EP3109059B1 - Materiel d'enregistrement sensible a la chaleur - Google Patents

Materiel d'enregistrement sensible a la chaleur Download PDF

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Publication number
EP3109059B1
EP3109059B1 EP15176526.0A EP15176526A EP3109059B1 EP 3109059 B1 EP3109059 B1 EP 3109059B1 EP 15176526 A EP15176526 A EP 15176526A EP 3109059 B1 EP3109059 B1 EP 3109059B1
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EP
European Patent Office
Prior art keywords
heat
sensitive recording
coating composition
recording layer
recording material
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.)
Active
Application number
EP15176526.0A
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German (de)
English (en)
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EP3109059A1 (fr
Inventor
Andreas Jagiello
Matthias Marx
Martin Schreer
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.)
Mitsubishi HiTec Paper Europe GmbH
Original Assignee
Mitsubishi HiTec Paper Europe GmbH
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Application filed by Mitsubishi HiTec Paper Europe GmbH filed Critical Mitsubishi HiTec Paper Europe GmbH
Priority to PL15176526T priority Critical patent/PL3109059T3/pl
Priority to RU2017125823A priority patent/RU2670521C1/ru
Priority to PCT/EP2016/064676 priority patent/WO2016207356A1/fr
Priority to ES16733414.3T priority patent/ES2693023T3/es
Priority to KR1020177024307A priority patent/KR102058570B1/ko
Priority to US15/537,359 priority patent/US10328735B2/en
Priority to EP16733414.3A priority patent/EP3221153B1/fr
Priority to JP2017541253A priority patent/JP2018509316A/ja
Priority to PL16733414T priority patent/PL3221153T3/pl
Priority to CN201680004448.8A priority patent/CN107107642B/zh
Publication of EP3109059A1 publication Critical patent/EP3109059A1/fr
Publication of EP3109059B1 publication Critical patent/EP3109059B1/fr
Application granted granted Critical
Priority to JP2019146584A priority patent/JP2019206188A/ja
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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
    • B41M5/40—Thermography ; Marking by high energetic means, e.g. laser otherwise than by burning, and characterised by the material used characterised by the base backcoat, intermediate, or covering layers, e.g. for thermal transfer dye-donor or dye-receiver sheets; Heat, radiation filtering or absorbing means or layers; combined with other image registration layers or compositions; Special originals for reproduction by thermography
    • B41M5/42—Intermediate, backcoat, or covering layers
    • B41M5/426—Intermediate, backcoat, or covering layers characterised by inorganic compounds, e.g. metals, metal salts, metal complexes
    • 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
    • B41M5/40—Thermography ; Marking by high energetic means, e.g. laser otherwise than by burning, and characterised by the material used characterised by the base backcoat, intermediate, or covering layers, e.g. for thermal transfer dye-donor or dye-receiver sheets; Heat, radiation filtering or absorbing means or layers; combined with other image registration layers or compositions; Special originals for reproduction by thermography
    • B41M5/42—Intermediate, backcoat, or covering layers
    • B41M5/44—Intermediate, backcoat, or covering layers characterised by the macromolecular compounds
    • B41M5/443—Silicon-containing polymers, e.g. silicones, siloxanes
    • 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
    • B41M5/323—Organic colour formers, e.g. leuco dyes
    • 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
    • B41M5/40—Thermography ; Marking by high energetic means, e.g. laser otherwise than by burning, and characterised by the material used characterised by the base backcoat, intermediate, or covering layers, e.g. for thermal transfer dye-donor or dye-receiver sheets; Heat, radiation filtering or absorbing means or layers; combined with other image registration layers or compositions; Special originals for reproduction by thermography
    • B41M5/42—Intermediate, backcoat, or covering layers
    • B41M5/44—Intermediate, backcoat, or covering layers characterised by the macromolecular compounds
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
    • B41M—PRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
    • B41M2205/00—Printing methods or features related to printing methods; Location or type of the layers
    • B41M2205/04—Direct thermal recording [DTR]
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
    • B41M—PRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
    • B41M2205/00—Printing methods or features related to printing methods; Location or type of the layers
    • B41M2205/40—Cover layers; Layers separated from substrate by imaging layer; Protective layers; Layers applied before imaging

Definitions

  • the present invention relates to a heat-sensitive recording material comprising a sheet-shaped substrate and a heat-sensitive recording layer disposed on the web-shaped substrate, said heat-sensitive recording layer containing at least one dye precursor and at least one (color) developer reactive with said at least one dye precursor.
