EP2505374B1 - Matériel d'enregistrement sensible à la chaleur, son utilisation et son procédé de fabrication - Google Patents

Matériel d'enregistrement sensible à la chaleur, son utilisation et son procédé de fabrication Download PDF

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Publication number
EP2505374B1
EP2505374B1 EP20110160791 EP11160791A EP2505374B1 EP 2505374 B1 EP2505374 B1 EP 2505374B1 EP 20110160791 EP20110160791 EP 20110160791 EP 11160791 A EP11160791 A EP 11160791A EP 2505374 B1 EP2505374 B1 EP 2505374B1
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Prior art keywords
coating composition
oxide
recording material
material according
calcium carbonate
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Not-in-force
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EP20110160791
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German (de)
English (en)
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EP2505374A1 (fr
Inventor
Gerhard Dr. Stork
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Mitsubishi HiTec Paper Europe GmbH
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Mitsubishi HiTec Paper Europe GmbH
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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
    • B41M5/333—Colour developing components therefor, e.g. acidic compounds
    • B41M5/3333—Non-macromolecular compounds
    • 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
    • B41M5/337—Additives; Binders
    • B41M5/3377—Inorganic compounds, e.g. metal salts of organic acids

Definitions

  • the invention further relates to the use of the recording material according to the invention in particular as a material for the formation of tickets and a method for its production.
  • Heat-sensitive recording materials of the type described in particular with paper as a web-shaped substrate are known since the early years of chemically reactive recording materials and enjoy a constantly growing popularity, which is due, inter alia, that their use is particularly associated with a ticket for the ticket issuing with great advantages . Because the color-forming components are stuck in the recording material itself in the heat-sensitive recording method, the toner and ink-cartridge-free printers, which in their function no longer need to be controlled by anyone and thus largely maintenance-free, can be set up in large numbers. So this innovative technology has become particularly important in public transport, on buses and trains as well as in air traffic, but as it were also enforced at stadium and museum funds and at parking detectors.
  • a not necessarily generic recording material having a web-shaped substrate and a heat-sensitive recording layer as an outwardly terminating outer layer containing as developer N- (p-toluenesulphonyl) -N'-3- (p-toluenesulphonyl-oxy-phenyl) -urea according to formula ( 1) contains, for example, from the EP 2 033 799 A1 known.
  • the subject matter of this disclosure is the combination of N- (p-toluenesulphonyl) -N'-3- (p-toluenesulphonyl-oxy-phenyl) -urea essential to the invention with a urea-urethane compound according to the following formula (2):
  • the published document provides the invention essential combination of N- (p-toluenesulphonyl) -N'-3- (p-toluenesulphonyl-oxy-phenyl) urea with 2- (2H-benzotriazol-2-yl) -p-cresol according to the following formula (3) as a sensitizer.
  • thermosensitive recording material having a leuco base dye precursor, N- (p-toluenesulphonyl) -N'-3- (p-toluenesulphonyl-oxy-phenyl) urea as a developer and at least one pigment selected from the list comprising aluminum hydroxide, amorphous Silica, kaolin and talc in the heat-sensitive recording layer.
  • a possible pigment in the heat-sensitive recording layer calcium carbonate is also disclosed.
  • heat-sensitive recording layers are disclosed without pigment (!) And with exactly one pigment selected from the list comprising aluminum hydroxide, amorphous silica, kaolin, talc and magnesium carbonate. It is significant that also this document no suggestions for the use of a pigment combination of two pigments, certainly not to be taken for a given pigment mixing ratio.
  • the present invention has, starting from the previously acknowledged writings the task of providing a suitable in particular as ticket and / or ticket heat-sensitive recording material available, which must be produced due to high sales volumes in a fiercely competitive market at low production costs and therefore a simple Construction has to dispose.
