EP0225383B1 - Verfahren zur herstellung eines thermofarbbandes für den thermotransferdruck und das danach erhältliche thermofarbband - Google Patents

Verfahren zur herstellung eines thermofarbbandes für den thermotransferdruck und das danach erhältliche thermofarbband Download PDF

Info

Publication number
EP0225383B1
EP0225383B1 EP86904125A EP86904125A EP0225383B1 EP 0225383 B1 EP0225383 B1 EP 0225383B1 EP 86904125 A EP86904125 A EP 86904125A EP 86904125 A EP86904125 A EP 86904125A EP 0225383 B1 EP0225383 B1 EP 0225383B1
Authority
EP
European Patent Office
Prior art keywords
thermo
solvent
solubiliser
thermal
wax
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
EP86904125A
Other languages
German (de)
English (en)
French (fr)
Other versions
EP0225383A1 (de
Inventor
Heinrich Krauter
Albert Schmedes
Norbert Mecke
Wieland Kuchenreuther
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.)
Pelikan Produktions AG
Original Assignee
Pelikan GmbH
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 Pelikan GmbH filed Critical Pelikan GmbH
Priority to AT86904125T priority Critical patent/ATE46660T1/de
Publication of EP0225383A1 publication Critical patent/EP0225383A1/de
Application granted granted Critical
Publication of EP0225383B1 publication Critical patent/EP0225383B1/de
Expired legal-status Critical Current

Links

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
    • B41M5/382—Contact thermal transfer or sublimation processes
    • B41M5/392—Additives, other than colour forming substances, dyes or pigments, e.g. sensitisers, transfer promoting agents
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10S428/00—Stock material or miscellaneous articles
    • Y10S428/913—Material designed to be responsive to temperature, light, moisture
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10S428/00—Stock material or miscellaneous articles
    • Y10S428/914—Transfer or decalcomania
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/24—Structurally defined web or sheet [e.g., overall dimension, etc.]
    • Y10T428/24802—Discontinuous or differential coating, impregnation or bond [e.g., artwork, printing, retouched photograph, etc.]
    • Y10T428/24893—Discontinuous or differential coating, impregnation or bond [e.g., artwork, printing, retouched photograph, etc.] including particulate material
    • Y10T428/24901—Discontinuous or differential coating, impregnation or bond [e.g., artwork, printing, retouched photograph, etc.] including particulate material including coloring matter

