EP3109059B2 - Materiel d'enregistrement sensible a la chaleur - Google Patents

Materiel d'enregistrement sensible a la chaleur

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Publication number
EP3109059B2
EP3109059B2 EP15176526.0A EP15176526A EP3109059B2 EP 3109059 B2 EP3109059 B2 EP 3109059B2 EP 15176526 A EP15176526 A EP 15176526A EP 3109059 B2 EP3109059 B2 EP 3109059B2
Authority
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
Other languages
German (de)
English (en)
Other versions
EP3109059B1 (fr
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
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Family has litigation
First worldwide family litigation filed litigation Critical https://patents.darts-ip.com/?family=53498810&utm_source=google_patent&utm_medium=platform_link&utm_campaign=public_patent_search&patent=EP3109059(B2) "Global patent litigation dataset” by Darts-ip is licensed under a Creative Commons Attribution 4.0 International License.
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 JP2017541253A priority patent/JP2018509316A/ja
Priority to KR1020177024307A priority patent/KR102058570B1/ko
Priority to EP16733414.3A priority patent/EP3221153B2/fr
Priority to US15/537,359 priority patent/US10328735B2/en
Priority to CN201680004448.8A priority patent/CN107107642B/zh
Priority to PCT/EP2016/064676 priority patent/WO2016207356A1/fr
Priority to ES16733414T priority patent/ES2693023T5/es
Priority to PL16733414T priority patent/PL3221153T3/pl
Priority to FIEP16733414.3T priority patent/FI3221153T4/fi
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
Publication of EP3109059B2 publication Critical patent/EP3109059B2/fr
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
    • B41M—PRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
    • B41M5/00—Duplicating or marking methods; Sheet materials for use therein
    • B41M5/26—Thermography ; Marking by high energetic means, e.g. laser otherwise than by burning, and characterised by the material used
    • B41M5/40—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 web-shaped substrate and a heat-sensitive recording layer arranged on the front side of the web-shaped substrate, wherein this heat-sensitive recording layer contains at least one dye precursor and at least one (color) developer reactive with this dye precursor.
  • This (color) developer reacts with this dye precursor upon sufficient external heat supply, forming a visually recognizable printed image.
  • the surface of the heat-sensitive recording material is non-adhesive with respect to adhesive layers that can be applied to the reverse side of the web-shaped substrate.
  • Heat-sensitive recording materials that react to external heat to form colors have been known for many years and enjoy continued popularity, partly due to the significant advantages they offer businesses issuing tickets, receipts, and admission tickets. Because the color-forming components—dye precursors and the (color) developers that react with heat (also called color acceptors)—are contained within the recording material itself, thermal printers, which do not require toner or ink cartridges and therefore do not need regular maintenance, can be deployed in large numbers.
  • heat-sensitive recording materials that feature a recording layer on the front (whose functional components have already been discussed above) and an adhesive layer on the back, allowing users to employ them as self-adhesive tickets.
  • This innovative technology has thus become widely established, especially in the retail sector – for example, for labeling self-weighing products – and in public transport – for example, as luggage stickers.
  • the adhesive layers on the back can be covered by a separate release paper until use; however, recording materials with front surfaces that are non-adhesive to the adhesive layers on the back are much more popular and practical to handle.
  • the adhesive layers on the back are covered by the non-adhesive front surfaces of the recording material itself, which is wound onto a roll where the front and back sides meet, until use.
  • a heat-sensitive recording material proposed therein has a protective layer comprising a UV-curing resin and a copolymer resin, including a silicone component as the copolymerizing agent. This document does not mention heat-sensitive recording materials for self-adhesive tickets, even though it has proven suitable for this application.
  • the EP 1 637 339 B1 A heat-sensitive recording material comprising a substrate, a heat-sensitive recording layer, and a protective layer is presented, in which the protective layer, in addition to binder resin, filler, and crosslinking agent, specifically includes a release agent.
  • This release agent is introduced as a spherical and particulate silicone compound with a specific formula.
  • a disadvantage of this known proposal is the complex and expensive manufacturing process involving the substrate, recording layer, and final protective layer.
  • the protective layer due to its filler and binder components, also affects the dynamic and static sensitivity of the known heat-sensitive recording material to externally applied heat. Formation of a visually recognizable printed image WO2013050531 A1 reveals a heat-sensitive recording material similar to that found in the EP1637339 B1 is described.
  • the object of the present invention is therefore to provide a heat-sensitive recording material with convincing sensitivity to applied external heat for the formation of a visually recognizable printed image, which can be manufactured at moderate production costs and designed as a self-adhesive ticket with a back adhesive layer without additional release paper.