  • the new recording material should require no additional protective layer to cover the heat-sensitive recording layer, because such a protective layer is too costly both in terms of the necessary raw materials as well as in terms of the necessary machinery and process energies.
  • the new recording material should have excellent resistance to ethanol solutions, water, plasticizers, and ideally also to glycol-containing liquid mists.
  • the novel recording material also has excellent running performance within the thermal-induced-image-type thermal printers, including low abrasiveness of the recording material to the thermal head, and particularly, keeping away the thermal head melt generated in the thermosensitive recording layer during the image formation.
  • the point of excellent running behavior on thermal printers is of such great importance because the new recording material should not have any protective layer with the help of which the running behavior on thermal printers can be optimized in a particularly targeted manner.
  • the barcode readability must be good.
  • N- (p-toluensulphonyl) -N'-3- (p-toluensulphonyl-oxy-phenyl) -urea is known as Pergafast ® 201 from Ciba Specialty Chemicals Inc., and in some illustrations, the CH 3 groups also be omitted.
  • thermosensitive recording material preferably has, as a dye precursor in the first coating composition, those selected from the list comprising:
  • ODB-2 3-dibutylamino-6-methyl-7-anilinofluoran
  • the first coating composition has more than one dye precursor, each selected from the dye precursors listed in the above paragraph.
  • the first coating composition may contain one or more of the following near infrared absorbing compounds:
  • the first coating composition contains at least calcium carbonate and silicon (di) oxide as the at least two pigments. Most preferably, the first coating composition contains only calcium carbonate and silicon (di) oxide as the at least two pigments.
  • the mixing ratio of calcium carbonate and silicon (di) oxide is particularly advantageous in terms of the underlying tasks, if this ratio of calcium carbonate to silicon (di) oxide in a ratio of 1% by weight in the first coating composition Range from 10: 1 to 1: 1, more preferably from 2: 1 to 1.2: 1.
  • the ratio of aluminum (hydr) oxide to silicon (di) oxide based on% by weight in the first coating composition is preferably in a range from 25: 1 to 5: 1.
  • the calcium carbonate which is preferably used in the first embodiment of the proposed embodiment is very particularly preferably in precipitated form with a crystal form as calcite and, in a very preferred embodiment, has an average particle size in a range from 0.1 ⁇ m to 0.3 ⁇ m, and a specific surface area (BET) according to DIN 66132 in a range of 5-15 m 2 / g.
  • BET specific surface area
  • An example of this is Socal P3 (company: Solvay) called.
  • the silicon (di) oxide preferably used in the first coating composition is most preferably in precipitated form and in a very preferred embodiment has an average particle size in a range from 3.0 ⁇ m to 6.0 ⁇ m , and a specific surface area (BET) according to DIN 66132 in a range of 40-200 m 2 / g.
  • BET specific surface area
  • An example of this is Sipernat 350 (company: Evonik).
  • the preferred aluminum hydroxide in the first coating composition is in platelet form, and in a very preferred embodiment has an average particle size in a range of 1.0 ⁇ m to 1.5 ⁇ m, and a specific surface area (BET ) according to DIN 66132 in a range of 5-15 m 2 / g.
  • BET specific surface area
  • An example of this is Martifin OL107 (company: Martinswerke) called.
  • the kaolin preferably used in the first embodiment of the proposed embodiments has an average particle size in a range from 0.5 ⁇ m to 1.0 ⁇ m, and a specific surface area (BET) according to DIN 66132 in one Range of 5-15 m 2 / g.
  • BET specific surface area
  • An example of this is Miragloss 90 (company: BASF).
  • Suitable binders for incorporation into the first coating composition are, for example, water-soluble binders such as starch, hydroxyethylcellulose, methylcellulose, carboxymethylcellulose, gelatin, casein, polyvinyl alcohols, modified polyvinyl alcohols, ethylene-vinyl alcohol copolymers, sodium polyacrylates, acrylamide-acrylate copolymers, acrylamide-acrylate-methacrylate Terpolymers and alkali metal salts of styrene-maleic anhydride copolymers or ethylene-maleic anhydride copolymers, which binders may be used alone or in combination with one another; Water-insoluble latex binders such as styrene-butadiene copolymers, acrylonitrile-butadiene copolymers and methyl acrylate-butadiene copolymers are also suitable as binders for incorporation into the first coating composition.
