EP2033800B1 - Matériel d'enregistrement sensible à la chaleur - Google Patents

Matériel d'enregistrement sensible à la chaleur Download PDF

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Publication number
EP2033800B1
EP2033800B1 EP07017264A EP07017264A EP2033800B1 EP 2033800 B1 EP2033800 B1 EP 2033800B1 EP 07017264 A EP07017264 A EP 07017264A EP 07017264 A EP07017264 A EP 07017264A EP 2033800 B1 EP2033800 B1 EP 2033800B1
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EP
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Prior art keywords
methyl
heat
sensitive recording
anilinofluoran
recording layer
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EP07017264A
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German (de)
English (en)
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EP2033800A1 (fr
Inventor
Gerhard Stork
Annette Schreiber
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Mitsubishi HiTech Paper Flensburg GmbH
Stora Spezialpapiere GmbH
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Mitsubishi HiTech Paper Flensburg GmbH
Stora Spezialpapiere GmbH
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Priority to ES07017264T priority Critical patent/ES2339166T3/es
Priority to EP07017264A priority patent/EP2033800B1/fr
Priority to DE502007002944T priority patent/DE502007002944D1/de
Priority to AT07017264T priority patent/ATE458620T1/de
Priority to US12/231,653 priority patent/US8198212B2/en
Publication of EP2033800A1 publication Critical patent/EP2033800A1/fr
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Publication of EP2033800B1 publication Critical patent/EP2033800B1/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
    • B41M5/30—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

