EP0116313B1 - Printable media for use in non-impact printing and methods of producing such media - Google Patents

Printable media for use in non-impact printing and methods of producing such media Download PDF

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Publication number
EP0116313B1
EP0116313B1 EP19840100443 EP84100443A EP0116313B1 EP 0116313 B1 EP0116313 B1 EP 0116313B1 EP 19840100443 EP19840100443 EP 19840100443 EP 84100443 A EP84100443 A EP 84100443A EP 0116313 B1 EP0116313 B1 EP 0116313B1
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.)
Expired
Application number
EP19840100443
Other languages
German (de)
English (en)
French (fr)
Other versions
EP0116313A2 (en
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/en
Publication of EP0116313A3 publication Critical patent/EP0116313A3/en
Application granted granted Critical
Publication of EP0116313B1 publication Critical patent/EP0116313B1/en
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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 current sensitive printable media for use in the non-impact non-electroerosion 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.
  • image forming techniques such as photography may be used.
  • the cost of image forming treated paper may be prohibitive.
  • paper cost becomes the major criterion for choice, and it becomes advantageous to make a significant investment in printer equipment in order to use plain paper.
  • the treated paper system 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 colour forming material together wiht 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 of facsimile printing.
  • the invention provides current sensitive printable medium for use in non-impact non-electroerosion printing, said medium comprising a substrate supporting a composite electrothermic layer comprising a carrier encompassing a thermally sensitive colour forming system and a conductive material.
  • 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 benhenate).
  • polymer polycarbonate, polyester, polyurethane, Kapton *
  • suspended conductive particles zinc oxide, tin oxide, titanium dioxide, zinc, silver, etc or a mixture of these.
  • a finely divided, thermally sensitive image forming material e.g., silver benhenate
  • 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 alos 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.
  • 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 confiquration 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.
  • FIG. 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 homogeneous. 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 of 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 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: Cellulose derivatives such as cellulose acetate butyrate, ethyl cellulose, cellulose acetate, hydroxyethyl cellulose, nitrocellulose, carboxymethyl cellulose, etc.
  • Acrylate polymers including polymethylmethacrylate, polyacrylonitrite, polyacrylamides, polyvinlyacetate, polyvinylacetal resins such as polyvinylbutyral.
  • Crosslinked polymers such as polyurethanes formed from the reaction of free hydroxyl carrying binders with polyisocyanates or melamines.
  • Hydroxyethylene polymers such as hydroxypropylene, poly(ethylene glycols), polyvinylalcohol, etc.
  • Various conductive materials that can be utilized for this application are: ZnO, Znl 2 , Cuts, Sb 2 0 3 , MoO, Cds, Ti0 2 , molydisulfide, conducting polymers that can be employed as alternate binders for inorganic conductive particles such as oligostyrene sulfonate, polyethylene imine salts, doped polyacetylenes, polyphenylenes, etc.
  • 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.
  • Leucoform dyes that undergo dye formation when subjected to electrical resistance heat generated during printing, e.g.
  • 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 polyzines 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 in situ generation of 5 metallic phthalocyamine. 5
  • 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 0 C to obtain 2-10 ⁇ m 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.
  • Alternate binders such as ethyl cellulose, cellulose acetate, cellulose acetage butyrate (CAB), polymethylmethacrylate, 2-methylstyrene - methylmethacrylate, etc. can be substituted for 5 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 2 pm-10 ⁇ m.
  • 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 colour 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 homogenous 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 0 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, Cucl 2 , Cul 2 , CuO, C U2 0 etc.
  • a variation of the above formulation includes the use of copper powder or copper paste as substitute for ZnO or TiO x 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 coating 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 Printable media for use in non-impact printing and methods of producing such media Expired EP0116313B1 (en)

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

Family

ID=23852697

Family Applications (1)

Application Number Title Priority Date Filing Date
EP19840100443 Expired EP0116313B1 (en) 1983-02-15 1984-01-17 Printable media for use in non-impact printing and methods of producing such media

Country Status (3)

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

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS63230388A (ja) * 1987-03-18 1988-09-26 Kanzaki Paper Mfg Co Ltd 感熱記録体

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

Also Published As

Publication number Publication date
JPS59196288A (ja) 1984-11-07
JPH0254795B2 (enExample) 1990-11-22
EP0116313A2 (en) 1984-08-22
DE3468375D1 (en) 1988-02-11
EP0116313A3 (en) 1985-06-19

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