EP0955182B1 - Ruban pour le transfert thermique - Google Patents

Ruban pour le transfert thermique Download PDF

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Publication number
EP0955182B1
EP0955182B1 EP99108563A EP99108563A EP0955182B1 EP 0955182 B1 EP0955182 B1 EP 0955182B1 EP 99108563 A EP99108563 A EP 99108563A EP 99108563 A EP99108563 A EP 99108563A EP 0955182 B1 EP0955182 B1 EP 0955182B1
Authority
EP
European Patent Office
Prior art keywords
thermal transfer
transfer ribbon
wax
amorphous polymer
carrier
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
EP99108563A
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German (de)
English (en)
Other versions
EP0955182A2 (fr
EP0955182A3 (fr
Inventor
Heinrich Krauter
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
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Pelikan Produktions AG
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Filing date
Publication date
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Publication of EP0955182A2 publication Critical patent/EP0955182A2/fr
Publication of EP0955182A3 publication Critical patent/EP0955182A3/fr
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Publication of EP0955182B1 publication Critical patent/EP0955182B1/fr
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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
    • B41M5/382—Contact thermal transfer or sublimation processes
    • B41M5/392—Additives, other than colour forming substances, dyes or pigments, e.g. sensitisers, transfer promoting agents
    • B41M5/395—Macromolecular additives, e.g. binders
    • 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 transfer ribbon with a support, with one on one Side of the carrier trained thermal transfer ink and optionally with other Layers, the thermal transfer color in addition to a colorant an amorphous Contains polymer and a wax.
  • a thermal transfer ribbon of the type described above goes from DE 36 13 846 out.
  • the thermal transfer ink of this known thermal transfer ribbon contains a amorphous polymer which has a weight average molecular weight Mw of no more than 10,000, a number average molecular weight Mn of less than 5,000 and one Glass transition temperature of 50 to 80 ° C has.
  • the amorphous polymer does at least 50% by weight of the thermal transfer ink, based on its solids content, out.
  • This thermal transfer ribbon is intended to provide clear color reproduction when printing enable and in terms of resolution, sensitivity, Transfer and fixation properties should be satisfactory.
  • EP-B-0 380 920 recommends for Achieving scratch-resistant prints that in the thermal transfer ink during printing non-melting, colorant-containing polymer spheres are included, which in a the heat treatment downstream of the printing process are fusible.
  • the after symbols immediately obtained during the printing process do not initially show the desirable scratch resistance. This is achieved by adding further symbols Heat is supplied. This creates a new structure of the printed Symbol.
  • This proposal is disadvantageous in that it follows the actual one Printing process requires a second heat treatment step.
  • Thermal transfer ribbon with a conventional carrier, with one on one side of the carrier trained layer of a thermal transfer ink and a separating layer between Carrier and layer of thermal transfer ink before.
  • the interface is wax-bound and contains waxes with a melting point of about 70 to 110 ° C and one polymeric wax plasticizer with a glass transition temperature Tg of -30 to + 70 ° C.
  • the Thermal transfer ink layer further contains at least about 20% by weight Natural resin, modified natural resin and / or synthetic resin.
  • the transferred one Thermal transfer ink when printing on paper labels in particular has good adhesion as well as good abrasion and scratch resistance, and when printing quickly and is delivered precisely with the underlying separation or release layer.