Definitions

  • the present invention relates to a thermosensitive recording material having a substrate, optionally a pigmented intermediate layer applied to the substrate, and a thermosensitive recording layer containing a color former and color acceptors.
  • the present invention also relates to the use of the thus proposed heat-sensitive recording material as a ticket or as a ticket.
  • Heat-sensitive recording materials of the type described above with, for example, a sheet of paper, a synthetic paper sheet or a plastic film as a 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 in particular as a ticket for the Ticket issuing is associated with great benefits. Because the color-forming components are stuck in the recording material itself in the heat-sensitive recording method, the toner and color-cartridge-free printers, which in their function no longer need to be controlled by anyone, can be set up in large numbers. Thus, this innovative technology has prevailed especially in public passenger transport, buses and trains as well as in air traffic, stadium and museum funds and parking ticket issuers.
  • thermoformed prints To increase the resistance of thermoformed prints to water, aqueous alcohol solutions and plasticizers suggests the DE10 2004 044 204A1 a heat-sensitive recording material, whose heat-sensitive recording layer has conventional dye precursors and the combination of a phenolic color developer and a urea-urethane-based color developer.
  • Urea urethane compounds as developers which can be used to increase the print density of thermoformed prints also in combination generally with Suffonylhamstoff are from the EP1 116 713A1 as well as from the DE 692 04 777T2 It is not known that these documents refer to the outstanding effect of N- (p-toluenesulphonyl) -N'-3- (p-toluenesulphonyl-oxy-phenyl) -urea.
  • thermosensitive recording material containing at least the components of two color forming systems to form an irreversible printed image, one being a chelate-type system and the other being a conventional leuco-dye system.
  • a variety of sulfonylureas including N- (p-toluenesulphonyl) -N'-3- (p-toluenesulphonyl-oxy-phenyl) urea, called in one embodiment in combination with urea urethane compounds can be combined as a second developer.
  • a disadvantage of the recording materials according to the writings discussed above is in particular in the first case too low plasticizer resistance, associated with very low whiteness of the recording material, as well as the much too complex manufacturing processes that often preclude the use of the proposals in everyday life.
  • the present invention therefore has the object to provide a suitable in particular as a ticket and / or as a 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 has to dispose of a simple structure.
  • the new recording material should not require an additional protective layer for covering 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 and plasticizers.
  • the new recording material requirements for good Bestkovbarkarkeit and Entwertraj are made, which is to be understood in the sense of this invention underlying task that stamped Entwerter Schweizer after about 10 seconds neither dry nor wet can be completely wiped away.
  • the present invention extends to the same extent to the use of such a heat-sensitive recording material described as a ticket or as a ticket.
  • thermo-print print For metrological recording of the print density, a black-and-white checkered thermo-print print is made with an Atlantek 400 from Viex (USA) using a thermal head with a resolution of 300 dpi and an energy per unit area of 9 mJ / mm 2 comes.
  • the print density even of the black-colored areas are measured with the densitometer Gretag MacBeth TYPE D19C NB / U (Gretag MacBeth, 8105 Regensdorf, Switzerland), where the dynamic printing densities are measured at three points for each measured value and the arithmetic mean is formed from the three individual values becomes.
  • each black / white checkered-designed Thermoprobeaustike with a device of the type Atlantek 400 made by Viex (USA) created using a thermal head with resolution of 300 dpi and an energy per unit area of 16 mJ / mm 2 is used.
  • the dynamic print density of the black-colored surfaces is first measured at a Thermoprobeaustik at three points with the densitometer Gretag MacBeth TYPE D19C NB / U (Fa Gretag MacBeth, 8105 Regensdorf, Switzerland). Subsequently, the respective treatment of the Thermoprobeausdrucks.
  • This treatment in the case of percent resistance to a 25% ethanol solution, provides immersion of the Thermoprobertextes in an ethanol bath (25 vol .-% solution, 23 ° C) over 20 minutes. The printout is then carefully blotted with blotting paper and allowed to rest for 24 hours at 23 ° and 50% humidity.
  • thermoprobe print In the case of percent resistance to water, the thermoprobe print is placed in a water bath (deionized water, 23 ° C) for 20 minutes. Dabing and resting is then carried out as in the ethanol treatment.
  • the determination of the dynamic print density at three points of the black-colored areas is carried out again with the Gretag MacBeth TYPE D19C NB / U densitometer.
  • the respective mean values of the measurements before / after the bath in the ethanol solution or in water are formed, and the average value after the bath as a percentage of the mean value before the bath.
  • TESA ® graphic film 57331 For each individual determination of the percentage resistance of a Thermoprobeaustikes against plasticizer, a 10 cm long piece of TESA ® graphic film 57331 is first glued to a prepared by means of equipment type Atlantek 400 from Viex (USA) Thermoprobeaustik. Subsequently, the dynamic print density of the black-colored areas is measured immediately at three points using the densitometer Gretag MacBeth TYPE D19C NB / U. The print will then rest for 24 hours at 23 ° and 50% humidity. After resting, the determination of the dynamic print density at three points of the black-colored areas is carried out again with the Gretag MacBeth TYPE D19C NB / U densitometer. The respective mean values of the measurements before / after resting are formed and the average value after resting can be left to rest before the mean value.
  • thermosensitive recording layer it is possible for the thermosensitive recording layer to comprise more than one color former, each selected from the color formers listed above in paragraph [0009].
  • the recording material according to the invention may, in addition to these substances specified as fabifiers, also contain one or more of the following compounds absorbing in the near infrared range:
  • the two dye acceptors of the formula (1) and the formula (2) can constitute up to 35% by weight, but preferably within the range of 25 to 30% by weight of the heat-sensitive recording layer.
  • the effect that the mixture of the two color acceptors brings about in their entirety is a combination resulting from the peculiarities of the two individual color acceptors: While N- (p-toluenesulphonyl) -N'-3- (p-toluenesulphonyl-oxy -phenyl) urea according to formula (1) has been recognized as a color acceptor after numerous individual and cross experiments, which is expected to high sensitivity of the heat-sensitive recording layer to energy exposure, urea-urethane compounds according to the formula (2) may be more such as color acceptors be described in which the induced by energy print image has a high stability against counterfeiting and environmental influences.
  • thermosensitive recording material which has a tendency of little background graying and has a heat-induced printed image resistant to environmental influences.