  • the diffusion layer (4) makes a significant contribution to the layer adhesion between the release agent-containing substrate (5) and the heat-sensitive recording layer (3). Without the diffusion layer (4), problems arose in the layer adhesion between the release agent-containing substrate (5) and the heat-sensitive recording layer (3), leading to problems in the use of the recording material.
  • the heat-sensitive recording material proposed herein has an intermediate layer (2) comprising hollow body pigments positioned between the web-shaped substrate (1) and the heat-sensitive recording layer (3).
  • Such heat-sensitive recording material is produced by a method wherein the method includes at least the method steps as defined in claim 11.
  • the coating composition and/or the silicone component has a viscosity of 50 to 1,000 mPas, preferably 50 to 100 mPas or 500 to 1,000 mPas. It is particularly preferred that the silicone component is an aqueous emulsion or a UV-curing silicone component, wherein the cross-linking occurs radically (preferably under a nitrogen protective atmosphere) or cationically. Within the scope of the present invention, it is particularly preferred that the silicone component is a UV-curing silicone component that cross-links radically (after appropriate irradiation with high-energy radiation (e.g., UV radiation)). Within the scope of the present invention, it is preferred that the silicone component is not a thermally cross-linking silicone component or a silicone component dissolved in an organic solvent.
  • a portion of the third coating composition diffuses into the upper region of the formed heat-sensitive recording layer (3), wherein a proportion of 5 to 50 wt.% of the total release agent of the third coating composition, preferably a proportion of 8 to 32 wt.%, diffuses into the upper region of the formed heat-sensitive recording layer (3).
  • This diffusion occurs through drying or, in the case of a radiation-curing third coating composition, through irradiation of the heat-sensitive recording material, including the applied third coating composition, with high-energy light.
  • Radiation from the third coating composition then fully forms the coating (5) containing a release agent, the anchoring of which to the heat-sensitive recording layer (3) located beneath it is ensured by the portion of the third coating composition that diffuses into the recording layer.
  • the upper region of the heat-sensitive recording layer (3) with the diffused portion of the third coating composition then forms the diffusion layer (4) through the drying or crosslinking described above.
  • an area-related mass in the range of 0.5 g/ m2 to 3 g/ m2 , preferably 0.8 g/ m2 to 1.85 g/ m2 , and particularly preferably 0.85 g/ m2 to 1.35 g/ m2 is particularly suitable, while at the same time the diffusion layer (4) as the upper region in the heat-sensitive recording layer (3) with a preferred thickness of 0.2 ⁇ m to 0.8 ⁇ m, preferably 0.2 ⁇ m to 0.5 ⁇ m, in which a portion of the third coating composition has diffused, with a preferred calculated area-related mass for the diffusion layer (4) of 0.15 g/ m2 to 0.65 g/ m2 , is particularly suitable.
  • the optimum was identified.
  • the inorganic pigment is platelet-shaped, as is the case, for example, with kaolinite and talc. Kaolinite and talc are therefore particularly preferred as inorganic pigments. It is also particularly preferred if the inorganic, platelet-shaped pigment (especially kaolinite and talc) has an aspect ratio (also called "shape factor") of 5 to 100, preferably 15 to 100, and more preferably 20 to 100. In a preferred embodiment, 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 before mixing with the other components. An aspect ratio of 20 means that the diameter of the platelet is 20 times larger than the thickness of the platelet.
  • a value of 8 to 18 wt.-% (atro) based on the total weight of the heat-sensitive recording layer (3) is considered particularly suitable, which is restricted downwards by the increasing risk of possible thermal printhead deposits and upwards by an increasing reduction in the sensitivity to the heat of the thermal printheads causing the print image.
  • the polyvinyl alcohol used as a binder has a degree of saponification of more than 99 mol% and a viscosity of more than 7 mPas, preferably more than 12 mPas, particularly preferably more than 15 mPas, as measured according to DIN 53015 on an aqueous solution with 4 wt% at 20 °C.
  • it is 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 a crosslinking (self- or 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 agent selected from the list comprising: boric acid, polyamine, epoxy resin, dialdehyde, formaldehyde oligomers, epiochlorohydrin resin, adipic acid dihydrazide, dimethyl urea, melamine formaldehyde, alone or in mixtures with each other.
  • crosslinking agent selected from the list comprising: boric acid, polyamine, epoxy resin, dialdehyde, formaldehyde oligomers, epiochlorohydrin resin, adipic acid dihydrazide, dimethyl urea, melamine formaldehyde, alone or in mixtures with each other.