  • the disadvantage is the fact that with a certain effort described separation layer is to be formed, which is at least one three-tier system.
  • the present invention the object of the above Develop thermal transfer ribbon so that no separation layer is required, and nevertheless that in connection with the description of the subject of DE 196 12 393 A1 achieved advantages can be achieved.
  • the thermal transfer ink as Binder is a polar polyethylene wax and an amorphous polymer that is a Weight average molecular weight Mw greater than about 10,000 and a number average of Has molecular weight Mn of less than about 6,000.
  • the thermal transfer color of the thermal transfer ribbon contains an amorphous polymer as an essential binder component, in particular of at least about 50% by weight, based on the dry matter content of the Thermal transfer ink. If one speaks of an "amorphous" polymer, then so this is supposed to mean that its structural characteristics appearing below radiographic aspects can be described as amorphous. As a result, Under the term “amorphous polymer”, such oligomers and / or Polymers fall that contain certain partially crystalline components, for example up to about 30% by weight, especially up to about 10% by weight. Contrary to the trend-setting According to DE 36 13 846 C2, the invention uses an amorphous polymer which has a weight average molecular weight Mw greater than about 10,000. This is surprising.
  • weight average molecular weight Mw is more than is about 10,000, probably explained by the fact that an additional and mandatory polar polyethylene wax must be present. If the Mw value of Below 10,000, which would be in accordance with DE 36 13 846 C2, then there is the disadvantageous effect that the adhesion of the thermal transfer ink to Carrier film is too high and there is no homogeneous color transfer during printing is guaranteed.
  • the amorphous polymer is a weight average Molar mass Mw from 10,000 to about 15,000 and a number average molar mass Mn less than about 5,000, especially about 2,000 to 3,000.
  • polar Polyethylene wax and amorphous polymer can be specified to 1 part by weight polar polyethylene wax about 3 to 5 parts by weight, in particular about 4 parts by weight, no amorphous polymer.
  • the amorphous polymer content is less than about 50% by weight, then this can lead to the desirable transparency of the thermal transfer ink and thus the color reproducibility is impaired. So in general it is preferred if the amorphous polymer content is more than about 50% by weight, in particular more than about 70 wt .-%, but the maximum is about 80 wt .-% could be specified to still have a sufficient amount of polar polyethylene wax.
  • Binding agents are present in small amounts in the thermal transfer ink, so in Thermal transfer ribbons usually used waxes, for example Paraffin wax, caranauba wax, montan wax, beeswax, japan wax, Candelilla wax as well as materials used as plastic binders, such as polyolefins with an average molecular weight of about 1,000 to 10,000, for example low molecular weight polyethylene, polypropylene or polybutylene and the same.
  • plastic binders such as polyolefins with an average molecular weight of about 1,000 to 10,000, for example low molecular weight polyethylene, polypropylene or polybutylene and the same.
  • plastic binders such as polyolefins with an average molecular weight of about 1,000 to 10,000, for example low molecular weight polyethylene, polypropylene or polybutylene and the same.
  • plastic binders such as polyolefins with an average molecular weight of about 1,000 to 10,000, for example low molecular weight polyethylene, polyprop
  • amorphous polymers examples include homo- and copolymers, styrene or their derivatives or substituted compounds thereof (e.g. styrene; Vinyl, toluene), acrylic acid esters, for example methyl acrylate, ethylene acrylate and butyl acrylate copolymers, especially polyester resins, by polycondensation saturated dibasic acid are available (for example phthalic acid, Phthalic anhydride), polycarbonates, polyamides, epoxy resins, polyurethanes, silicone resins, Phenolic resins, terpene resins, petroleum resins, hydrogenated petroleum resins, alkyd resins and Cellulose derivatives.