  • the recording layer of the heat-sensitive recording material of the present invention may also preferably contain sensitisers having a melting point of preferably from 60 ° C to 180 ° C, more preferably having a melting point of from 80 ° C to 140 ° C, to increase the thermal responsiveness.
  • Such sensitizers are, for example: benzyl p-benzyloxybenzoate, stearamide, N-methylol stearamide, p-benzylbiphenyl, 1,2-di (phenoxy) ethane, 1,2-di (m-methylphenoxy) ethane, m-terphenyl, Dibenzyl oxalate, benzyl naphthyl ether and diphenyl sulfone, with benzyl naphthyl ether, diphenyl sulfone, 1,2-di (m-methylphenoxy) ethane and 1,2-di (phenoxy) ethane being preferred.
  • Suitable binders for incorporation into the heat-sensitive recording layer are, for example, water-soluble binders such as starch, hydroxyethyl cellulose, methyl cellulose, carboxymethyl cellulose, gelatin, casein, polyvinyl alcohols, modified polyvinyl alcohols, sodium polyacrylates, acrylamide-acrylate copolymers, acrylamide-acrylate-methacrylate terpolymers, alkali metal salts of styrene.
  • water-soluble binders such as starch, hydroxyethyl cellulose, methyl cellulose, carboxymethyl cellulose, gelatin, casein, polyvinyl alcohols, modified polyvinyl alcohols, sodium polyacrylates, acrylamide-acrylate copolymers, acrylamide-acrylate-methacrylate terpolymers, alkali metal salts of styrene.
  • 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 heat-sensitive recording layer.
  • polyvinyl alcohol in combination with acrylate copolymers are considered to be particularly preferred binders which are incorporated together in the heat-sensitive recording layer in a range of 12 to 21% by weight, based on the total weight of the recording layer.
  • the coating composition for forming the heat-sensitive recording layer may further contain lubricants 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.
  • Further constituents of the recording layer are, for example, pigments, preferably inorganic pigments such as, for example, aluminum (hydr) oxide, silica and calcium carbonate, in which case in particular calcium carbonate, preferably in an amount of from 10 to 20% by weight, based on the total weight of the recording layer the recording layer is to be included as being preferred.
  • the recording layer preferably has a whiteness in a range of 79 to 85% when using light with no UV content and a whiteness ranging from 87 to 93% when using UV light. Proportion measured in accordance with ISO 2469 / ISO 2470, but D65 light is used at a viewing angle of 8 °.
  • roller coater, knife coater, curtain coater or air brush are particularly suitable as coating apparatus for applying the heat-sensitive recording layer.
  • the coating composition used to form the recording layer is aqueous.
  • the subsequent drying of the coating composition is usually done by a method in which heat is supplied, as is done by hot-air floating dryer or contact dryer. Proven is also a combination of the listed dry processes.
  • the basis weight of the heat-sensitive recording layer is preferably from 2 to 6 g / m 2, and more preferably from 2.3 to 5.8 g / m 2 .
  • a pigmented intermediate layer is expediently arranged between the recording layer and the substrate of the heat-sensitive recording material according to the invention.
  • the intermediate layer is applied in a preferred embodiment with leveling coating devices, such as, for example, roller coater, doctor blade or doctor blade coaters, the intermediate layer can also make a positive contribution to equalization of the substrate surface, thus increasing the amount necessarily applied to apply coating composition for the heat-sensitive recording layer.
  • leveling coating devices such as, for example, roller coater, doctor blade or doctor blade coaters
  • the intermediate layer can also make a positive contribution to equalization of the substrate surface, thus increasing the amount necessarily applied to apply coating composition for the heat-sensitive recording layer.
  • For the basis weight of the intermediate layer a preferred range between 5 and 20 g / m 2 and even better between 7 and 12 g / m 2 has proven.
  • inorganic oil-absorbing pigments When inorganic oil-absorbing pigments are incorporated into the intermediate layer sandwiched between the recording layer and the substrate, these pigments can absorb the thermoset liquefied wax components of the thermosensitive recording layer in the typeface formation and thus promote still safer and faster operation of the thermally-induced recording, thus such an embodiment preferably applies.
  • the pigments of the intermediate layer has an oil absorption of at least 80 cm3 / 100 g, and more preferably 100 cm3 / 100 g, determined according to the Japanese standard JIS K 5101, is having.
  • Calcined kaolin has proven particularly useful due to its large absorption reservoir in the cavities.
  • the following inorganic pigments are also very well suited as constituents of the intermediate layer: silicon oxide, bentonite, calcium carbonate and aluminum oxide and, in particular, boehmite here. Also mixtures of several different types of inorganic pigments are conceivable.
  • 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 pigmented intermediate layer 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 the admixture of at least one natural polymer, more preferably starch, is a particularly suitable embodiment.
  • a non-surface treated base paper is to be understood as meaning a base paper which has not been treated in a size press or in a coating device.
  • a non-surface-treated, sized in the mass base paper with an inorganic pigment, in particular calcium carbonate is considered suitable in the mass.
  • films of, for example, polyolefin and polyolefin-coated papers as a substrate are possible to the same extent, without such an embodiment having an exclusive character.
  • a 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 as engine sizing and other conventional admixtures, based on the total solids content (atro) of the pulp fed pulp, a backing paper having a basis weight of 53 g / m 2 made.
  • a calcined kaolin pigment, styrene-butadiene latex as a binder and, in addition to other aids, starch as cobinder-containing intermediate layer having a basis weight of 9 g / m 2 is applied using a doctor blade.
  • heat-sensitive recording layer which are not stated in percent and based on the total weight in% by weight (atro) include dispersants, defoamers, optical brighteners, thickeners, waxes and crosslinkers.
  • this ratio is 11: 1, which means that the very little amount of urea-urethane compound according to formula (2) relative to N- (p-toluenesulphonyl) -N'-3- (p-toluenesulphonyl) Oxy-phenyl) urea according to formula (1) is used in the heat-sensitive recording layer.
  • this ratio is 1: 2, which means that a lot of urea-urethane compound of formula (2) in proportion to N- (p-toluenesulphonyl) -N'-3- (p-toluenesulphonyl-oxy-phenyl) -urea of the formula (1) is used in the heat-sensitive recording layer.
  • thermosensitive recording materials Upon completion of patterns of thermosensitive recording materials according to the two Comparative Examples 1 and 3 and Example 2 of the present invention, dynamic pressure densities and percent resistances to a 25% ethanol solution versus water and plasticizer are described in detail in the specification - created black and white checkered thermoprobaus réellee with a device of the type Atlantek 400 of the company Viex (USA), wherein a thermal head with resolution of 300 dpi and an energy per unit area of 9 mJ / mm 2 (dynamic printing densities) and 16 mJ / mm 2 (percent resistances) is used.