Definitions

  • the invention relates to a method for producing a rewritable thermal ink ribbon for thermal transfer printing with a layer of a melting ink on one side of a plastic film as a carrier, the melting ink containing a wax or a wax-like substance, a colorant and an organic binder and optionally other additives, and a thermal ribbon available afterwards.
  • Thermal ribbons have been known for a long time. They point to a film-like carrier which e.g. can consist of paper or plastic, a layer of a melting ink, in particular in the form of a wax-bound dye or soot layer. In these thermal ribbons, the melting ink is melted by means of a thermal print head and transferred to a recording paper. This is generally referred to as a TCR band (“Thermal Carbon Ribbon”).
  • Thermal printers that emboss a thermal symbol during the printing process are e.g. known from DE-ASen 2 062 494 and 2 406 613 and DE-OS 3 224 445. The procedure for printing is as follows: The print head of a thermal printer presses the thermal ribbon onto the recording paper.
  • the printhead develops temperatures that can reach a maximum of around 400 ° C.
  • the uncoated back of the thermal ribbon or the film-like carrier is thus in direct contact with the print head or the thermal symbol formed thereon during the printing process.
  • the relative speed between the thermal ink ribbon and the printing paper is zero. Due to the action of the thermal symbol, the melting ink in the form of the symbol to be printed is transferred from the thermal ink ribbon to the printing paper by a melting process. When the thermal ink ribbon is removed from the printing paper, the melted symbol sticks to the printing paper and solidifies.
  • thermal ribbons in which the heat symbol is not generated by a thermal print head, but by resistance heating of a specially designed film-like carrier.
  • the melting ink which is the actual “functional layer” during the printing process, also contains the materials already described above. Experts refer to this as an “ETR” thermal ribbon (“Electro Thermal Ribbon”).
  • ETR Electro Thermal Ribbon
  • thermal ribbons that advertise several times (keyword: «multiuse»). Such thermal ribbons are described for example in EP-A-0 063 000.
  • the melting ink of the thermal ink ribbon is then a particulate material which is insoluble in the solvent of the coating liquid and does not melt below 100 ° C, and incorporates another particulate material with a melting point between 40 and 100 ° C.
  • the particulate material not melting below 100 ° C should preferably be a metal oxide, a metal, an organic resin or carbon black.
  • This special particulate material is intended to give the layer of the melting ink, which is a solid mixture, a heterogeneous structure which can only consume a small amount of the molten colored material to be transferred in each individual printing operation.
  • the invention was therefore based on the object of developing the method described at the outset in such a way that a thermal ink ribbon is obtainable which, when used, leads to particularly sharp prints.
  • this object is achieved in that a coating liquid which contains a dissolved thermoplastic binder and the meltable wax or the meltable wax-like substance in finely divided solid form in a ratio of about 1: 1 to 1: 5, in a manner known per se the carrier of the thermal ink ribbon is applied, the coating liquid being a mixture of a solvent for the thermoplastic binder at room temperature and a non-solvent therefor, and the non-solvent / solvent mixture is evaporated while reducing its solvency for the thermoplastic binder.
  • any plastic films are suitable, which are also used as carriers in the conventional carbon ribbons of typewriters, but which also withstand the high temperatures mentioned during the briefly running printing process and furthermore readily release the melting ink at these temperatures at the heated point .
  • the plastic film consists in particular of thermoplastic plastics with a higher glass transition temperature.
  • the focus here is on the following materials: polyesters used in the prior art, in particular polyethylene terephthalates, polycarbonates, polyamides, polyvinyl compounds, in particular polyvinyl chloride, polyvinyl acetate, polyvinyl alcohol and polyvinyl propionate, polyethylene, polypropylene and polystyrene.
  • the plastic film to be used according to the invention can also be one which consists of a fabric laminated on one or both sides.
  • similarly designed composite films that are known to the person skilled in the art can also be used within the scope of the invention.
  • a plasticizer into the selected plastic carrier in order to achieve improved flexibility.
  • a substance that increases the thermal conductivity can also be incorporated.
  • the thickness of the plastic film is determined according to the respective requirements. As a rule, however, it is relatively thin, eg 3 to 6 ⁇ m, in order to allow the necessary heat transfer to take place optimally. Self Ver this range can also be exceeded or fallen below.
  • wax used in connection with the invention is to be understood as far as possible. Such a material should generally have the following properties: not kneadable at 20 ° C, solid to brittle-hard, coarse to fine crystalline, translucent to opaque, but not glassy, meltable above 40 ° C without decomposition, but a little above Melting point relatively low viscosity and not stringy.
  • wax-like substances should be understood to mean those materials which are largely similar to waxes with regard to physical and chemical properties. It can also be a material that melts below 40 ° C, but shows similar or similar properties in the molten state as occurs with waxes above 40 ° C.
  • the coating liquid contains the wax or the wax-like material in finely divided solid form.
  • the particle size is usually in the range from about 0.1 to 2 pm. According to the invention, particularly good process products are obtained in this particle size range.
  • the suspension of these materials can be prepared in various ways. This can be done, for example, by suspending fine solid particles of these materials, by emulsifying in the melt and subsequent cooling, and also by dissolving in the heat with subsequent cooling with precipitation of the solid material.
  • thermoplastics are hard or even brittle plastics at normal temperature, which soften reversibly when heated and become mechanically easily deformable, in order to finally change into a viscous liquid state at high temperatures. They go through a softening or melting range. According to the invention, they must be soluble in the dispersant (solvent / non-solvent) at room temperature. Taking this requirement into account, it is easily possible for the person skilled in the art to select suitable thermoplastic binders. These include e.g. Polystyrene, polyvinyl acetate, polyvinyl acetal, polyvinyl chloride, copolymers of vinyl acetate and vinyl chloride and cellulose acetobutyrate.