  • styrene Vinyl, toluene
  • acrylic acid esters for example methyl acrylate, ethylene acrylate and butyl acrylate copolymers
  • polyester resins by polycondensation saturated dibasic acid are available (for example phthalic acid, Phthalic anhydride)
  • An amorphous polyester resin with an MFI value (105 ° C / 2.16 kg) is preferred from about 1.3 to 2.3, especially from about 1.5 to 2.0 g / min and a glass transition temperature Tg of about 45 to 65 ° C, especially about 52 to 56 ° C, used.
  • An amorphous polyester resin that meets these framework conditions and in particular is advantageously used is a polyester resin based on bisphenol A, such as the commercial product Setafix P 120 (distributed by Akzo Noble Resins B.V., Netherlands), which is characterized by the following characteristics: MFI value (105 ° C / 2.16 kg) of about 1.5 to 2.0 g / min, glass transition temperature Tg of 52 up to 56 ° C and acid number from 14 to 24 mg KOH / g, Mn value about 2,500 and Mw value about 12,000.
  • a polyester resin of the trade name is also suitable Atlac T 500 (sold by ICI Specialty Chemicals, Great Britain).
  • polar polyethylene wax is obtained either by oxidation of polyethylene wax or by oxidative degradation of plastic-like polyethylene. This creates a range of polar, emulsifiable polyethylene waxes.
  • Hoechst waxes PED and the type designations 521 and 522 are particularly suitable. These belong to the series of more flexible emulsifiable polyethylene waxes, the melting point of which allows emulsification in an open vessel.
  • a preferred dropping point of about 100 to 110 ° C, in particular about 102 to 108 ° C and very particularly preferably of about 102 to 106 ° C, measured according to DIN 51 801, is the preferred framework for the polar polyethylene waxes polar polyethylene wax, the following sizes are given: ball indentation hardness according to the test method DGF-M III-90 (57) of approx. 1 to 3 ⁇ 10 7 Pa (100 to 300 bar), a flow hardness of approx. 1 to 3 ⁇ 10 -7 Pa (100 up to 300 bar) and a viscosity, measured according to DIN 51 550 at a temperature of about 120 ° C, of about 50 to 700 mPas, in particular from about 100 to 500 mPas.
  • the coloring of the thermal transfer color can be done by any Colorants are made. It can be pigments, especially soot, but also to solvent and / or binder-soluble colorants, such as the commercial product Basoprint, organic color pigments and various acco colorants (Cerces and Sudan dyes) act. Soot is considered in the context of the present invention particularly suitable.
  • the thermal transfer ink preferably contains the colorant, in particular color pigment, in an amount of about 20 to 40 wt .-%.
  • the thermal transfer color shows preferably a viscosity of about 500 to 3,000 mPas, measured with a Brookfield rotational viscometer at 140 ° C. In particular, the range of 600 to 1,500 mPas aimed for.
  • the thickness of the thermal transfer ink or the ink layer is not critical. A thickness of approximately 1 to 5 g / m 2 application, in particular approximately 1 to 3 g / m 2 application, is preferred on the carrier.
  • the type of carrier is also not critical here. It is preferably a film made of polyethylene terephthalate (PET) or a capacitor paper.
  • PET polyethylene terephthalate
  • the selection parameters are the highest possible tensile elongation values and thermal stability with small film thicknesses, for example in the range of approximately 1 to 6 ⁇ m.
  • the PET films are available up to about 2.5 ⁇ m, capacitor paper up to about 6 ⁇ m.
  • This back coating material preferably consists of paraffin, silicone, natural waxes, in particular carnauba wax, beeswax, ozocerite and paraffin wax or synthetic waxes, in particular acid waxes, ester waxes, partially saponified ester waxes and polyethylene waxes, glycols or polyglycols and / or surfactants.