  • ethylene-vinyl acetate copolymer is considered as the sole binder or in combination with polyvinyl alcohol as a particularly preferred binder, which is incorporated into the heat-sensitive recording layer (3) in a range of 10 to 20 wt.%, based on the total weight of the heat-sensitive recording layer (3).
  • the proposed method involves preparing a second coating composition to form a heat-sensitive recording layer (3) arranged on the front side of the web-shaped substrate (1), for which the use of container scales for the precise supply and dosing of bulk components and liquid components is particularly suitable.
  • the heat-sensitive recording material preferably comprises, as dye precursors in the second coating composition for the formation of the heat-sensitive recording layer (3), those selected from the list, comprising: 3-diethylamino-6-methyl-7-anilinofluorane, 3-dibutylamino-6-methyl-7-anilinofluorane, 3-(N-methyl-N-propyl)amino-6-methyl-7-anilinofluorane, 3-(N-ethyl-N-isoamyl)amino-6-methyl-7-anilinofluorane, 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. Particularly preferred is 3-dibutylamin
  • the second coating composition for forming the heat-sensitive recording layer (3) can contain at least one sensitizer selected from the list comprising stearic acid amide, dimethyl sulfone, 2-(2H-benzotriazol-2-yl)-p-cresol, and dimethyl terephthalate to increase the thermal response sensitivity.
  • these sensitizers are used alone, i.e., not in combination with the three other sensitizers from the preceding list.
  • a second, equally preferred embodiment ...
  • At least two sensitizers selected from the list comprising stearic acid amide, dimethyl sulfone, 2-(2H-benzotriazol-2-yl)-p-cresol, and dimethyl terephthalate, are incorporated into the second coating composition.
  • dimethyl sulfone and dimethyl terephthalate are considered particularly preferred.
  • Suitable coating devices for applying the second coating composition to form the heat-sensitive recording layer (3) include, in particular, a roller squeegee, knife squeegee, curtain coater, or air brush.
  • the mass per unit area of the heat-sensitive recording layer (3), including the preferred calculated mass per unit area for the diffusion layer (4) of 0.15 g/ m2 to 0.65 g/ m2, is preferably between 2.5 and 6.2 g/ m2 , and even better between 2.4 and 4.9 g/ m2 .
  • the material preferably includes an intermediate layer (2) containing hollow pigments positioned between the web-shaped substrate (1) and the heat-sensitive recording layer (3), as already described earlier.
  • the importance of the organic hollow pigments in the intermediate layer (2) is due to the fact that such organic pigments are particularly conducive to a high heat reflectivity of the intermediate layer (2).
  • the hollow pigments contain air within them, which acts as a good thermal insulator.
  • the intermediate layer (2) thus optimized as a heat-reflecting layer, specifically enhances the heat sensitivity of the recording layer (3).
  • the intermediate layer (2) particularly preferably also contains inorganic pigments, wherein the inorganic pigments are selected individually or in combination from the list, which includes: natural and calcined kaolin, silicon dioxide, and especially bentonite, calcium carbonate, and aluminum hydroxide, and especially boehmite.
  • the thermal head which triggers the color-forming reaction of the dye precursors with the (color) developers in the heat-sensitive recording layer (3), causes waxy components in the recording layer (3) to melt.
  • the preferably incorporated inorganic pigments of the intermediate layer (2) also cause this melt to be absorbed.
  • the inorganic pigments of the intermediate layer (2) have an oil absorption of at least 80 cm3 /100 g and even better of 100 cm3 /100 g, determined according to the Japanese standard JIS K 5101.
  • the inorganic pigments named above meet this requirement.
  • the ratio of the total organic hollow-body pigments to the total inorganic pigments within the intermediate layer (2) is a compromise between the effects of the two pigment types, which is particularly advantageous when the pigment mixture consists of 5 to 30 wt.%, or preferably 8 to 20 wt.%, of organic pigment and 95 to 70 wt.%, or preferably 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, yielding particularly good results.
  • a synthetic binder with the addition of at least one natural polymer, such as preferably starch, represents a particularly suitable embodiment.
  • a binder-pigment ratio within the intermediate layer of between 3:7 and 1:9, in each case based on wt.%, represents a particularly suitable embodiment.
  • the first coating composition for forming the intermediate layer (2) is applied using an equalizing coating method selected from the list, including: roller coating, coating knife coating, and (roller) doctor blade coating.
  • the intermediate layer (2) can make a positive contribution to equalizing the substrate surface, thereby reducing the amount of the second coating composition required to form the heat-sensitive recording layer (3).