  • Suitable known plasticizers can also be incorporated to control the hardness of the organic binder in the finished melting ink, e.g. Phthalic acid esters, such as di-2-ethylhexyl phthalate, di-isononyl phthalate and di-isodecyl phthalate, aliphatic dicarboxylic acid esters, such as esters of adipic acid, in particular di-2-ethyl-hexyl adipate and diisodecyl adipate, phosphates, such as tricresyl phosphate and triphenyl phosphate, such as diethylene glycol, fatty acid ester (2-ethyl butyrate) and the like. In individual cases it can also be advantageous to incorporate stabilizers into the thermoplastic binder.
  • Phthalic acid esters such as di-2-ethylhexyl phthalate, di-isononyl phthalate and di-isodecyl phthalate
  • the solids content of the coating liquid or starting solution originally used can also be within wide limits, e.g. between about 20 and 80% by weight, preferably between about 30 and 60% by weight.
  • Aromatic, cycloaliphatic as well as branched and unbranched aliphatic hydrocarbons, substituted or unsubstituted, are particularly suitable as non-solvents for the thermoplastic binder of the coating liquid, the conditions being set at room temperature.
  • the aliphatic and cycloaliphatic petroleum components play a special role here, in particular crude gasoline (gasoline) or its sub-fractions in the form of petroleum ether, light petrol, ligroin (mineral spirits), heavy gasoline, light oil (kerosene), i.e.
  • Natural gasoline is also suitable, which represents gasoline gas components present in the natural gas and has been removed from the gas by compression or absorption.
  • the above-mentioned aliphatic petroleum fractions are based on a petroleum that mainly contains straight-chain paraffins.
  • petroleum such as Soviet naphtha
  • the liquid naphthen fractions can also be used advantageously for the purposes of the invention.
  • the most important representatives include cyclopentane, cyclohexane and cycloheptane.
  • oils are also possible which, in terms of their composition, occupy a middle position between the “paraffinic " and the “naphthenic” oils.
  • various low-boiling aromatic compounds such as benzene, toluene and xylene, are also suitable as non-solvents.
  • the combination of solvent / non-solvent is advantageously carried out in such a way that the solvent evaporates first in the course of evaporation of the solvent mixture of the coating liquid which is applied to the support of the thermal ink ribbon. This ensures that the dissolving power of the dispersing agent of the applied coating liquid decreases in the course of the progressive evaporation of the liquid portion and thus the solid layer of the melting ink is finally formed by the continuous precipitation of solids from the coating liquid.
  • the type of colorant, which is then the finished on are included in the enamel is not decisive for the desired effects. It can be both inorganic and organic colorants, each in natural or synthetic form.
  • the inorganic colorants are pigments, such as carbon black, and may also have a filler character.
  • the dyes include colorants which are soluble in solvents and / or binders.
  • triphenylmethane dyes such as Victoria Blue B (CI Basic Blue 26), Ink Blue G (CI Acid Blue 93) and Water Blue TBA (CI Acid Blue 22), azo dyes such as Sudan Deep Black BB (CI Solvent Black 3) and Sudan Brown 1 (CI Solvent Brown 1), metal complex dyes such as Neozapon Black RE (CI Solvent Black 27) and Neozapon Blue FLE (CI Solvent Blue 70) and spirit-soluble dyes such as Spirit Blue (CI Solvent Blue 3) and Spirit Soluble Fast Black (CI Solvent Blue 70).
  • triphenylmethane dyes such as Victoria Blue B (CI Basic Blue 26), Ink Blue G (CI Acid Blue 93) and Water Blue TBA (CI Acid Blue 22)
  • azo dyes such as Sudan Deep Black BB (CI Solvent Black 3) and Sudan Brown 1 (CI Solvent Brown 1)
  • metal complex dyes such as Neozapon Black RE (CI Solvent Black 27) and Neozapon Blue FLE (CI Solvent Blue 70)
  • spirit-soluble dyes such as Spirit Blue (
  • the coating liquid can be evaporated or concentrated in any way, e.g. by transferring warm air. In general, of course, work can also be carried out at room temperature, although the passage of air takes a long time.
  • the starting point is a coating liquid which contains the wax or the wax-like substance in the finest dispersion, namely emulsified and / or suspended. The type of dispersion naturally also depends on the type of solvent / non-solvent system and on the starting temperature.
  • the invention can be explained as follows: by evaporation of the solvent / non-solvent mixture, the non-solvent accumulates in the liquid phase of the coating system and continuously causes the framework substance or the thermoplastic resin to fail. In this precipitation process, the substances already in solid form, e.g. the pigments or the other precipitated solid substances are incorporated into the framework. There they act as a fault or predetermined breaking point during the transfer process. This predetermined breaking point ensures that not all of the ink mass present, but only a fraction of it, is transferred to the point heated during the thermal transfer printing process. This makes it possible to produce a thermal ribbon for thermal transfer printing that can be overwritten more than 20 times. Such favorable values are not known in the prior art.
  • the following system is first melted at 80 ° C. in a water bath to form a homogeneous system: 18 g toluene, 10.4 g methyl ethyl ketone, 12 g behenyl alcohol and 6 g vinyl chloride / vinyl acetate copolymer, dissolved in 17.8 g MEK, and 0. 2 g polyvinyl chloride stabilizer. This is followed by cooling to room temperature with stirring.
  • a disperse system of 3.1 g of carbon black, 3.1 g of triphenylmethane reflex blue (dye) and 16 g of methyl ethyl ketone and 23.6 g of toluene is added.
  • the same grinding is carried out as in the previous examples.
  • toluene 45 g of toluene, 45 g of ethyl alcohol, 12 g of oleic acid amide, 10 g of vinyl chloride / vinyl acetate copolymer, dissolved in 30 g of MEK, 0.2 g of polyvinyl chloride stabilizer, 5 g of beeswax and 7.5 g of azo dye (CI Solvent Black 3) melted into a homogeneous system on a water bath.
  • the coating composition is cooled to room temperature with constant stirring. The grinding and coating is carried out as in the previous examples.