  • water-soluble binders such as starch, hydroxyethyl
  • polyvinyl alcohol, styrene-butadiene copolymer or, better, polyvinyl alcohol in combination with styrene-butadiene copolymer are particularly preferred binders which, based on the total weight of the first coating composition, are in a range from 10 to 20% by weight. % are included in the first coating composition.
  • the ratio total pigment: total binder, based on weight percent in the first coating composition ideally ranges from 1: 1 to 5: 1, more preferably from 2.5: 1 to 3.5: 1.
  • the first coating composition for forming the thermosensitive recording layer may further contain slip and release agents such as metal salts of higher fatty acids, for example, zinc stearate, calcium stearate and waxes such as paraffin, oxidized paraffin , Polyethylene, polyethylene oxide, stearamides and castor wax.
  • slip and release agents such as metal salts of higher fatty acids, for example, zinc stearate, calcium stearate and waxes such as paraffin, oxidized paraffin , Polyethylene, polyethylene oxide, stearamides and castor wax.
  • the first coating composition contains at least one sensitiser selected from the list comprising: stearic acid amide, dimethylsulfone, 2- (2H-benzotriazol-2-yl) -p-cresol - also known as Tinuvin ® P from Ciba Specialty Chemicals Inc., dimethyl terephthalate - also abbreviated to DMT, methylol stearamide, benzyl p-benzyloxy benzoate, p-benzylbiphenyl, 1,2-di (phenoxy) ethane, di (4-methylphenoxy ) ethane - also known by the abbreviation EGTE, dibenzyl oxalate, benzyl naphthyl ether - also known as BNE, and diphenyl sulfone.
  • di (4-methylphenoxy) ethane and benzyl naphthyl ether are very particularly preferred.
  • a total developer : sensitizer ratio based on the weight percent in the first coating composition is in a range of 1.2: 1 to 2.0: 1.
  • the proposed recording material provides for the formation of a pigmented intermediate layer of a second coating composition arranged between the heat-sensitive recording layer and the substrate.
  • This second coating composition contains binders and preferably a mixture of organic pigments and inorganic pigments.
  • the inorganic pigments are thereby preferred, individually or in combination with one another, selected from the list, comprising: silicon (di) oxide, bentonite, talc, calcined kaolin, calcium carbonate and aluminum oxide and here in particular boehmite.
  • the above inorganic pigments, individually or in combination with one another, selected from the list above, are quoted as one of the list comprising: calcined kaolin, calcium carbonate and aluminum oxide, and here especially boehmite.
  • the ratio between organic and inorganic pigment is a compromise of the effects caused by the two types of pigments, which is particularly advantageously solved when the pigment mixture to 5 to 30 wt .-% or better to 8 to 20 wt .-% of organic and 95 to 70 wt .-% or better to 92 to 80 wt .-% consists of inorganic pigment.
  • Pigment mixtures of different organic pigments are conceivable.
  • the second coating composition contains at least one binder, preferably based on a synthetic polymer, wherein, for example, styrene-butadiene latex gives particularly good results.
  • a synthetic Binder with admixture of at least one natural polymer, more preferably starch, is a particularly suitable embodiment.
  • a binder to pigment ratio within the second coating composition is between 3: 7 and 1: 9, in each case based on wt .-%, a particularly suitable embodiment is present.
  • the web-shaped substrate is formed, for example, on a paper machine in which a paper pulp of different pulps, optionally groundwood, fillers and water is applied in at least one upstream mixing chest is and where to this paper pulp before being fed to the paper machine preferably further ingredients such as resin size for engine sizing and other conventional additives such as pigments, Nuancierfarbstoffe and / or optical brightener may be added.
  • a paper machine is a fourdrinier paper machine, it is a preferred embodiment if a dandy is placed above the papermachine screen with the aid of which a genuine watermark is pressed into the paper web.
  • the second coating composition for forming the pigmented intermediate layer is applied by means of a leveling coating process selected from the list comprising: roller coater, doctor blade or doctor blade coater.
