EP0304673B1 - Thermofarbband für den Thermotransferdruck sowie dessen Herstellung - Google Patents

Thermofarbband für den Thermotransferdruck sowie dessen Herstellung Download PDF

Info

Publication number
EP0304673B1
EP0304673B1 EP88112416A EP88112416A EP0304673B1 EP 0304673 B1 EP0304673 B1 EP 0304673B1 EP 88112416 A EP88112416 A EP 88112416A EP 88112416 A EP88112416 A EP 88112416A EP 0304673 B1 EP0304673 B1 EP 0304673B1
Authority
EP
European Patent Office
Prior art keywords
wax
substance
thermal
thermoplastic binder
aqueous
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
EP88112416A
Other languages
German (de)
English (en)
French (fr)
Other versions
EP0304673A1 (de
Inventor
Norbert Dr. Mecke
Albert Schmedes
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 AT88112416T priority Critical patent/ATE69768T1/de
Publication of EP0304673A1 publication Critical patent/EP0304673A1/de
Application granted granted Critical
Publication of EP0304673B1 publication Critical patent/EP0304673B1/de
Anticipated expiration legal-status Critical
Expired - Lifetime 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

Definitions

  • the invention relates to a thermal ink ribbon for thermal transfer printing with a layer of melting ink on one side of a carrier film, the melting ink containing a wax and / or a wax-like substance, a colorant, a thermoplastic binder and, if appropriate, further additives, and a process for the production thereof.
  • Thermal ribbons have been known for a long time. They point to a film-like carrier which, for. B. can consist of paper or plastic, a layer of a melting ink, so in the form of a meltable wax-bound or plastic-bound colorant or carbon black layer.
  • the melting ink is melted by means of a thermal print head and transferred to a recording paper or film. This is generally referred to as a thermal transfer ribbon or TCR ribbon ("Thermal Carbon Ribbon").
  • Thermal printers that emboss a thermal symbol during the printing process are e.g. B. from DE-ASen 2 062 494 and 2 406 613 and DE-OS 3 224 445 known.
  • the printing process is as follows: The print head of a thermal printer presses the thermal ink ribbon onto the recording substrate.
  • 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 in direct contact with the printhead or the thermal symbol formed thereon during the printing process.
  • the relative speed between the thermal ink ribbon and the printing paper or film is zero.
  • the melting ink in the form of the symbol to be printed is transferred from the thermal ink ribbon to the recording substrate by a melting process.
  • the thermal ink ribbon is detached from the recording substrate, the molten symbol adheres to it and solidifies.
  • thermal ribbons with simple film-like carriers
  • heat symbol is not generated by a thermal print head but by resistance heating of a specially designed film-like carrier.
  • the melting color which represents the actual "functional layer” during the printing process, also contains the materials already described above. In professional circles this is called an electro-thermal transfer process ("Electro Thermal Ribbon”).
  • electro-thermal transfer process Such a thermal transfer printing system is described, for example, in US Pat. No. 4,309,117.
  • thermal ribbons that advertise several times (keyword: "multiuse”). Such thermal ribbons are described for example in EP-A-0 063 00.
  • 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 allows only a small amount of the molten colored material to be transferred to be used in each individual printing operation.
  • the invention was therefore based on the object of developing the thermal ink ribbon described at the outset in such a way that it precludes the need to use environmentally harmful solvents in its production.
  • thermoplastic binder is the framework substance, in the cavities of which particles of a fat-soluble dye, a pigment and a wax or a wax-like substance are present side by side.