  • a dye precursor in the context of the present invention in all its embodiments proposed here, means that this at least one (color) developer reacts with this at least one dye precursor with sufficient supply of external heat to form a visually recognizable printed image.
  • the surface of the thermosensitive recording material is formed dephasesiv against adhesive layers, which are applicable to the back of the web-shaped substrate.
  • Heat-sensitive and color-sensitive to the supply of external heat recording materials have been known for many years and enjoy a basically unbroken popularity, which is due, inter alia, that their use for the ticket and / or purchase receipts and / or tickets issuing businessman with large Benefits connected.
  • the color-forming components that is, dye precursors and (color) developers reacting with them upon the introduction of heat, are also called color acceptors heat-sensitive recording method stuck in the recording material itself, therefore, the toner and color cartridge-free thermal printer, whose function no longer need to be controlled by anyone regularly, can be set up in large numbers.
  • the backside adhesive layers may be covered by a separate release paper until their use, but much more popular and practical in handling them are those recording materials which have surfaces on the front which are dehesive to the backside adhesive layers. In this case, the backside adhesive layers are covered until they are used by the front surface surfaces of the recording materials themselves wound up as a roll where front and back sides come together.
  • a heat-sensitive recording material proposed therein has a protective layer comprising a UV-curing resin and a copolymer resin comprising a silicone component as a copolymerizing component. From heat-sensitive recording materials for self-adhesive tickets is not mentioned in this document, even if it turned out to be suitable.
  • the EP 1 637 339 B1 a heat-sensitive recording material having a substrate, a heat-sensitive recording layer and a protective layer, in which the protective layer has, in particular, a release agent in addition to binder resin, filler and crosslinking agent.
  • This release agent is introduced as a spherical and particulate silicone compound with a special formula.
  • a disadvantage of this known proposal is the complex and expensive production with substrate, recording layer and final protective layer, the protective layer because of their filler and binder components to all abundance also the dynamic and static sensitivity of the known heat-sensitive recording material against supplied external heat to form a visually recognizable print image
  • the WO2013050531 A1 discloses a thermosensitive recording material similar to that shown in U.S. Patent Nos. 5,496,074 EP1637339 B1 is described.
  • the diffusion layer (4) makes a significant contribution to the ply adhesion between the impingement having a release agent (5) and the heat-sensitive recording layer (3). Without the diffusion layer 4, there were problems in sheet adhesion between the release agent (5) and the heat-sensitive recording layer (3), which causes problems in the use of the recording material.
  • the heat-sensitive recording material proposed on this side has an intermediate layer (2) having hollow-body pigments positioned between the web-shaped substrate (1) and the heat-sensitive recording layer (3).
  • Such a heat-sensitive recording material is produced by a method, which method comprises at least the method steps as defined in claim 12.
  • the coating composition and / or the silicone component has a viscosity of from 50 to 1000 mPas, preferably from 50 to 100 mPas or from 500 to 1000 mPas.
  • the silicone component is an aqueous emulsion or a UV-crosslinking silicone component, wherein the crosslinking takes place radically (preferably under a nitrogen-protective atmosphere) or cationically.
  • the silicone component is not a thermally crosslinking silicone component or a silicone component dissolved in an organic solvent.
  • thermosensitive recording layer (3) After the third coating composition is applied to the finished thermosensitive recording layer (3), a part of the third coating composition diffuses into the upper portion of the formed thermosensitive recording layer (3), wherein a content of 5 to 50 wt%. the entirety of the release agent of the third coating composition, preferably a content of 8 to 32% by weight, is diffused into the upper portion of the formed heat-sensitive recording layer (3).