  • the subsequent drying of the coating composition for forming the intermediate layer (2) is usually carried out by applying heat, as is done using hot air drying dryers or contact dryers. A combination of hot air drying dryers and contact dryers has also proven effective.
  • a preferred range for the mass per unit area of the intermediate layer (2) is between 5 and 20 g/ m2 , and even better, between 7 and 12 g/ m2 .
  • an intermediate layer is used between the web-shaped substrate (1) and the heat-sensitive recording layer (3) which does not have hollow body pigments but inorganic pigments, wherein the inorganic pigments are preferably selected individually or in combination with each other from the list comprising: natural or calcined kaolin, silicon dioxide and here especially bentonite, calcium carbonate and aluminum hydroxide and here especially boehmite.
  • paper Although not limited to paper as a web-shaped substrate (1), paper, and here specifically a non- Surface-treated coated base paper is the substrate that has become established on the market, also due to its good environmental compatibility and recyclability, and is preferred for the purposes of the invention.
  • Untreated coated base paper is understood to mean coated base paper that has not been treated in a size press or coating device.
  • films made of, for example, polypropylene, polyolefin, and papers coated with polyolefin are equally suitable as web-like substrates (1), without any such design being exclusive.
  • 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 admission ticket, self-adhesive receipt, self-adhesive label, or self-adhesive admission ticket.
  • Another aspect of the present invention is the use of a silicone component in a method for producing a heat-sensitive recording material according to the invention as defined in claim 13.
  • a paper with a basis weight of 64 g/m2 is produced on a Fourdrinier paper machine from bleached and ground hardwood and softwood pulps, using a web-shaped substrate with the addition of 0.8 wt% AKD sizing as bulk sizing, based on the total solids content ( atro ) of the pulp supplied to the paper machine, as well as other usual additives.
  • a calcined kaolin pigment, styrene-butadiene latex binder and, in addition to other additives, starch as a cobinder intermediate layer with a surface mass of 9 g/ m2 is applied using a coating knife.
  • a heat-sensitive recording layer with a mass per unit area of 2.5 g/ m2 is applied to this pigmented intermediate layer using a roller squeegee.
  • the aqueous coating compound used contains the following components according to the formula shown in Table 1: Table 1: Values in wt.% (atro), based on the total weight of the heat-sensitive recording layer Dye precursor 3-dibutylamino-6-methyl-7-anilinofluorane (ODB-2) 9 (Color) developer N-(p-toluensulphonyl)-N'-3-(p-toluensulphonyl-oxyphenyl)-urea (Pergafast ® 201 (BASF)) 20 sensitizer Benzyl 2-naphthyl ether (BNE) 16 binder Polyvinyl alcohol-co-ethylene copolymer (EVOH) 15 Cobinder Acrylate copolymers 10 Methylcellulose 2 pigment Talc (platelet-shaped with an aspect
  • heat-sensitive recording layer includes dispersants, defoamers, optical brighteners, thickeners, waxes and crosslinking agents.
  • the heat-sensitive recording layer After the application of the heat-sensitive recording layer, it is dried and smoothed, with a value of 500 Bekk/sec (DIN ISO 53107) being measured for the front surface smoothness.
  • the manufactured web-shaped substrate with intermediate layer and heat-sensitive recording layer is coated on the front side (onto the heat-sensitive recording layer) using an anilox roller deposition unit with a radical Coated with a standard UV-curing silicone system.
  • the solvent-free Evonik standard silicone system used contains a formulation shown in Table 2. The silicone application rate is approximately 1.2 g/ m2 .
  • 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 resulting coating containing the release agent is cured with a UV lamp (80 W/cm) under a protective atmosphere of nitrogen.
  • the invention yields a heat-sensitive recording material in which the release agent-containing layer does not separate from the heat-sensitive recording layer. Even after storage for 30 days, the release agent-containing layer cannot be separated from the heat-sensitive recording layer. The resulting recording material exhibits good sensitivity.
  • Example 1 was repeated, except that the composition of the pigmented intermediate layer was changed.
  • the changed composition of the pigmented intermediate layer 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
  • the invention yields a heat-sensitive recording material in which the release agent-containing layer does not separate from the heat-sensitive recording layer. Even after storage for 30 days, the release agent-containing layer cannot be separated from the heat-sensitive recording layer. The resulting recording material exhibits very good sensitivity.
  • An adhesive layer was produced on the reverse side of the web-shaped substrate of the heat-sensitive recording layer produced in Example 1 by applying a polyacrylic resin adhesive.