  • the range of 1.4 to 2.0 g / m 2 , in particular approximately 1.6 to 1.8 g / m 2 is very particularly preferred for the strength of the thermal transfer ink.
  • the above-mentioned backside coating is optionally applied on the back in a thickness of about 0.01 to 1 g / m 2 , in particular about 0.05 to 0.10 g / m 2 .
  • These layers can be formed in a variety of ways using customary application methods. This can be done, for example, by spraying or printing on a solution or dispersion, be it with water or an organic solvent, by application from the melt, which is particularly true for the thermal transfer layer, or by application by means of a doctor blade in the form of an aqueous suspension with finely divided therein material to be applied. Coating methods such as reverse roll and / or gravure coating have proven to be particularly advantageous for applying the thermal transfer layer.
  • the particular advantages associated with the invention can be as follows represent:
  • the invention surprisingly requires compared to DE 196 12 393 A1 no additional separating layer and comes with a total of two layers from, advantageously a back coating for the reasons mentioned is provided. It will not only be scratch-resistant but also achieved solvent-resistant prints on plastic labels, especially in Connection with so-called barcode labels.
  • amorphous Polymers with an Mw of more than 10,000.
  • the polar polyethylene wax used according to the invention has a functional effect Working together in such a way that the essential properties of a such a tape must not be impaired, but that in printing transferred thermal transfer ink a good one, especially on plastic labels Adhesion and good abrasion and scratch resistance shows and quickly and precisely is transmitted.
  • plastic labels such as. made of polyethylene, polypropylene, vinyl chloride, for coated PET films and glossy papers. In doing so, these favorable results are in the upper energy level of the thermal transfer printer.
  • the polyethylene waxes are used apparently to convey a good release function and thus make the Adhesion to the printed film. They mediate because of their good gliding behavior the particularly favorable scratch resistance of the printouts.
  • a material of the following recipe is applied to a conventional carrier made of polyethylene terephthalate with a thickness of about 4.5 ⁇ m to form a thermal transfer color layer: Parts by weight Polyester resin based on a bisphenol A (trade name: Setafix P 120, sold by Akzo Nobel Resins BV) 60 Polar polyethylene wax (trade name: PED 521, sold by Hoechst AG) 7.5 Polar polyethylene (trade name: P 522, sold by Hoechst AG) 7.5 Hoechst AG) soot 25 total 100
  • the properties of the above binder components are as follows: PED 521 Dropping point: 105 ° C (DIN 51 801), acid number: 17 mg KOH / g (DIN 53 402), saponification number: 35 mg KOH / g (DIN 53 401), density: 0.95 g / cm 3 at 20 ° C (DIN 53 479), ball pressure hardness: 1 to 3 ⁇ 10 7 Pa (100-300 bar) (DGF-M III-90 (57)), flow hardness: 1 to 3 ⁇ 10 7 Pa (100-300 bar) and viscosity 100-500 mPas at 120 ° C (DIN 51 550).
  • PED 522 Dropping point: 103 ° C (DIN 51 801), acid number: 25 mg KOH / g (DIN 53 402), saponification number: 55 mg KOH / g (DIN 53 401), density: 0.96 g / cm 3 at 20 ° C (DIN 53 479), ball pressure hardness: 1 to 3 ⁇ 10 7 Pa (100-300 bar) (DGF-M III-90 (57)), flow hardness: 1 to 3 ⁇ 10 7 Pa (100-300 bar) and viscosity 100-500 mPas at 120 ° C (DIN 51 550).
  • the above material is reversed in a solvent dispersion about 20% (toluene / isopropanol: 80:20) in a dry strength of about 1.5 ⁇ m applied.
  • the solvent is evaporated off by passing it over hot air at a temperature of around 100 ° C.
  • the material obtained proved when printing in the high energy level of a thermal transfer printer as scratch and solvent resistant.