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

Claims (7)

  1. Matériau d'enregistrement thermosensible avec un substrat, ainsi qu'une couche d'enregistrement thermosensible contenant des agents chromogènes et des accepteurs de couleurs, caractérisé en ce que
    ■ les agents chromogènes sont choisis dans le groupe comprenant le 3-diéthylamino-6-méthyl-7-anilinofluorane, le 3-dibutylamino-6-méthyl-7-anilinofluorane, le 3-(N-méthyl-N-propyl)amino-6-méthyl-7-anilinofluorane, le 3-(N-éthyl-N-isoamyl)-amino-6-méthyl-7-anilinofluorane, le 3-(N-méthyl-N-cyclohexyl)amino-6-méthyl-7-anilinofluorane, le 3-(N-éthyl-N-tolyl)amino-6-méthyl-7-anilinofluorane et le 3-(N-éthyl-N-tétrahydrofuryl)amino-6-métlryl-7-anilinofluorane,
    ■ la couche d'enregistrement thermosensible présente deux accepteurs de couleurs, qui sont la N-(p-toluènesulfonyl)-N'-3-(p-toluènesulfonyloxyphényl)urée selon la formule suivante (1):
    Figure imgb0011
     ainsi qu'un composé d'urée-uréthanne selon la formule suivante (2) :
    Figure imgb0012
    ■ dans lequel le rapport se référant au % en poids dans la couche d'enregistrement thermosensible des deux accepteurs de couleurs, à savoir de la N-(p-toluènesulfonyl)-N'-3-(p-toluènesulfonyloxyphényl)urée selon la formule (1) au composé d'urée-uréthanne selon la formule (2), se situe dans une plage de 10:1 à 1:1.
  2. Matériau d'enregistrement thermosensible selon la revendication 1, caractérisé en ce que la densité d'impression dynamique d'un imprimé d'essai thermique, réalisé avec une tête d'impression thermique avec une résolution de 300 dpi et une énergie par unité de surface de 9 mJ/mm2, se situe dans une plage de 0,91 à 1,03 ODU.
  3. Matériau d'enregistrement thermosensible selon l'une quelconque des revendications 1 et 2, caractérisé en ce que la résistance en pourcentage d'un imprimé d'essai thermique, réalisé avec une tête d'impression thermique avec une résolution de 300 dpi,
    - se situe par rapport à une solution d'éthanol à 25 % dans une plage de 91,5 % à 96,5 %,
    - se situe par rapport à l'eau dans une plage de 95,5 % à 99,5 %, et
    - se situe par rapport à un plastifiant (TESA®-Grafik-Film 57331) dans une plage de 90,5 % à 95,5 %.
  4. Matériau d'enregistrement thermosensible selon l'une quelconque des revendications 1 à 3, caractérisé en ce que la couche d'enregistrement présente une blancheur dans une plage de 79 à 85 % en utilisant de la lumière sans fraction de rayonnements UV, que l'on mesure selon les normes ISO 2469/ISO 2470 en utilisant de la lumière de type D65 sous un angle d'observation de 8 °.
  5. Matériau d'enregistrement thermosensible selon la revendication 4, caractérisé en ce que la couche d'enregistrement présente une blancheur dans une plage de 87 à 93 % en utilisant de la lumière avec une fraction de rayonnements UV, que l'on mesure selon les normes ISO 2469/ISO 2470 en utilisant de la lumière de type D65 sous un angle d'observation de 8°.
  6. Matériau d'enregistrement thermosensible selon l'une quelconque des revendications 1 à 5, caractérisé en ce qu'une couche intermédiaire pigmentée est formée entre le substrat et la couche d'enregistrement thermosensible.
  7. Utilisation d'un matériau d'enregistrement thermosensible avec un substrat, ainsi qu'une couche d'enregistrement thermosensible contenant des agents chromogènes et des accepteurs de couleurs, comme ticket ou titre de transport, dans laquelle
    ■ les agents chromogènes sont choisis dans le groupe comprenant le 3-diéthylamino-6-méthyl-7-anilinofluorane, le 3-dibutylamino-6-méthyl-7-anilinofluorane, le 3-(N-méthyl-N-propyl)amino-6-méthyl-7-anilinofluorane, le 3-(N-éthyl-N-isoamyl)-amino-6-méthyl-7-anilinofluorane, le 3-(N-méthyl-N-cyclohexyl)amino-6-méthyl-7-anilinofluorane, le 3-(N-éthyl-N-tolyl)amino-6-méthyl-7-anilinofluorane et le 3-(N-éthyl-N-tétrahydrofuryl)amino-6-méthyl-7-anilinofluorane,
    ■ la couche d'enregistrement thermosensible présente deux accepteurs de couleurs, qui sont la N-(p-toluènesulfonyl)-N'-3-(p-toluènesulfonyloxyphényl)urée selon la formule suivante (1):
    Figure imgb0013
     ainsi qu'un composé d'urée-uréthanne selon la formule suivante (2) :
    Figure imgb0014
    ■ dans laquelle le rapport se référant au % en poids dans la couche d'enregistrement thermosensible des deux accepteurs de couleurs, à savoir de la N-(p-toluènesulfonyl)-N'-3-(p-toluènesulfonyloxyphényl)urée selon la formule (1) au composé d'urée-uréthanne selon la formule (2), se situe dans une plage de 10:1 à 1:1.
EP07017264A 2007-09-04 2007-09-04 Matériel d'enregistrement sensible à la chaleur Active EP2033800B1 (fr)