Landscapes

  • Physics & Mathematics (AREA)
  • Optics & Photonics (AREA)
  • Thermal Transfer Or Thermal Recording In General (AREA)
  • Application Of Or Painting With Fluid Materials (AREA)
  • Paints Or Removers (AREA)
EP86904125A 1985-06-07 1986-06-04 Verfahren zur herstellung eines thermofarbbandes für den thermotransferdruck und das danach erhältliche thermofarbband Expired EP0225383B1 (de)

Priority Applications (1)

Application Number Priority Date Filing Date Title
AT86904125T ATE46660T1 (de) 1985-06-07 1986-06-04 Verfahren zur herstellung eines thermofarbbandes fuer den thermotransferdruck und das danach erhaeltliche thermofarbband.

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE19853520308 DE3520308A1 (de) 1985-06-07 1985-06-07 Verfahren zur herstellung eines thermofarbbandes fuer den thermotransferdruck und das danach erhaeltliche thermofarbband
DE3520308 1985-06-07

Publications (2)

Publication Number Publication Date
EP0225383A1 EP0225383A1 (de) 1987-06-16
EP0225383B1 true EP0225383B1 (de) 1989-09-27

Family

ID=6272588

Family Applications (1)

Application Number Title Priority Date Filing Date
EP86904125A Expired EP0225383B1 (de) 1985-06-07 1986-06-04 Verfahren zur herstellung eines thermofarbbandes für den thermotransferdruck und das danach erhältliche thermofarbband

Country Status (5)

Country Link
US (1) US4820551A (enrdf_load_stackoverflow)
EP (1) EP0225383B1 (enrdf_load_stackoverflow)
JP (1) JPS63500023A (enrdf_load_stackoverflow)
DE (2) DE3520308A1 (enrdf_load_stackoverflow)
WO (1) WO1986007311A1 (enrdf_load_stackoverflow)