  • the thermal ribbon according to the invention can be produced particularly advantageously by applying an aqueous coating dispersion which contains the thermoplastic binder, the wax or the wax-like substance and a fat-soluble dye in finely divided solid form to the carrier of the thermal ribbon in a manner known per se and the aqueous portion of the dispersion is evaporated.
  • the essence of the invention is therefore that an aqueous coating dispersion containing the necessary fine-particle solids is applied to the carrier film and the aqueous portion of the dispersion is evaporated below the melting point of the integrated wax particles or particles of the wax-like substance.
  • any plastic films are suitable, which are also used as supports in conventional carbon ribbons of typewriters, but which also withstand the high temperatures mentioned during the briefly running printing process and also release the melting ink at these temperatures.
  • the plastic film consists in particular of thermoplastic plastics with a higher glass transition temperature.
  • 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.
  • polyethylene terephthalates and polycarbonates are preferred.
  • the plastic film to be used according to the invention can also be a fabric laminated on one or both sides.
  • similarly designed common composite films can be used within the scope of the invention.
  • plasticizer 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, e.g. B. about 3 to 6 microns to allow the necessary heat transfers to run optimally. This range can also be exceeded or fallen below to a greater or lesser extent.
  • 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 the melting point relatively low-viscosity and non-stringy.
  • “wax-like substances” should be understood to mean those materials which largely resemble the waxes with regard to the physical and chemical properties.
  • the aqueous coating dispersion contains the mentioned solid particles, i.e. H. the thermoplastic, the wax or the wax-like substance and the fat-soluble dye and the pigment, preferably in a particle size of 0.5 to 100 micrometers and in particular of about 5 to 50 micrometers. Particularly good process products are obtained in this particle size range.
  • the aqueous coating dispersion or suspension of these materials can be prepared in various ways. This can be done, for example, by suspending fine, solid particles of these materials or else by emulsifying in the melt and then cooling, preferably with stirring to maintain the finest dispersion.
  • An essential component of the layer of the melting ink to be formed according to the invention is a thermoplastic.
  • 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.
  • thermoplastics which do not melt during the final thermal treatment, or which at most soften at most. Taking this requirement into account, it is easily possible for the person skilled in the art to select suitable thermoplastic binders. These include in particular polystyrene, polyvinyl acetate, polyvinyl acetal, polyvinyl chloride, polyamides, polyethylene, copolymers of vinyl acetate and vinyl chlorides, polyvinyl ethers, polyvinyl propionates, polyacrylates, ethylene / vinyl acetate copolymers.
  • thermoplastic binders serve as a framework substance in the layer of the melting ink designed according to the invention.
  • suitable known plasticizers can also be incorporated into the thermoplastic binder.
  • phthalic acid esters such as di-2-ethylhexyl phthalate, di-isononyl phthalate and di-isodecyl phthalate
  • aliphatic dicarboxylic acid esters such as that of adipic acid, in particular di-2-ethylhexyl adipate and diisodecyl adipate
  • phosphates such as tricresyl phosphate and triphenyl phosphate, such as diethylene glycol, (2-ethyl butyrate) and the like.
  • stabilizers into the thermoplastic binder.
  • the ratio of wax or wax-like substance to the thermoplastic binder in the aqueous coating dispersion can vary widely and is not critical for the purposes of the invention.
  • the weight ratio can easily be between about 10: 1 to 1: 5.
  • a weight ratio of approximately 5: 1 to 1: 1 is preferred.