  • a radiation-crosslinking third coating composition by irradiating the heat-sensitive recording material including the applied third coating composition with high-energy radiation from the third coating composition then the release agent having an adhesion (5) is formed, the anchoring of which with the below them thermosensitive recording layer (3 ) is ensured by the part of the third coating composition diffused into the recording layer.
  • the upper portion of the heat-sensitive recording layer (3) having the diffused portion of the third coating composition then forms the diffusion layer (4) through the above-mentioned drying.
  • loading (5) having the release agent had a basis weight in a range of 0.5 g / m 2 to 3 g / m 2 0.8 g / m 2 to 1.85 g / m 2 , more preferably 0.85 g / m 2 to 1.35 g / m 2 , are particularly suitable, while at the same time the diffusion layer (4) as the upper region in the heat-sensitive recording layer (3) having a preferred thickness of 0.2 ⁇ m to 0.8 ⁇ m, preferably 0.2 ⁇ m to 0.5 ⁇ m, in which a part of the third coating composition is diffused with a preferred calculated area-related mass for the diffusion layer (4 ) from 0.15 g / m 2 to 0.65 g / m 2 , was recognized as optimum.
  • the inorganic pigment is shaped like a platelet, as is the case, for example, with kaolinite and talc. Kaolinite and talc as the inorganic pigment are therefore particularly preferred.
  • the inorganic, platelet-shaped pigment in particular kaolinite and talc
  • has an aspect ratio also called “aspect ratio” or “shape factor” of from 5 to 100, preferably from 15 to 100, particularly preferably from 20 to 100 having.
  • the aspect ratio of the inorganic pigment is greater than 20.
  • the aspect ratio is the quotient between the diameter and the thickness of the platelet of the inorganic pigment prior to mixing with the other components.
  • An aspect ratio of 20 means that the diameter of the plate is 20 times larger than the thickness of the plate.
  • the polyvinyl alcohol used as the binder has a saponification degree of more than 99 mol% and a viscosity of more than 7 mPas, preferably more than 12 mPas, measured according to DIN 53015 on an aqueous solution with 4% by mass at 20.degree , particularly preferably more than 15 mPas.
  • it is preferably a polyvinyl alcohol (PVA) 15-99 or a corresponding PVA with a higher degree of saponification and / or higher viscosity than PVA 15-99.
  • the binder is crosslinking (self- or externally crosslinking) and / or modified polyvinyl alcohol, wherein the modified polyvinyl alcohol is preferably diacetone-modified polyvinyl alcohol, silanol group-modified polyvinyl alcohol or carboxyl group-modified polyvinyl alcohol, preferably diacetone-modified polyvinyl alcohol or silanol group-modified polyvinyl alcohol.
  • the heat-sensitive recording layer (3) contains at least one crosslinking aid selected from the list comprising: boric acid, polyamine, epoxy resin, dialdehyde, formaldehyde oligomers , Epiochlorohydrin resin, adipic dihydrazide, dimethylurea, melamine formaldehyde, alone or in admixture with one another.
  • crosslinking aid selected from the list comprising: boric acid, polyamine, epoxy resin, dialdehyde, formaldehyde oligomers , Epiochlorohydrin resin, adipic dihydrazide, dimethylurea, melamine formaldehyde, alone or in admixture with one another.
  • ethylene-vinyl acetate copolymer as the sole binder or in combination with polyvinyl alcohol as a particularly preferred binder, based on the total weight of the heat-sensitive recording layer (3), in a range of 10 to 20 wt .-% in the heat-sensitive recording layer (3) is integrated.
  • the proposed method provides for preparing a second coating composition to form a front surface of the sheet substrate (1) arranged heat-sensitive recording layer (3), which offer this to a particular extent, the use of container scales for accurate feeding and metering of bulk components and liquid components.
  • thermosensitive recording material has as a dye precursor in the second coating composition for forming the heat-sensitive Recording layer (3) preferably includes those selected from the list, comprising: 3-diethylamino-6-methyl-7-anilinofluoran, 3-dibutylamino-6-methyl-7-anilinofluoran, 3- (N-methyl-N-propyl) amino-6-methyl-7-anilinofluoran, 3- (N- ethyl-N-isoamyl) amino-6-methyl-7-anilinofluoran, 3- (N-methyl-N-cyclohexyl) amino-6-methyl-7-anilinofluoran, 3- (N-ethyl-N-tolyl) amino 6-methyl-7-anilinofluoran and 3- (N-ethyl-N-tetrahydrofuryl) amino-6-methyl-7-anilinofluoran.