  • the intermediate layer can make a positive contribution to leveling of the substrate surface, thereby reducing the amount of applied mass of the first coating composition for forming the thermosensitive recording layer.
  • the subsequent drying of the coating composition of this second coating composition is usually carried out by a method in which heat is supplied, as is done by hot-air floatation dryer or contact dryer. Proven is also a combination of the listed dry processes.
  • a preferred range between 5 and 20 g / m 2 and even better between 7 and 12 g / m 2 has proven.
  • the method for producing a heat-sensitive recording material provides, in a preferred variant, for smoothing the substrate with the first coating composition now applied and dried.
  • the aim of such a smoothing by a calender or a calender is to create a flattened, possibly shiny surface, with which applied typefaces appear more colorful and lively. Further, a smoother surface of the thermosensitive recording layer by improved contact with the thermal head promotes heat transfer and thus the sensitivity of this thermosensitive recording layer.
  • the recording material finished in this way is preferably rolled up on a spool and is then ready for use according to the customer's wishes, in particular as a ticket.
  • thermosensitive recording material in addition to the disclosed methods for producing a thermosensitive recording material in all the embodiments and variants already proposed herein and in addition to the recording material itself, also claims the use of the here proposed record material for issuing tickets and / or tickets at a correspondingly suitable thermal printer.
  • the tickets have excellent resistance to moisture and moisture on the one hand and plasticizers on the other.
  • the recording material proposed here in their use as tickets by excellent running behavior within the often used in the operators of bus lines and rail thermal printer, including the low abrasiveness of the recording material to the thermal head out as well as in particular the keeping away in the heat-sensitive Recording layer during typeface formation resulting melt from the thermal head.
  • the surface mass,% by weight (% by weight) and parts by weight (parts by weight) given in the specification and claims refer to the "atro" weight, respectively. absolutely dry parts by weight.
  • the relevant figures are calculated from the "lutro" weight, i. air-dry parts by weight, minus the proportion by weight of water around and inside the pigments in their form of delivery.
  • a web-shaped substrate is on a fourdrinier paper machine from bleached and ground hardwood and softwood pulps with the addition of 0.6 wt .-% (atro) resin size, based on the total solids content (atro) of the paper machine supplied pulp, and with the addition of more conventional additives a backing paper having a basis weight of 53 g / m 2 produced.
  • the web-shaped substrate obtains a true watermark incorporated into the fiber mass.
  • aqueous coating compositions used for this purpose comprise the following components according to the formulations reproduced in Table 1, the numbers in Table 1 in each case representing parts by weight:
  • Examples 1 to 4 and Comparative Examples 5 and 6 are each a Thermoprobeaustik with a device of the type Atlantek 400 Fa. Atlantek (USA) formed and to determine the sensitivity the printing density determined with the densitometer Gretag MacBeth TYPE D19C NB / U (Gretag MacBeth, 8105 Regensdorf, Switzerland).
  • samples of the four examples according to the invention and the two comparative examples with the respective thermoprobeable printings are immersed for 20 minutes in a water bath (deionized water, 23 ° C.). Then the samples are allowed to drain, then allowed to rest for 24 hours at 23 ° C and 50% humidity. This is followed by a visual assessment of the thermal printouts after the water bath with reference thermoprinting prints without aftertreatment.
  • stamp impressions are applied with any stamp using a commercially available stamp pad on samples of the four examples according to the invention and the two comparative examples. 10 seconds after the stamping an attempt is made to manually wipe the respective typeface with a dry filter paper. Not wipeable applies the typeface, if it is still readable.
  • a barcode is printed on samples of the four examples according to the invention and the two comparative examples using a device of the Atlantek 400 type from Atlantek (USA).
  • the barcode is analyzed and rated according to ANSI according to international standard ISO 15416.