  • the solids content of the coating dispersion or starting dispersion originally used can also vary within wide limits, for example. B. between about 20 and 80 wt .-%, preferably between about 30 and 60 wt .-%.
  • fat-soluble dyes or "fat dyes” meet this requirement.
  • This class includes, for example, simply structured azo and anthraquinone dyes.
  • the pigments used are: carbon blacks, organic and / or inorganic color pigments, but also so-called fillers such as chalk, china clay, kaolin, clay, etc.
  • aqueous coating dispersion Preferably only water is contained in the aqueous coating dispersion discussed as a dispersing agent.
  • polar and / or non-polar solvents that are more or less harmful to the environment should be excluded as far as possible. Nevertheless, it can be accepted in individual cases that smaller amounts of such solvents are contained in the coating dispersion, for example ethanol.
  • the aqueous coating dispersion can be applied to the support in any manner, for example with a doctor knife.
  • the application technology is therefore not critical. You can also be evaporated or concentrated in any way, for. B. by transferring warm air.
  • the temperature during evaporation or concentration of the aqueous portion of the applied aqueous coating dispersion should only be chosen so high that the wax particles or the particles of the wax-like substance are not melted as much as possible during the thermal treatment.
  • work can also be carried out at room temperature, whereby the thermal treatment or the transfer of air would require a longer time.
  • the layer thickness of the melting ink should generally be between about 5 and 30 micrometers and preferably 10 to 20 micrometers (dry layer). If appropriate, an adhesion-promoting layer with a thickness of approximately 0.1 to 5 micrometers, preferably approximately 0.5 to 2 micrometers, can be arranged between the color layer and the carrier film. This preferably consists of polymeric materials of a known type.
  • aqueous coating dispersion was prepared using the following recipe: Ethylene-vinyl acetate copolymer (Ehaflex 5601 / Akzo Chemie) 15 parts by weight Carbon black (Regal 400 R / Cabot Corp.) 2.5 " Disazo Dye Solvent Red 18 Ceresrot 3R / Bayer AG) 0.1 " Disazo dye solvent black 3 (neozapone black / BASF) 0.9 " distilled water 2.5 " Ethanol 2.5 " Defoamer for the aqueous dispersion (Additol VX W 4932 / Hoechst AG) 1 " Polyethylene wax / paraffin dispersion Südranol 340 / South German emulsion chemistry) 25 " Polysiloxane (organo-modified) (Forbest G 23 / Lukas Meier) 0.1 "
  • the dispersion which made up a total of 49.6 parts by weight, was applied by means of a doctor blade in a layer thickness of about 20 micrometers (based on the product which was subsequently dried) to a polyester support. By passing warm air at a temperature of 80 ° C, the aqueous portion of the applied dispersion was evaporated within a few minutes.
  • the product obtained could be used directly as a thermal ribbon. It allowed an 8x multiuse.
  • a thermal ink ribbon was produced using the following recipe, the application and further treatment taking place in accordance with the measures of Example 1 while achieving the same quality of the process product: Ethylene-vinyl acetate copolymer (Ehaflex 222 / Akzo Chemie) 15 parts by weight Streichclay (Colloid Clay Supreme / English China Clay Sales Co) 2.5 " Wax ester (Loxiol G 32 / Henkel) 10 " Disazo dye solvent Red 18 (Ceresrot 3 R / Bayer AG) 0.1 " Disazo dye solvent Black 3 (Neptune Black X 60 / BASF) 0.9 " Defoamer for aqueous dispersions (Additol VX W 4932 / Hoechst AG) 1 " Polyethylene wax / paraffin dispersion (Südranol 41 / Südd. Emulsion chemistry) 25 "
  • Ethylene-vinyl acetate copolymer (Ehaflex 222 / Akzo Chemie) 15 parts by weight Wax ester (containing amide groups) (Kahl wax 2888 A / K & Co.) 10 " Streichclay (Colloid Clay Supereme / English China Clay Sales Co) 2.5 " Disazo dye solvent Red 18 (Ceresrot 3 R / Bayer AG) 0.1 " Disazo Dye Solvent Black 3 (Neptune Black X60 / BASF) 0.9 " distilled water 5 " Defoamer for aqueous systems (Additol VX W 4932 / Hoechst AG) 1 " Polyethylene wax / paraffin dispersion (Südranol 340 / Südd. Emulsion chemistry) 25 "