  • 3-dibutylamino-6-methyl-7-anilinofluoran preferably includes those selected
  • the second coating composition for forming the thermosensitive recording layer (3) may contain at least one sensitiser selected from the list consisting of stearic acid amide, dimethylsulfone, 2- (2H-benzotriazol-2-yl) -p-cresol and dimethyl terephthalate, for increasing thermal responsiveness according to a first preferred embodiment alone, that is, not used in combination with the other three mentioned sensitizers from the above list.
  • at least two sensitisers selected from the list comprising stearic acid amide, dimethylsulfone, 2- (2H-benzotriazol-2-yl) -p-cresol and dimethyl terephthalate are included in the second coating composition.
  • dimethylsulfone on the one hand and dimethyl terephthalate on the other hand are considered to be very particularly preferred.
  • the basis weight of the heat-sensitive recording layer (3) is preferably between 2.5 and 6.2 g / m 2 and more preferably between 2.4 and 4.9 g / m 2 .
  • the recording material proposed here preferably has an intermediate layer (2) positioned between the sheet-shaped substrate (1) and the heat-sensitive recording layer (3), as already described was executed in the front of the description.
  • the high importance of organic hollow body pigments in the intermediate layer (2) is based on the fact that such organic pigments are to a particular extent a high heat reflectivity of the intermediate layer (2) conducive.
  • the hollow body pigments have in their interior air, which is a good heat insulator.
  • the thus optimized as a heat reflection layer intermediate layer (2) increases so far specifically the response of the recording layer (3) to heat.
  • the intermediate layer (2) very particularly preferably also inorganic pigments, wherein the inorganic pigments selected from the list individually or in combination, comprising: natural and calcined kaolin, silica and here especially bentonite, calcium carbonate and aluminum hydroxide and here especially boehmite.
  • the thermal head initiating the color-forming reaction of the dye precursors with the (color) developers in the heat-sensitive recording layer (3) causes the wax-like components to melt in the recording layer (3).
  • the preferred incorporated inorganic pigments of the intermediate layer (2) also cause absorption of this melt.
  • the inorganic pigments of the intermediate layer (2) 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, have. This requirement is met by the above-mentioned inorganic pigments.
  • the ratio between the total of organic hollow body pigments and the total of inorganic pigments within the intermediate layer (2) is a compromise of the effects caused by the two types of pigments, which is particularly advantageously solved if 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 .-% of inorganic pigment.
  • Pigment mixtures of different organic and / or different inorganic pigments are conceivable.
  • the intermediate layer (2) contains at least one binder, preferably based on a synthetic polymer, with styrene-butadiene latex, for example, giving particularly good results.
  • a synthetic binder in admixture with at least one natural polymer, more preferably starch, is a particularly suitable embodiment.
  • the first coating composition for forming the intermediate layer (2) is applied by means of a leveling coating process selected from the list comprising: roller coater, doctor blade and doctor blade coater.
  • the intermediate layer (2) can make a positive contribution to the leveling of the substrate surface, which reduces the amount to be applied for the second coating composition for forming the heat-sensitive recording layer (3).
  • the subsequent drying of the coating composition for forming the intermediate layer (2) is usually done by supplying heat, as is done by hot-air flotation or contact dryer. Also proven is a combination of hot-air floatation dryer and contact dryer.
  • a preferred range between 5 and 20 g / m 2 and even better between 7 and 12 g / m 2 has proven.
  • an intermediate layer is used between the sheet-shaped substrate (1) and the heat-sensitive recording layer (3) which contains no hollow body pigments but inorganic pigments, the inorganic pigments preferably being used singly or in combination selected among themselves from the list, comprising: natural or calcined kaolin, silica and here especially bentonite, calcium carbonate and aluminum hydroxide and here especially boehmite.