Priority Applications (5)

Application Number Priority Date Filing Date Title
ES07017264T ES2339166T3 (es) 2007-09-04 2007-09-04 Material de registro sensible al calor.
EP07017264A EP2033800B1 (fr) 2007-09-04 2007-09-04 Matériel d'enregistrement sensible à la chaleur
DE502007002944T DE502007002944D1 (de) 2007-09-04 2007-09-04 Wärmeempfindliches Aufzeichnungsmaterial
AT07017264T ATE458620T1 (de) 2007-09-04 2007-09-04 Wärmeempfindliches aufzeichnungsmaterial
US12/231,653 US8198212B2 (en) 2007-09-04 2008-09-04 Heat-sensitive recording material

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
EP07017264A EP2033800B1 (fr) 2007-09-04 2007-09-04 Matériel d'enregistrement sensible à la chaleur

Publications (2)

Publication Number Publication Date
EP2033800A1 EP2033800A1 (fr) 2009-03-11
EP2033800B1 true EP2033800B1 (fr) 2010-02-24

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US (1) US8198212B2 (fr)
EP (1) EP2033800B1 (fr)
AT (1) ATE458620T1 (fr)
DE (1) DE502007002944D1 (fr)
ES (1) ES2339166T3 (fr)

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CN102232250A (zh) * 2008-10-01 2011-11-02 三星Led株式会社 使用液晶聚合物的发光二极管封装件

Family Cites Families (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5246906A (en) * 1991-08-02 1993-09-21 Oji Paper Co., Ltd. Thermosensitive recording material
WO2000014058A1 (fr) * 1998-09-04 2000-03-16 Asahi Kasei Kabushiki Kaisha Nouveau compose chromo-sensible
EP1243437B1 (fr) 2001-03-23 2004-11-17 Ricoh Company, Ltd. Dispersion de colorant leuco et matériau thermosensible utilisant ladite dispersion
FI110677B (fi) * 2001-10-12 2003-03-14 Jujo Thermal Oy Lämpöherkkä tallennusmateriaali
DE102004004204A1 (de) 2004-01-27 2005-08-11 Mitsubishi Hitec Paper Bielefeld Gmbh Wärmeempfindliches Aufzeichnungsmaterial

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DE502007002944D1 (de) 2010-04-08
US20090088321A1 (en) 2009-04-02
ATE458620T1 (de) 2010-03-15
ES2339166T3 (es) 2010-05-17
US8198212B2 (en) 2012-06-12
EP2033800A1 (fr) 2009-03-11

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