Families Citing this family (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE3728076A1 (de) * 1987-08-22 1989-03-02 Pelikan Ag Verfahren zur herstellung eines thermofarbbandes fuer den thermotransferdruck und das danach erhaeltliche thermofarbband
DE3728075A1 (de) * 1987-08-22 1989-03-02 Pelikan Ag Thermofarbband fuer den thermotransferdruck sowie dessen herstellung
US4925324A (en) * 1987-10-02 1990-05-15 Alps Electric Co., Ltd. Color ink ribbon for thermal printer
DE3889527T2 (de) * 1987-12-02 1994-12-08 Matsushita Electric Ind Co Ltd Thermische Farbstoffübertragungsdruckschicht.
US5171639A (en) * 1988-05-16 1992-12-15 Pelikan Aktiengesellschaft Method of making a thermocolor ribbon for a thermal printing process
DE3816636A1 (de) * 1988-05-16 1989-11-23 Pelikan Ag Verfahren zur herstellung eines thermofarbbandes fuer den thermotransferdruck
DE4000249C1 (en) * 1990-01-06 1991-05-08 Renker Gmbh & Co Kg, 5160 Dueren, De Producing heat sensitive material for thermal printers etc. - by applying adhesive polymer to both sides of strip substrate, precipitating polymer etc.
JP2665851B2 (ja) * 1990-11-22 1997-10-22 株式会社リコー 可逆性感熱記録材料
GB9410273D0 (en) * 1994-05-20 1994-07-13 Prestek Ltd Printing apparatus
US5707082A (en) * 1995-07-18 1998-01-13 Moore Business Forms Inc Thermally imaged colored baggage tags
DE102007027784B4 (de) * 2007-06-16 2010-06-02 Bischof + Klein Gmbh & Co. Kg Verpackungsbehälter

Family Cites Families (18)

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Publication number Priority date Publication date Assignee Title
US2872340A (en) * 1954-02-18 1959-02-03 Columbia Ribbon Carbon Mfg Transfer element and method of making the same
US3002858A (en) * 1955-05-10 1961-10-03 Columbia Ribbon Carbon Mfg Ink receptive coating composition
US3119014A (en) * 1960-12-09 1964-01-21 Columbia Ribbon & Carbon Novel duplicating system
US3287153A (en) * 1963-08-22 1966-11-22 Royal Typewriter Co Inc Pressure sensitive sponge-like transfer device
GB1175065A (en) * 1966-09-12 1969-12-23 Kores Mfg Company Ltd Copy Sheet and Method of Making the Same
US3852091A (en) * 1971-01-25 1974-12-03 Columbia Ribbon Carbon Mfg Thermographic transfer sheets
US3935362A (en) * 1973-10-25 1976-01-27 Bell & Howell Company Image control means and structured transfer sheet for thermal reproduction processes
JPS5468253A (en) * 1977-11-09 1979-06-01 Gen Corp Heat sensitive transfer medium
DE2911798C2 (de) * 1979-03-26 1983-08-18 Pelikan Ag, 3000 Hannover Anordnung zum Erzeugen hellfarbiger Markierungen auf einem dunkelfarbigen Untergrund für die Overhead-Projektion
US4309117A (en) * 1979-12-26 1982-01-05 International Business Machines Corporation Ribbon configuration for resistive ribbon thermal transfer printing
JPS57160691A (en) * 1981-03-31 1982-10-04 Fujitsu Ltd Ink composition for heat transfer recording and heat transfer recording ink sheet employing said composition
JPS5849296A (ja) * 1981-09-18 1983-03-23 Ricoh Co Ltd 感熱転写用記録材料
JPS58128897A (ja) * 1982-01-27 1983-08-01 Dainippon Printing Co Ltd 感熱転写記録紙の製造方法
JPS5924693A (ja) * 1982-07-30 1984-02-08 Pilot Pen Co Ltd:The 転写型感熱シ−ト用インク
JPS59145191A (ja) * 1983-02-09 1984-08-20 Fujitsu Ltd インクシ−トの製造方法
JPS59194892A (ja) * 1983-04-21 1984-11-05 Konishiroku Photo Ind Co Ltd 感熱転写記録媒体
DE3315249C2 (de) * 1983-04-27 1987-01-22 Renker GmbH & Co KG, 5160 Düren Wärmeempfindliches Aufzeichnungs/Übertragungsmaterial sowie Verfahren zu dessen Herstellung
DE3328990C2 (de) * 1983-08-11 1985-12-12 Pelikan Ag, 3000 Hannover Thermofarbband sowie Verfahren zu dessen Herstellung

Also Published As

Publication number Publication date
WO1986007311A1 (fr) 1986-12-18
DE3665834D1 (en) 1989-11-02
EP0225383A1 (de) 1987-06-16
JPS63500023A (ja) 1988-01-07
DE3520308A1 (de) 1986-12-11
US4820551A (en) 1989-04-11
DE3520308C2 (enrdf_load_stackoverflow) 1987-12-03

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