  • paper and especially a non-surface treated base paper is the substrate that has prevailed on the market with regard to good environmental compatibility because of good recyclability and is preferred for the purposes of the invention
  • 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.
  • films of polypropylene, polyolefin and polyolefin-coated papers, for example, are possible to the same extent as a web-shaped substrate (1), without such an embodiment having an exclusive character.
  • Another aspect of the present invention is the use of a heat-sensitive recording material according to the invention as a self-adhesive ticket, self-adhesive ticket, self-adhesive proof of purchase, self-adhesive label or self-adhesive tickets.
  • Another aspect of the present invention is the use of a silicone component in a process for producing a thermosensitive recording material of the invention as defined in claim 14.
  • a web-shaped substrate is on a fourdrinier paper machine from bleached and ground deciduous and softwood pulps with the addition of, based on the total solids content (atro) of the pulp fed pulp, 0.8 wt .-% AKD glue as engine sizing and other conventional admixtures a backing paper having a basis weight of 64 g / m 2 made.
  • styrene-butadiene latex as a binder and, in addition to other aids starch cobinder-containing intermediate layer having a basis weight of 9 g / m 2 applied using a doctor blade.
  • a heat-sensitive recording layer having a basis weight of 2.5 g / m 2 is applied by means of a roller doctor coater.
  • the aqueous coating used for this purpose contains the following components according to the recipe given in Table 1: Table 1: Data in wt .-% (atro), based on the total weight of the heat-sensitive recording layer dye precursor 3-dibutylamino-6-methyl-7-anilinofluoran (ODB-2) 9 (Color) Developer N- (p-toluenesulphonyl) -N'-3- (p-toluenesulphonyl-oxyphenyl) urea (Pergafast® 201 (BASF)) 20 sensitizer Benzyl 2-naphthyl ether (BNE) 16 binder Polyvinyl alcohol co-ethylene copolymer (EVOH) 15 co-binder Acrylate copolymers 10 methylcellulose 2 pigment Talc (platelet-shaped with an aspect ratio
  • 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.
  • the prepared web-shaped substrate with intermediate layer and heat-sensitive recording layer is coated on the front side (on the heat-sensitive recording layer) by an anilox roller coater with a radically curing standard UV-silicone system.
  • the solvent-free Evonik standard silicone system used for this purpose contains a formulation given in Table 2.
  • the silicone coating is about 1.2 g / m 2 .
  • Table 2 RC-711 silicone acrylate 25 parts by weight RC-902 silicone acrylate 50 parts by weight RC-1772 silicone acrylate (mixture with matting agent) 25 parts by weight TEGO photoinitiator A-18 2 parts by weight
  • the thus obtained release agent is cured with a UV lamp (80 W / cm) under a protective gas atmosphere of nitrogen.
  • a heat-sensitive recording material according to the invention is obtained in which the application layer comprising the release agents does not detach from the heat-sensitive recording layer. Even after storage for 30 days, the release agent-containing coating layer can not be detached from the heat-sensitive recording layer.
  • the produced recording material has a good sensitivity.
  • Example 1 was repeated except that the composition of the pigmented interlayer was changed.
  • the altered composition of the pigmented interlayer is given in Table 3.
  • Table 3 water 100 parts by weight 30% dispersion of fine hollow particles (particle size: 0.45 ⁇ m) 300 parts by weight 25% solution of oxidized starch 24 parts by weight 48% latex (glass transition temperature: 0 ° C) 25 parts by weight
  • a heat-sensitive recording material according to the invention is obtained in which the application layer comprising the release agents does not detach from the heat-sensitive recording layer. Even after storage for 30 days, the release agent-containing coating layer can not be detached from the heat-sensitive recording layer.
  • the produced recording material has a very good sensitivity.
  • an adhesive layer was prepared by applying a polyacrylic resin adhesive.
  • the web-shaped substrate was then rolled up, so that the adhesive layer is on the release agent layer having a release agent. Even after storage for 30 days, individual layers of the thermosensitive recording material can be unrolled without dissipating the releasing layer having the releasing agent from the thermosensitive recording layer or leaving residues of the adhesive layer on the impurity-containing impingement layer.
  • an adhesive layer was formed by applying a polyacrylic resin adhesive.