Landscapes

  • Physics & Mathematics (AREA)
  • Optics & Photonics (AREA)
  • Thermal Transfer Or Thermal Recording In General (AREA)
  • Paints Or Removers (AREA)
  • Inks, Pencil-Leads, Or Crayons (AREA)
  • Impression-Transfer Materials And Handling Thereof (AREA)
  • Laminated Bodies (AREA)
EP88112416A 1987-08-22 1988-07-30 Thermofarbband für den Thermotransferdruck sowie dessen Herstellung Expired - Lifetime EP0304673B1 (de)

Priority Applications (1)

Application Number Priority Date Filing Date Title
AT88112416T ATE69768T1 (de) 1987-08-22 1988-07-30 Thermofarbband fuer den thermotransferdruck sowie dessen herstellung.

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE3728075 1987-08-22
DE19873728075 DE3728075A1 (de) 1987-08-22 1987-08-22 Thermofarbband fuer den thermotransferdruck sowie dessen herstellung

Publications (2)

Publication Number Publication Date
EP0304673A1 EP0304673A1 (de) 1989-03-01
EP0304673B1 true EP0304673B1 (de) 1991-11-27

Family

ID=6334289

Family Applications (1)

Application Number Title Priority Date Filing Date
EP88112416A Expired - Lifetime EP0304673B1 (de) 1987-08-22 1988-07-30 Thermofarbband für den Thermotransferdruck sowie dessen Herstellung

Country Status (7)

Country Link
US (1) US5132139A (enrdf_load_stackoverflow)
EP (1) EP0304673B1 (enrdf_load_stackoverflow)
JP (1) JP2656082B2 (enrdf_load_stackoverflow)
AT (1) ATE69768T1 (enrdf_load_stackoverflow)
DE (2) DE3728075A1 (enrdf_load_stackoverflow)
ES (1) ES2026976T3 (enrdf_load_stackoverflow)
GR (1) GR3003226T3 (enrdf_load_stackoverflow)

Families Citing this family (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE3825437C1 (enrdf_load_stackoverflow) * 1988-07-27 1989-11-16 Pelikan Ag, 3000 Hannover, De
DE69004132T2 (de) * 1989-03-28 1994-03-24 Dainippon Printing Co Ltd Wärmeempfindliche Übertragungsschicht.
US5707082A (en) * 1995-07-18 1998-01-13 Moore Business Forms Inc Thermally imaged colored baggage tags
GB2324163B (en) * 1997-04-11 2002-03-20 Ncr Int Inc Thermal transfer medium
US6231964B1 (en) 1998-06-30 2001-05-15 Ncr Corporation Thermal transfer ribbons with large size wax or resin particles
US6171690B1 (en) 1998-08-28 2001-01-09 Ncr Corporation Thermal transfer media with a mixture of non-melting solid particles of distinct sizes
JP7074262B2 (ja) * 2020-03-12 2022-05-24 大日本印刷株式会社 熱転写シート及び印画物

Family Cites Families (13)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS58188690A (ja) * 1982-04-30 1983-11-04 Nippon Telegr & Teleph Corp <Ntt> 多数回カラ−熱転写用リボン
JPS59129195A (ja) * 1983-01-13 1984-07-25 Ricoh Co Ltd 熱転写記録媒体
JPS59138494A (ja) * 1983-01-28 1984-08-08 General Kk 感熱転写材及びその製造方法
JPS59145191A (ja) * 1983-02-09 1984-08-20 Fujitsu Ltd インクシ−トの製造方法
JPS59165696A (ja) * 1983-03-11 1984-09-18 Brother Ind Ltd 感熱多数回転写シ−ト及びその製造方法
JPS6049993A (ja) * 1983-08-31 1985-03-19 Toyo Ink Mfg Co Ltd 感熱転写材
JPS60189488A (ja) * 1984-03-09 1985-09-26 Canon Inc 感熱転写材
JPS6110490A (ja) * 1984-06-26 1986-01-17 Fuji Kagakushi Kogyo Co Ltd 多数回使用型熱転写記録媒体
US4769258A (en) * 1984-09-12 1988-09-06 Brother Kogyo Kabushiki Kaisha Multiple-time ink-bearing medium for thermal printing
DE3520308A1 (de) * 1985-06-07 1986-12-11 Pelikan Ag, 3000 Hannover Verfahren zur herstellung eines thermofarbbandes fuer den thermotransferdruck und das danach erhaeltliche thermofarbband
US4783360A (en) * 1985-07-22 1988-11-08 Canon Kabushiki Kaisha Thermal transfer material
GB2178553B (en) * 1985-07-29 1990-01-04 Canon Kk Thermal transfer material
US4818591A (en) * 1985-10-07 1989-04-04 Konishiroku Photo Industry Co., Ltd. Thermal transfer recording medium

Also Published As

Publication number Publication date
DE3728075A1 (de) 1989-03-02
ES2026976T3 (es) 1992-05-16
DE3866471D1 (de) 1992-01-09
EP0304673A1 (de) 1989-03-01
DE3728075C2 (enrdf_load_stackoverflow) 1989-10-19
GR3003226T3 (en) 1993-02-17
ATE69768T1 (de) 1991-12-15
US5132139A (en) 1992-07-21
JPS6471786A (en) 1989-03-16
JP2656082B2 (ja) 1997-09-24

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