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Physics & Mathematics (AREA)
  • Optics & Photonics (AREA)
  • Inorganic Chemistry (AREA)
  • Heat Sensitive Colour Forming Recording (AREA)

Claims (16)

  1. Matériel d'enregistrement comportant un substrat sous forme de feuille continue et une couche d'enregistrement thermosensible, en tant que couche extérieure fermée vers l'extérieur, la couche d'enregistrement thermosensible étant constituée d'une première composition de revêtement, comportant au moins :
    un ou plusieurs précurseurs de colorants,
    en tant que révélateur, la N-(p-toluènesulfonyl)-N'-3-(p-toluènesulfonyl-oxy-phényl)-urée selon la formule (1) suivante :
    Figure imgb0011
    un liant,
    un pigment choisi parmi la liste comprenant : le kaolin, le (di)oxyde de silicium, la bentonite, le talc, le carbonate de calcium, ainsi que l'oxyde d'aluminium et ici, en particulier, la boehmite,
    caractérisé en ce que
    la première composition de revêtement contient en tant que pigment au moins une combinaison de pigments, la combinaison de pigments étant choisie parmi la liste comprenant :
    - le carbonate de calcium et le (di)oxyde de silicium,
    - l'(hydr)oxyde d'aluminium et le (di)oxyde de silicium,
    - le carbonate de calcium et l'(hydr)oxyde d'aluminium.
  2. Matériel d'enregistrement selon la revendication 1, caractérisé en ce que le rapport carbonate de calcium/(di)oxyde de silicium, rapporté au pourcentage en poids de la première composition de revêtement, est situé dans la plage allant de 2/1 à 1,2/1.
  3. Matériel d'enregistrement selon la revendication 1, caractérisé en ce que le rapport (hydr)oxyde d'aluminium/(di)oxyde de silicium, rapporté au pourcentage en poids dans la première composition de revêtement, est situé dans la plage allant de 25/1 à 5/1.
  4. Matériel d'enregistrement selon la revendication 1, caractérisé en ce que le rapport carbonate de calcium/(hydr)oxyde d'aluminium, rapporté au pourcentage en poids dans la première composition de revêtement, est situé dans la plage allant de 10/1 à 3/1.
  5. Matériel d'enregistrement selon l'une quelconque des revendications 1, 2 et 4, caractérisé en ce que le carbonate de calcium est un carbonate de calcium précipité dont une granulométrie moyenne est située dans la plage allant de 0,1 à 0,3 µm et une aire spécifique (BET) selon DIN 66132 est située dans la plage allant de 5 à 15 m2/g.
  6. Matériel d'enregistrement selon l'une quelconque des revendications 1 à 3, caractérisé en ce que le (di)oxyde de silicium présente une granulométrie moyenne située dans la plage allant de 3 à 6 µm et une aire spécifique (BET) selon DIN 66132 située dans la plage allant de 40 à 200 m2/g.
  7. Matériel d'enregistrement selon l'une quelconque des revendications 1, 3 et 4, caractérisé en ce que l'hydroxyde d'aluminium présente une granulométrie moyenne située dans la plage allant de 1 à 1,5 µm et une aire spécifique (BET) selon DIN 66132 située dans la plage allant de 5 à 15 m2/g.
  8. Matériel d'enregistrement selon la revendication 1, caractérisé en ce que le kaolin présente une granulométrie moyenne située dans la plage allant de 0,5 à 1,0 µm et une aire spécifique (BET) selon DIN 66132 située dans la plage allant de 5 à 15 m2/g.
  9. Matériel d'enregistrement selon l'une quelconque des revendications 1 à 8, caractérisé en ce que le liant, destiné à être incorporé dans la première composition de revêtement, est ou contient au moins un liant hydrosoluble choisi parmi la liste comprenant : l'amidon, l'hydroxyéthylcellulose, la méthylcellulose, la carboxyméthylcellulose, la gélatine, la caséine, les alcools polyvinyliques, les alcools polyvinyliques modifiés.
  10. Matériel d'enregistrement selon l'une quelconque des revendications 1 à 9, caractérisé en ce que le liant, destiné à être incorporé dans la première composition de revêtement, est ou contient au moins un liant de type latex insoluble dans l'eau, choisi parmi la liste comprenant : les copolymères styrène-butadiène, les copolymères acrylonitrile-butadiène et les copolymères acrylate de méthyle-butadiène.
  11. Matériel d'enregistrement selon l'une quelconque des revendications 1 à 10, caractérisé en ce que le rapport pigmenttotal/lianttotal, rapporté au pourcentage en poids dans la première composition de revêtement, est située dans la plage allant de 2,5/1 à 3,5/1.
