Download PDF

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Publication number
EP0116313A2
EP0116313A2 EP84100443A EP84100443A EP0116313A2 EP 0116313 A2 EP0116313 A2 EP 0116313A2 EP 84100443 A EP84100443 A EP 84100443A EP 84100443 A EP84100443 A EP 84100443A EP 0116313 A2 EP0116313 A2 EP 0116313A2
Authority
EP
European Patent Office
Prior art keywords
mixture
printable medium
medium
weight
approximately
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.)
Granted
Application number
EP84100443A
Other languages
German (de)
English (en)
Other versions
EP0116313B1 (fr
EP0116313A3 (en
Inventor
Keith Samuel Pennington
Krishna Gandhi Sachdev
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 EP0116313A2 publication Critical patent/EP0116313A2/fr
Publication of EP0116313A3 publication Critical patent/EP0116313A3/en
Application granted granted Critical
Publication of EP0116313B1 publication Critical patent/EP0116313B1/fr
Expired legal-status Critical Current

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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
    • B41M5/26—Thermography ; Marking by high energetic means, e.g. laser otherwise than by burning, and characterised by the material used
    • B41M5/30—Thermography ; Marking by high energetic means, e.g. laser otherwise than by burning, and characterised by the material used using chemical colour formers
    • 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 invention relates to printable media for use in non-impact printing and methods of producing such media.
  • the invention is particularly concerned with an electrothermic printing material on which printing takes place without impact and without application of external heat, by application of electric currents at selected print element positions.
  • the treated paper systems in order of paper cost, are:
  • thermal techniques provide a high quality but are relatively slow because of the need for the print element to cool between activations. Electroerosion does not require print element cooling but can be unreliable because the removed material often tends to be redeposited on the print head and significantly affect print quality.
  • the print element may be subjected to wear because of the need for good thermal contact or because of arc-sputtering electrode loss.
  • the invention is a composite electrothermic printing material i.e. a printable medium operating by selective application of electric current to selected print elements.
  • the material includes a substrate treated with a conductive composite electrothermic layer of polymer containing a thermally sensitive image forming material together with conductive material.
  • Selective application of electric current provides for localized heating of areas of conductive material within the composite electrothermic layer. This localized heating causes thermally sensitive image forming material to change colour.
  • the result of the localized selective current caused heating of appropriate print elements is matrix character or facsimile printing.
  • the invention provides printable medium for use in non-impact printing, said medium comprising a substrate supporting a composite electrothermic layer comprising a thermally sensitive image forming compound and a finely divided conductive material embedded in a carrier.
  • the printing material includes a substrate coated with a conductive composite electrothermic printing layer of polymer (polycarbonate, polyester, polyurethane, Kapton * ) made conductive by suspended conductive particles (zinc iodide, zinc oxide, tin oxide, titanium dioxide, zinc, silver, etc. or a mixture of these). Also incorporated in the polymer layer along with the conductive material is a finely divided, thermally sensitive image forming material (e.g., silver behenate). * TM
  • the printing stylus does not need to be hot in order to print but must merely carry current.
  • the localized current passing from a printing stylus into the treated paper provides a localized hot spot which changes colour.
  • the amount then dissipates into a broad area of the conductive polymer to a broad area return electrode for return to ground.
  • An optional aluminium thin layer between the paper base and the thermally sensitive resistive polymer layer provides a convenient and effective dissipating current flow path for return to the broad area return electrode and also results in increased current localization and hence higher resolution and quality printing.
  • the current is dissipated over such a broad area at the broad area return electrode that it does not raise the temperature above the threshold for printing.
  • FIG. 1 illustrates the preferred embodiment.
  • the printing head 3 or the treated paper composite 1 is driven by means not shown, so that the motion of the paper composite relative to the printhead is as shown by the direction of arrow 2 so as to pass multi- element stylus printing head 3 in a fashion to present spot printing elements in any one of several well known dot printing attitudes toward the moving paper.
  • Broad area return electrode 5 makes broad area contact to paper 1 at the surface of the paper.
  • Paper 1 is actually a composite of:
  • the printhead has its several styli 31-35 selectively energized via conductors 36 so as to provide selective spot producing currents at respective styli 31, 32, 33, 34 and 35 as required by the configuration of the desired character (P shown in FIG. 1).
  • a representative spot producing circuit includes a potential on the appropriate conductor of conductor bundle 36 to provide a potential at a selected stylus, e.g., stylus 31.
  • a conductive path for electrical current from stylus 31 is via resistance 14 to a surrounding area on aluminium film 12; and thence via aluminium film 12 to the area under broad area return electrode 5 and thence back through the conductive material in polyester composite 13 and broad area return electrode 5 to ground.
  • F IG. 2 is a simplified elevation diagram showing operation of another preferred embodiment.
  • Composite thermographic printing paper 1 is drawn in the direction of arrow 2 under printhead 3 so as to provide selective printed dots 4 by application of respectively related currents.
  • the currents are dissipated via the conductive capability 12' of the printing composite carried by paper substrate 11 and returned via broad area electrode 5 to ground.
  • the resolution of printed spots in this latter embodiment is usually not as good as is obtained by using the thin metallic aluminium return conductor beneath the electrothermic polymer due to greater current spreading in the conductive electrothermic polymer.