  • the web-shaped substrate was then rolled up, so that the adhesive layer is on the release agent layer having a release agent. Even after storage for 30 days, individual layers of the thermosensitive recording material can be unrolled without dissipating the releasing layer having the releasing agent from the thermosensitive recording layer or leaving residues of the adhesive layer on the impurity-containing impingement layer.

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

Claims (14)

  1. Matériau d'enregistrement thermosensible, comprenant
    - un substrat (1) en forme de feuille continue, présentant une face avant et une face arrière opposée à la face avant,
    - une couche d'enregistrement thermosensible (3), disposée côté face avant du substrat (1) en forme de feuille continue,
    ce matériau d'enregistrement thermosensible (3) contenant au moins un précurseur de colorant et au moins un révélateur (chromogène) pouvant réagir avec cet au moins un précurseur de colorant,
    - une surface (6) côté face avant du matériau d'enregistrement thermosensible, qui a une structure déhésive vis-à-vis de couches adhésives (7), qui peuvent être appliquées sur la face arrière du substrat (1) en forme de feuille continue,
    le matériau d'enregistrement thermosensible présentant, pour la réalisation de sa surface déhésive (6) côté face avant,
    - une couche de couverture (5), disposée par-dessus la couche d'enregistrement thermosensible (3), présentant au moins un agent antiadhésif, la couche de couverture (5) contenant, en tant qu'un ou plusieurs agents antiadhésifs, un composant silicone,
    et
    - une couche de diffusion (4), formée entre la couche de couverture (5) présentant au moins un agent antiadhésif et la couche d'enregistrement thermosensible (3),
    la couche de diffusion (4) étant formée par pénétration par diffusion en pleine surface de parties du ou des agents antiadhésifs provenant de la couche de couverture (5) dans la zone supérieure, orientée vers la couche de couverture (5), de la couche d'enregistrement thermosensible (3) appliquée avant application de la couche de couverture (5), et
    une proportion de 5 à 50 % en poids de la totalité des agents antiadhésifs de la couche de couverture (5) pénétrant par diffusion dans la zone supérieure de la couche d'enregistrement thermosensible (3) formée,
    la couche d'enregistrement thermosensible (3) contenant au moins un pigment inorganique choisi dans la liste consistant en la kaolinite, le silicate de magnésium hydraté (talc), l'hydroxyde d'aluminium, le carbonate de calcium et le dioxyde de silicium (silice).
  2. Matériau d'enregistrement thermosensible selon la revendication 1, caractérisé en ce qu'on a fait pénétrer par diffusion dans la zone supérieure de la couche d'enregistrement thermosensible (3) formée une proportion de 8 à 32 % en poids de la totalité des agents antiadhésifs de la couche de couverture (5).
  3. Matériau d'enregistrement thermosensible selon l'une des revendications 1 et 2, caractérisé en ce que le matériau d'enregistrement thermosensible (3) contient au moins un pigment lamellaire, et que le pigment lamellaire présente de préférence un rapport d'aspect de 5 à 100, plus préférentiellement un rapport d'aspect de 15 à 100, d'une manière particulièrement préférée de 20 à 100.
  4. Matériau d'enregistrement thermosensible selon l'une des revendications 1 à 3, caractérisé en ce que a) le composant silicone a été soumis à une réticulation radicalaire ou cationique, et/ou b) en ce que la couche de couverture (5) est réticulée à l'aide d'un rayonnement de haute énergie, et/ou c) la couche de couverture (5) est réalisée réticulable aux UV.
  5. Matériau d'enregistrement thermosensible selon l'une des revendications 1 à 4, caractérisé en ce que le matériau d'enregistrement thermosensible présente une couche adhésive (7) disposée sur la face arrière du substrat (1) en forme de feuille continue.
  6. Matériau d'enregistrement thermosensible selon l'une des revendications 1 à 5, caractérisé en ce que le matériau d'enregistrement thermosensible présente une couche intermédiaire (2), présentant des pigments à corps creux positionnés entre le substrat (1) en forme de feuille continue et la couche d'enregistrement thermosensible (3).