  • the web-shaped substrate was then rolled up so that the adhesive layer lay on the release agent-containing contact layer. Even after storage of 30 days, individual layers of the heat-sensitive recording material can be unrolled without the release agent-containing contact layer separating from the heat-sensitive recording layer or leaving any adhesive residue on the release agent-containing contact layer.
  • An adhesive layer was produced on the reverse side of the web-shaped substrate of the heat-sensitive recording layer produced in Example 2 by applying a polyacrylic resin adhesive.
  • the web-shaped substrate was then rolled up so that the adhesive layer lay on the release agent-containing contact layer. Even after storage of 30 days, individual layers of the heat-sensitive recording material can be unrolled without the release agent-containing contact layer separating from the heat-sensitive recording layer or leaving any adhesive residue on the release agent-containing contact 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 (13)

  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 au moins de l'agent antiadhésif 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)
    le matériau d'enregistrement thermosensible (3) contenant au moins un pigment lamellaire, et au moins un liant hydrophile.
  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 un rapport d'aspect de 5 à 100, de préférence 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 la revendication 1, 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.
  11. Procédé de fabrication d'un matériau d'enregistrement thermosensible selon l'une des revendications 1 à 10, 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) ;
    cette deuxième composition de revêtement contenant au moins un pigment lamellaire et au moins un liant hydrophile ;
    - 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.
  12. Utilisation en tant que ticket autoadhésif d'un matériau d'enregistrement thermosensible selon l'une des revendications 1 à 10.
  13. Utilisation d'un composant silicone dans un procédé de fabrication d'un matériau d'enregistrement thermosensible selon la revendication 11, 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 EP3109059B2 (fr)

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Application Number Priority Date Filing Date Title
PL15176526T PL3109059T3 (pl) 2015-06-24 2015-07-13 Ciepłoczuły materiał rejestrujący
ES16733414T ES2693023T5 (es) 2015-06-24 2016-06-24 Material de registro termosensible
FIEP16733414.3T FI3221153T4 (fi) 2015-06-24 2016-06-24 Lämpöherkkä tallennusmateriaali
KR1020177024307A KR102058570B1 (ko) 2015-06-24 2016-06-24 감열 기록 재료
EP16733414.3A EP3221153B2 (fr) 2015-06-24 2016-06-24 Matériel d'enregistrement sensible à la chaleur
US15/537,359 US10328735B2 (en) 2015-06-24 2016-06-24 Heat-sensitive recording material
CN201680004448.8A CN107107642B (zh) 2015-06-24 2016-06-24 热敏性记录材料
PCT/EP2016/064676 WO2016207356A1 (fr) 2015-06-24 2016-06-24 Matériau d'impression thermosensible
RU2017125823A RU2670521C1 (ru) 2015-06-24 2016-06-24 Термочувствительный материал для регистрации информации
PL16733414T PL3221153T3 (pl) 2015-06-24 2016-06-24 Termoczuły materiał rejestrujący
JP2017541253A JP2018509316A (ja) 2015-06-24 2016-06-24 感熱記録材料
JP2019146584A JP2019206188A (ja) 2015-06-24 2019-08-08 感熱記録材料

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EP (2) EP3109059B2 (fr)
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KR (1) KR102058570B1 (fr)
CN (1) CN107107642B (fr)
DE (1) DE202015009476U1 (fr)
ES (2) ES2684629T5 (fr)
FI (2) FI3109059T4 (fr)
PL (2) PL3109059T3 (fr)
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WO (1) WO2016207356A1 (fr)

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FI3221153T4 (fi) 2026-06-03
PL3109059T3 (pl) 2018-10-31
US10328735B2 (en) 2019-06-25
US20170368859A1 (en) 2017-12-28
ES2693023T3 (es) 2018-12-07
EP3221153B1 (fr) 2018-08-15
EP3221153A1 (fr) 2017-09-27
EP3221153B2 (fr) 2026-04-29
FI3109059T4 (fi) 2026-06-03
ES2684629T3 (es) 2018-10-03
PL3221153T3 (pl) 2018-12-31
JP2018509316A (ja) 2018-04-05
JP2019206188A (ja) 2019-12-05
CN107107642B (zh) 2019-04-19
EP3109059B1 (fr) 2018-06-27
KR102058570B1 (ko) 2019-12-23
DE202015009476U1 (de) 2017-12-07
KR20170109032A (ko) 2017-09-27
ES2684629T5 (es) 2026-07-22
EP3109059A1 (fr) 2016-12-28
CN107107642A (zh) 2017-08-29
RU2670521C1 (ru) 2018-10-23
WO2016207356A1 (fr) 2016-12-29
ES2693023T5 (es) 2026-07-22

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