  • a second preferred embodiment eliminates the specific return layer 12 by providing sufficient conductivity 12' (FIG. 2) within composite polyester layer 13 to carry the desired currents.
  • This conductivity may be provided by a homogenous dispersion of current carrying particles within polyester layer 13 or by a graded dispersion with the heavier occurrence of conductive particles on the inside next to substrate paper layer 11. The greater current spreading in the conductive polymer, however, usually results in adequate, but lower resolution printing compared to the prior embodiment.
  • the electrothermal recording sheet consists of a paper or polymer substrate 11 such as polyester (e.g., MYLAR * ) or polypropylene, on which is deposited an electrically conductive film 12 of aluminium by vacuum evaporation or sputtering.
  • the aluminium film 12 is overcoated with a chromogenic resistive layer 13 composed of one or a mixture of conductive particulate materials (zinc iodide, zinc oxide, tin oxide, titanium dioxide) dispersed in a binder containing thermally sensitive additives.
  • a roughening agent selected from silica, alumina, aluminium hydroxide, CaCo 3 , Ti0 2 , etc., can also be incorporated in the resistive formulations in order to eliminate polymer debris accumulation on the print head during writing.
  • an electric signal to the printing device is accompanied by the generation of resistance heat which results in facsimile printing or direct image formation characterised by localized bleaching, colour formation or colour change.
  • the intensity, contrast and hue of the imaged region depends on the chemical system selected for image definition.
  • the electric signal may be on the order of 5-25 volts, 10-30 milliamperes as short as .02 milliseconds.
  • binders suitable for dispersion of semiconductive particles and other additives to form resistive coatings can be selected from the following classes:
  • Image definition can be obtained by incorporation of various thermally sensitive additives in the resistive formulations so that their heat-induced chemical reactions are accompanied by bleaching, colour formation or colour change.
  • thermally sensitive additives in the resistive formulations so that their heat-induced chemical reactions are accompanied by bleaching, colour formation or colour change.
  • Dye precursors such as sulfamino derivatives of 4-amino diphenylamine can be incorporated in the resistive coatings to obtain deep black images due to the formation of poly- zines similar to "Aniline Black,” Solanile Black” (and related systems) in the presence of metal salts at 180°-200°C, as shown in FORMULA 4. Solanile Black gives a fast black image on cellulosic polymers.
  • Electrothermal printing can also be accomplished by resistive heat induced in situ generation of metallic phthalocyamine.
  • Preferred materials for these pigments are 0-cyanobenzamide or phthalonitrile and a small amount of copper salts such as cuprous or cupric chloride which can be incorporated in the resistive formulations prior to coatings, as shown in FORMULA 5.
  • Similar phthalocyanine derivatives can be formed from other metals as nickel, cobalt, zinc, aluminium are generally brilliant blue and green.
  • Mixture A and B are ball milled separately to form uniform dispersions which are then combined and briefly ball milled (1-2 hours) to insure thorough mixing.
  • the resulting composition is coated on aluminized plastic (e.g., Mylar * , polypropylene, etc.) or paper support and dried/ cured at 50-60°C to obtain 2-10 pm thick dry resistive film.
  • Resistive heat generated during the electrothermal printing according to the present invention is accompanied by reduction of ionic silver to silver metal to provide a permanent black image.
  • binders such as ethyl cellulose, cellulose acetate, cellulose acetate butyrate (CAB), polymethylmethacrylate, 2-methyl - styrene - methylmethacrylate, etc. can be substituted for polyvinylbutyral resin.
  • the mixture is ball milled to form a uniform dispersion and combined with 10 parts of a leuco form of triphenylmethane dyes or fluorene analogs of crystal violet.
  • the final composition is thoroughly mixed and applied on aluminized plastic or paper support as described in Example 1 to obtain a resistive layer with thickness of the dry coating between 2mm - 10mm.
  • Electric resistant coatings formed with urethane-crosslinked cellulose derivatives as binders for semiconductive particulate material are urethane-crosslinked cellulose derivatives as binders for semiconductive particulate material:
  • the ingredients are thoroughly mixed together and approved on a plastic or paper support as described in Examples 1 and 2, and cured at 80-90°C for 10 minutes.
  • a solution of ethylcellulose is first prepared in a part of the solvent mixture, combined with the rest of the ingredients and the final composition is ball milled for 6 to 16 hours to form a uniform dispersion. After adjustment of viscosity to a desired consistency the formulation is coated on plastic or paper support as described in Example 1. The resulting structure when subjected to electrothermal printing according to this invention, an intense black image is formed due to resistive heat medicated oxidative transformation of the color forming ingredients (sulfonic derivatives of 4-amino diphenylamine) to polyazine dyes such as "Solanil Black.”
  • Alternate binder systems that can be substituted for ethyl cellulose are: CAB, cellulose acetate, nitrocellulose, polyvinylbutyral, etc.
  • CAB is first dissolved in a portion of the solvent mixture, combined with the rest of the ingredients, and ball milled for 6-16 hours to form a homogeneous slurry which is applied onto the aluminized support to obtain a dry coating thickness of 2mm to 10mm after dry/cure cycle at 80-90°C.
  • Electrothermal printing on such a recording material is accompanied by colour image formation due to copper phthalocyanine generated in the electric resistance layer containing colour forming precursors such as orthocyanobenzanide and the copper salts such as Cucl, Cucl2, CuI 2 , CuO, Cu 2 O etc.
  • a variation'of the above formulation includes the use of copper powder or copper paste as substitute for ZnO or TiO in cellulosic binders such as CAB or ethylcellulose with the rest of the ingredients being the same as in Example 5, to form electric resistant coatings of this invention.