  12. Matériel d'enregistrement selon l'une quelconque des revendications 1 à 11, caractérisé en ce que la première composition de revêtement contient au moins un sensibilisateur choisi parmi la liste comprenant : le di(4-méthylphénoxy)-éthane et le benzylnapthyléther.
  13. Matériel d'enregistrement selon l'une quelconque des revendications 1 à 12, caractérisé en ce qu'entre la couche d'enregistrement thermosensible et le substrat est disposée une couche intermédiaire pigmentée contenant un liant, des pigments organiques et des pigments inorganiques.
  14. Procédé de fabrication d'un matériel d'enregistrement thermosensible selon l'une quelconque des revendications 1 à 13, comprenant au moins les étapes suivantes :
    la réalisation d'un substrat sous forme de feuille continue,
    la préparation d'une première composition de revêtement, cette première composition de revêtement comprenant au moins :
    - un ou plusieurs précurseurs de colorants,
    - en tant que révélateur, la N-(p-toluènesulfonyl)-N'-3-(p-toluènesulfonyl-oxy-phényl)-urée selon la formule (1) suivante :
    Figure imgb0012
    - un liant,
    - un pigment choisi parmi la liste comprenant : le kaolin, le (di)oxyde de silicium, la bentonite, le talc, le carbonate de calcium, ainsi que l'oxyde d'aluminium et ici en particulier la boehmite,
    la première composition de revêtement contenant en tant que pigment au moins une combinaison de pigments, et la combinaison de pigments étant choisie parmi la liste comprenant :
    - le carbonate de calcium et le (di)oxyde de silicium,
    - l'(hydr)oxyde d'aluminium et le (di)oxyde de silicium,
    - le carbonate de calcium et l'(hydr)oxyde d'aluminium ;
    l'application sur le substrat de la première composition de revêtement préparée, pour réaliser une couche d'enregistrement thermosensible ;
    le séchage de la première composition de revêtement ;
    l'enroulement de la couche d'enregistrement thermosensible ainsi formée sur le substrat sous forme de feuille continue.
  15. Procédé selon la revendication 14, caractérisé en ce que le procédé comprend au moins trois étapes supplémentaires :
    la préparation d'une deuxième composition de revêtement, la deuxième composition de revêtement comprenant des pigments organiques et des pigments inorganiques, les pigments inorganiques étant choisis parmi la liste comprenant : le kaolin calciné, le carbonate de calcium, ainsi que l'oxyde d'aluminium et ici, en particulier, la boehmite ;
    l'application de la deuxième composition de revêtement préparée, pour former une couche intermédiaire pigmentée disposée entre le substrat et la couche d'enregistrement thermosensible ;
    le séchage de la deuxième composition de revêtement ;
    ces au moins trois étapes supplémentaires devant être insérées avant l'étape d'« application sur le substrat de la première composition de revêtement préparée pour réaliser une couche d'enregistrement thermosensible ».
  16. Utilisation du matériel d'enregistrement selon l'une des revendications 1 à 13 destinée à l'établissement de titres de transport sur une imprimante thermique appropriée.
EP20110160791 2011-04-01 2011-04-01 Matériel d'enregistrement sensible à la chaleur, son utilisation et son procédé de fabrication Not-in-force EP2505374B1 (fr)

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP3746308B1 (fr) 2018-01-31 2022-02-23 Mitsubishi HiTec Paper Europe GmbH Composition de revêtement, couche d'enregistrement thermosensible, matériau d'enregistrement thermosensible et utilisations et procédés correspondants

Family Cites Families (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP1208994B2 (fr) * 2000-11-24 2011-05-25 Oji Paper Co., Ltd. Matériau thermosensible pour l'enregistrement
ATE508883T1 (de) 2007-09-04 2011-05-15 Mitsubishi Hitec Paper Europe Wärmeempfindliches aufzeichnungsmaterial
DE502007002945D1 (de) * 2007-09-10 2010-04-08 Mitsubishi Hitec Paper Flensbu Wärmeempfindliches Aufzeichnungsmaterial

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP3746308B1 (fr) 2018-01-31 2022-02-23 Mitsubishi HiTec Paper Europe GmbH Composition de revêtement, couche d'enregistrement thermosensible, matériau d'enregistrement thermosensible et utilisations et procédés correspondants

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