  7. Matériau d'enregistrement thermosensible selon l'une des revendications 1 à 6, caractérisé en ce que la couche d'enregistrement thermosensible (3) contient au moins un révélateur (chromogène) choisi dans la liste comprenant :
    - le 4-[(4-1-méthyléthoxy)phényl)sulfonyl]-phénol,
    - la N-(p-toluènesulfonyl)-N'-3-(p-toluènesulfonyl-oxy-phényl)-urée,
    - le diisipropyldiphénol,
    - le 4,4'-sulfonyldiphénol,
    - le N-[2-(3-phényluréido)phényl]benzènesulfonamide
  8. Matériau d'enregistrement thermosensible selon la revendication 7, caractérisé en ce que la couche d'enregistrement thermosensible (3) contient au moins un révélateur (chromogène) choisi dans la liste comprenant :
    - la N-(p-toluènesulfonyl)-N'-3-(p-toluènesulfonyl-oxy-phényl)-urée,
    - le N-[2-(3-phényluréido)phényl]benzènesulfonamide
  9. Matériau d'enregistrement thermosensible selon l'une des revendications 1 à 8, caractérisé en ce que la couche d'enregistrement thermosensible (3) contient en tant que précurseur de colorant du 3-dibutylamino-6-méthyl-7-anilinofluorane.
  10. Matériau d'enregistrement thermosensible selon l'une des revendications 1 à 9, caractérisé en ce que la couche d'enregistrement thermosensible (3) contient au moins un liant hydrophile.
  11. Matériau d'enregistrement thermosensible selon la revendication 10, caractérisé en ce que la couche d'enregistrement thermosensible (3) contient en tant que liant au moins un composant choisi dans la liste comprenant :
    - un copolymère éthylène-acétate de vinyle
    - un poly(alcool vinylique)
    - un latex de styrène-butadiène
    - un latex de styrène-acrylate
    - de l'amidon
  12. Procédé de fabrication d'un matériau d'enregistrement thermosensible selon l'une des revendications 1 à 11, le procédé comprenant au moins les étapes suivantes :
    - réalisation d'un substrat (1) en forme de feuille continue, présentant une face avant et une face arrière opposée à la face avant,
    - en option :
    - préparation d'une première composition de revêtement, cette première composition de revêtement comprenant au moins des pigments à corps creux,
    - application de la première composition de revêtement préparée, pour réaliser une couche intermédiaire (2) présentant des pigments à corps creux,
    - séchage de la première composition de revêtement,
    - préparation d'une deuxième composition de revêtement, cette deuxième composition de revêtement comprenant au moins un précurseur de colorant et au moins un révélateur (chromogène) pouvant réagir avec cet au moins un précurseur de colorant, cette deuxième composition de revêtement contenant au moins un pigment inorganique choisi dans la liste consistant en la kaolinite, le silicate de magnésium hydraté (talc), l'hydroxyde d'aluminium, le carbonate de calcium et le dioxyde de silicium (silice),
    - application de la deuxième composition de revêtement préparée, pour réaliser une couche d'enregistrement thermosensible (3), disposée côté face avant du substrat (1) en forme de feuille continue,
    - séchage de la deuxième composition de revêtement,
    - préparation d'une troisième composition de revêtement, cette troisième composition de revêtement comprenant au moins un agent antiadhésif, l'agent antiadhésif étant un composant silicone,
    - application de la troisième composition de revêtement préparée,
    - réalisation d'une couche de diffusion (4) par pénétration par diffusion en pleine surface de parties au moins de l'agent antiadhésif provenant de la troisième composition de revêtement appliquée, dans la zone supérieure de la couche d'enregistrement thermosensible (3) formée, une proportion de 5 à 50 % en poids de la totalité des agents antiadhésifs de la troisième composition de revêtement appliquée pénétrant par diffusion dans la zone supérieure de la couche d'enregistrement thermosensible (3) formée,
    - réticulation de la troisième composition de revêtement à l'aide d'un rayonnement de haute énergie, pour réaliser la couche de couverture (5) présentant un agent antiadhésif,
    - en option :
    - préparation d'une quatrième composition de revêtement,
    - application de la quatrième composition de revêtement préparée pour réaliser une couche adhésive (7) disposée sur la face arrière du substrat (1) en forme de feuille continue,
    - séchage ou la réticulation de la quatrième composition de revêtement.