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Physics & Mathematics (AREA)
  • Optics & Photonics (AREA)
  • Heat Sensitive Colour Forming Recording (AREA)
EP19840100443 1983-02-15 1984-01-17 Matériel imprimable pour l'impression sans frappe et procédé pour le fabriquer Expired EP0116313B1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US46668183A 1983-02-15 1983-02-15
US466681 1983-02-15

Publications (3)

Publication Number Publication Date
EP0116313A2 true EP0116313A2 (fr) 1984-08-22
EP0116313A3 EP0116313A3 (en) 1985-06-19
EP0116313B1 EP0116313B1 (fr) 1988-01-07

Family

ID=23852697

Family Applications (1)

Application Number Title Priority Date Filing Date
EP19840100443 Expired EP0116313B1 (fr) 1983-02-15 1984-01-17 Matériel imprimable pour l'impression sans frappe et procédé pour le fabriquer

Country Status (3)

Country Link
EP (1) EP0116313B1 (fr)
JP (1) JPS59196288A (fr)
DE (1) DE3468375D1 (fr)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0283032A3 (en) * 1987-03-18 1989-08-30 Kanzaki Paper Manufacturing Company Limited Heat-sensitive recording material

Family Cites Families (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR2293727A1 (fr) * 1974-12-03 1976-07-02 Cellophane Sa Nouveau materiau d'enregistrement
GB1474136A (en) * 1975-11-24 1977-05-18 Wiggins Teape Ld Electrosensitive recording material

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0283032A3 (en) * 1987-03-18 1989-08-30 Kanzaki Paper Manufacturing Company Limited Heat-sensitive recording material
US4904636A (en) * 1987-03-18 1990-02-27 Kanzaki Paper Mfg. Co., Ltd. Heat-sensitive recording material

Also Published As

Publication number Publication date
DE3468375D1 (en) 1988-02-11
EP0116313B1 (fr) 1988-01-07
EP0116313A3 (en) 1985-06-19
JPS59196288A (ja) 1984-11-07
JPH0254795B2 (fr) 1990-11-22

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