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  • Physics & Mathematics (AREA)
  • Optics & Photonics (AREA)
  • Thermal Transfer Or Thermal Recording In General (AREA)

Claims (11)

  1. Ruban de transfert thermique comprenant un support, une encre de transfert thermique formée d'un côté du support et, le cas échéant, d'autres couches, l'encre de transfert thermique contenant, à côté d'une matière colorante, un polymère amorphe et une cire, caractérisé en ce que l'encre de transfert thermique contient comme liant une cire polyéthylénique polaire et un polymère amorphe qui présente une moyenne pondérale Mp de masse molaire de plus d'environ 10 000 et une moyenne numérique Mn de masse molaire de moins d'environ 6000.
  2. Ruban de transfert thermique suivant la revendication 1, caractérisé en ce que le polymère amorphe a une moyenne pondérale Mp de masse molaire de 10 000 à environ 15 000 et une moyenne numérique Mn de masse molaire de moins d'environ 5000, notamment d'environ 2000 à 3000.
  3. Ruban de transfert thermique suivant l'une des revendications précédentes, caractérisé en ce qu'une partie en poids de cire polyéthylénique polaire correspond à environ 3 à 5 parties en poids, notamment à environ 4 parties en poids, de polymère amorphe.
  4. Ruban de transfert thermique suivant l'une des revendications précédentes, caractérisé en ce que le polymère amorphe est une résine de polyester amorphe, notamment à base d'un bisphénol A.
  5. Ruban de transfert thermique suivant la revendication 3, caractérisé en ce que la cire polyéthylénique polaire a un point de goutte d'environ 100 à 110°C, notamment d'environ 102 à 108°C.
  6. Ruban de transfert thermique suivant la revendication 5, caractérisé en ce que le point de goutte a une valeur d'environ 102 à 106°C.
  7. Ruban de transfert thermique suivant l'une au moins des revendications précédentes, caractérisé en ce que la cire polyéthylénique polaire a une dureté à la bille selon la méthode d'essai DGF-M III-90 (57) d'environ 1 à 3.107 Pa (100 à 300 bars), une dureté d'étirage d'environ 1 à 3.107 Pa (100 à 300 bars) et une viscosité, mesurée selon la norme DIN 51 550 à une température d'environ 120°C, d'environ 50 à 700 mPa.s, en particulier d'environ 100 à 500 mPa.s.
  8. Ruban de transfert thermique suivant l'une au moins des revendications 4 à 7, caractérisé en ce que la résine de polyester amorphe a une valeur MFI (105°C/2,16 kg) d'environ 1,3 à 2,3, en particulier d'environ 1,5 à 2,0 g/10 min et une température Tg de transition vitreuse d'environ 45 à 65°C, en particulier d'environ 52 à 56°C.
  9. Ruban de transfert thermique suivant l'une au moins des revendications précédentes, caractérisé en ce que l'encre de transfert thermique a un poids surfacique d'environ 1 à 5 g/m2, en particulier d'environ 1 à 3 g/m2.
  10. Ruban de transfert thermique suivant l'une au moins des revendications précédentes, caractérisé en ce que le support est en polymère de téréphtalate d'éthylène.
  11. Ruban de transfert thermique suivant l'une au moins des revendications précédentes, caractérisé en ce qu'une couche formée d'une cire ou d'une matière cireuse est appliquée en un poids surfacique d'environ 0,01 à 1 g/m2, en particulier d'environ 0,05 à 0,10 g/m2 au verso du support.
EP99108563A 1998-05-08 1999-05-05 Ruban pour le transfert thermique Expired - Lifetime EP0955182B1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE19820778 1998-05-08
DE19820778A DE19820778C2 (de) 1998-05-08 1998-05-08 Thermotransferband

Publications (3)

Publication Number Publication Date
EP0955182A2 EP0955182A2 (fr) 1999-11-10
EP0955182A3 EP0955182A3 (fr) 2000-09-06
EP0955182B1 true EP0955182B1 (fr) 2003-08-27

Family

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Family Applications (1)

Application Number Title Priority Date Filing Date
EP99108563A Expired - Lifetime EP0955182B1 (fr) 1998-05-08 1999-05-05 Ruban pour le transfert thermique

Country Status (4)

Country Link
US (1) US6461721B1 (fr)
EP (1) EP0955182B1 (fr)
CA (1) CA2271434A1 (fr)
DE (2) DE19820778C2 (fr)

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE10152849A1 (de) * 2001-10-29 2003-05-28 Emtec Magnetics Gmbh Beschichtung eines Thermotransfer- und/oder Thermosublimationsproduktes, Verfahren zu dessen Herstellung sowie dessen Verwendung

Family Cites Families (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3941596A (en) * 1962-10-24 1976-03-02 E. I. Du Pont De Nemours And Company Thermographic processes using polymer layer capable of existing in metastable state
DE3328990C2 (de) * 1983-08-11 1985-12-12 Pelikan Ag, 3000 Hannover Thermofarbband sowie Verfahren zu dessen Herstellung
DE3613846C2 (de) * 1985-04-24 1997-04-24 Fuji Xerox Co Ltd Wärmeempfindliches Aufzeichnungsmaterial und dessen Verwendung
GB2178553B (en) * 1985-07-29 1990-01-04 Canon Kk Thermal transfer material
US4762734A (en) * 1986-11-24 1988-08-09 Xerox Corporation Processes for thermal transfer ink donor films
EP0351794A3 (fr) * 1988-07-19 1991-03-13 Nitto Denko Corporation Encre fixable par la chaleur, feuille de dessins l'utilisant et méthode pour la formation d'un dessin

Also Published As

Publication number Publication date
DE59906727D1 (de) 2003-10-02
DE19820778C2 (de) 2003-02-20
EP0955182A2 (fr) 1999-11-10
US6461721B1 (en) 2002-10-08
CA2271434A1 (fr) 1999-11-08
EP0955182A3 (fr) 2000-09-06
DE19820778A1 (de) 1999-11-11

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