  13. Utilisation en tant que ticket autoadhésif d'un matériau d'enregistrement thermosensible selon l'une des revendications 1 à 11.
  14. Utilisation d'un composant silicone dans un procédé de fabrication d'un matériau d'enregistrement thermosensible selon la revendication 12, dans lequel on applique sur la couche d'enregistrement thermosensible une composition de revêtement pour la réalisation d'une couche de revêtement présentant au moins un agent antiadhésif, l'agent antiadhésif étant un composant silicone, et une couche de diffusion (4) étant réalisée par introduction par diffusion en pleine surface de parties d'au moins l'agent antiadhésif provenant de la composition de revêtement appliquée, dans la zone supérieure de la couche d'enregistrement thermosensible (3) formée, une proportion de 5 à 50 % en poids de la totalité des agents antiadhésifs de la composition de revêtement pénétrant par diffusion dans la zone supérieure de la couche d'enregistrement thermosensible (3) formée.
EP15176526.0A 2015-06-24 2015-07-13 Materiel d'enregistrement sensible a la chaleur Active EP3109059B1 (fr)

Priority Applications (11)

Application Number Priority Date Filing Date Title
PL15176526T PL3109059T3 (pl) 2015-06-24 2015-07-13 Ciepłoczuły materiał rejestrujący
EP16733414.3A EP3221153B1 (fr) 2015-06-24 2016-06-24 Materiel d'enregistrement sensible a la chaleur
PL16733414T PL3221153T3 (pl) 2015-06-24 2016-06-24 Termoczuły materiał rejestrujący
ES16733414.3T ES2693023T3 (es) 2015-06-24 2016-06-24 Material de registro termosensible
KR1020177024307A KR102058570B1 (ko) 2015-06-24 2016-06-24 감열 기록 재료
US15/537,359 US10328735B2 (en) 2015-06-24 2016-06-24 Heat-sensitive recording material
RU2017125823A RU2670521C1 (ru) 2015-06-24 2016-06-24 Термочувствительный материал для регистрации информации
JP2017541253A JP2018509316A (ja) 2015-06-24 2016-06-24 感熱記録材料
PCT/EP2016/064676 WO2016207356A1 (fr) 2015-06-24 2016-06-24 Matériau d'impression thermosensible
CN201680004448.8A CN107107642B (zh) 2015-06-24 2016-06-24 热敏性记录材料
JP2019146584A JP2019206188A (ja) 2015-06-24 2019-08-08 感熱記録材料

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EP15173719 2015-06-24

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KR (1) KR102058570B1 (fr)
CN (1) CN107107642B (fr)
DE (1) DE202015009476U1 (fr)
ES (2) ES2684629T3 (fr)
PL (2) PL3109059T3 (fr)
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DE102016219569A1 (de) * 2016-10-07 2018-04-12 Mitsubishi Hitec Paper Europe Gmbh Wärmeempfindliches Aufzeichnungsmaterial
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EP4384398A2 (fr) 2021-08-11 2024-06-19 Koehler Innovation & Technology GmbH Matériau d'enregistrement thermosensible, procédé de décoloration d'un matériau d'enregistrement thermosensible, mélange de matériaux fibreux, procédé de fabrication d'un papier recyclé et papier recyclé
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EP3221153A1 (fr) 2017-09-27
CN107107642A (zh) 2017-08-29
WO2016207356A1 (fr) 2016-12-29
EP3221153B1 (fr) 2018-08-15
KR102058570B1 (ko) 2019-12-23
RU2670521C1 (ru) 2018-10-23
JP2018509316A (ja) 2018-04-05
EP3109059A1 (fr) 2016-12-28
JP2019206188A (ja) 2019-12-05
PL3221153T3 (pl) 2018-12-31
US10328735B2 (en) 2019-06-25
ES2693023T3 (es) 2018-12-07
US20170368859A1 (en) 2017-12-28
PL3109059T3 (pl) 2018-10-31

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