EP3765303B1 - Revêtements en papier thermoréactifs à base de dérivés de cellulose - Google Patents

Revêtements en papier thermoréactifs à base de dérivés de cellulose Download PDF

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Publication number
EP3765303B1
EP3765303B1 EP19722558.4A EP19722558A EP3765303B1 EP 3765303 B1 EP3765303 B1 EP 3765303B1 EP 19722558 A EP19722558 A EP 19722558A EP 3765303 B1 EP3765303 B1 EP 3765303B1
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Prior art keywords
heat
recording material
sensitive recording
material according
thermoresponsive
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EP19722558.4A
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German (de)
English (en)
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EP3765303A1 (fr
Inventor
Maximilian Nau
Markus BIESALSKI
Michael Horn
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Technische Universitaet Darmstadt
Koehler Paper SE
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Technische Universitaet Darmstadt
Koehler Paper SE
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    • 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
    • B41M5/36—Thermography ; Marking by high energetic means, e.g. laser otherwise than by burning, and characterised by the material used using a polymeric layer, which may be particulate and which is deformed or structurally changed with modification of its' properties, e.g. of its' optical hydrophobic-hydrophilic, solubility or permeability properties
    • 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
    • B41M5/36—Thermography ; Marking by high energetic means, e.g. laser otherwise than by burning, and characterised by the material used using a polymeric layer, which may be particulate and which is deformed or structurally changed with modification of its' properties, e.g. of its' optical hydrophobic-hydrophilic, solubility or permeability properties
    • B41M5/366—Thermography ; Marking by high energetic means, e.g. laser otherwise than by burning, and characterised by the material used using a polymeric layer, which may be particulate and which is deformed or structurally changed with modification of its' properties, e.g. of its' optical hydrophobic-hydrophilic, solubility or permeability properties using materials comprising a polymeric matrix containing a polymeric particulate material, e.g. hydrophobic heat coalescing particles
    • 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
    • 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
    • B41M5/36—Thermography ; Marking by high energetic means, e.g. laser otherwise than by burning, and characterised by the material used using a polymeric layer, which may be particulate and which is deformed or structurally changed with modification of its' properties, e.g. of its' optical hydrophobic-hydrophilic, solubility or permeability properties
    • B41M5/361—Thermography ; Marking by high energetic means, e.g. laser otherwise than by burning, and characterised by the material used using a polymeric layer, which may be particulate and which is deformed or structurally changed with modification of its' properties, e.g. of its' optical hydrophobic-hydrophilic, solubility or permeability properties using a polymeric matrix with inorganic particles forming an image by orientation or agglomeration

Definitions

  • the present invention relates to a heat-sensitive recording material, a process for its production and a heat-sensitive recording material obtainable by this process.
  • Heat-sensitive recording materials comprising a carrier substrate which is black or colored on at least one side, in particular paper, synthetic paper and/or a plastic film and which is coated with an opaque material on this black or colored side, are known.
  • a carrier substrate which is black or colored on at least one side, in particular paper, synthetic paper and/or a plastic film and which is coated with an opaque material on this black or colored side.
  • the black or colored carrier substrate appears white on the outside.
  • the opaque coating loses opacity at these points and becomes transparent, so that the black or colored carrier substrate becomes visible.
  • EP 2 345 678 A1 a heat-sensitive recording material comprising a coating of nanoparticles, a shell and a core each having different polymers with different glass transition temperatures.
  • the U.S. 8,054,323 B2 discloses a heat-sensitive recording material comprising a coating containing an opaque polymer, for example a styrene/acrylate copolymer.
  • the EP 2 678 167 B1 discloses a heat-sensitive recording material comprising a thermoresponsive layer with particles of a thermoplastic polymer based on ethylenically unsaturated monomers, these particles having an outer diameter of 200 nm to 1500 nm.
  • the heat-sensitive recording materials known from the prior art have the disadvantage that the structure of the heat-sensitive layer is often quite complex. For example, nanoparticles that are made up of different layers of different polymers have to be provided, which are complex to produce and therefore often expensive. In addition, many of the polymers used are questionable in terms of their sustainability and toxicity. Many heat-sensitive recording materials known from the prior art are also in need of improvement with regard to the sharpness and contrast of the printed image. In addition, many known heat-sensitive recording materials have deficiencies in storage stability.
  • the object of the present invention is to eliminate the aforementioned disadvantages of the prior art.
  • the object of the present invention is to provide a heat-sensitive recording material that comprises a thermoresponsive layer that is made up of sustainable, ie as natural and/or renewable raw materials as possible, and has as little toxicity as possible or no toxicity at all.
  • the material of the thermoresponsive layer should be able to be provided as simply and easily as possible.
  • the heat-sensitive recording material should enable a sharp and high-contrast printed image and, moreover, should not be impaired even after prolonged storage.
  • the heat-sensitive recording material should be able to be produced by a process that is as simple and inexpensive as possible.
  • the melting point of the substances used in the thermoresponsive layer should preferably be above 90°C, so that the process temperatures of up to 90°C that are common during production do not have a negative effect on the product.
  • a heat-sensitive recording material which has a carrier substrate which is black or colored on at least one side and a thermoresponsive layer on the at least one black or colored side of the carrier substrate, wherein the thermoresponsive layer comprises nanoparticles of at least one cellulose ester.
  • thermoresponsive layer comprises nanoparticles of modified cellulose, i.e. at least one cellulose ester, since the cellulose ester is non-toxic and therefore essentially harmless to health.
  • this cellulose ester is available relatively inexpensively in large quantities.
  • the cellulose ester also has high opacity and a favorable melting point and glass transition temperature for thermal printing applications.
  • a heat-sensitive recording material comprising a thermoresponsive layer comprising nanoparticles of at least one cellulose ester can also be produced relatively easily and inexpensively. In addition, it has a high storage stability and an excellent print image.
  • the cellulose ester has a relatively high melting point, so that the process temperatures of up to 90° C. that are customary in the production of the heat-sensitive recording material can be tolerated.
  • the carrier substrate of the heat-sensitive recording material according to the invention comprises at least one black or colored side.
  • the term "colored page" means that the page is a color other than white or black.
  • the heat-sensitive recording material includes at least one side that is not white.
  • Embodiments are also possible in which the at least one black or colored side has several different colors, also in combination with the color black.
  • thermoresponsive layer comprising nanoparticles of at least one cellulose ester, is applied to this at least one side of the carrier substrate that is not white, but rather colored or black.
  • thermoresponsive layer comprising the nanoparticles of at least one cellulose ester is preferably substantially white.
  • Nanoparticles of cellulose esters and production processes therefor are generally known.
  • the alcohol groups of the cellulose are usually esterified first.
  • cellulose esterifications are preferably carried out using the respective acid anhydrides and a catalyst, typically sulfuric acid.
  • a catalyst typically sulfuric acid.
  • the cellulose is initially suspended in the reaction mixture, but as the acetylation progresses, the cellulose becomes more and more soluble in the glacial acetic acid, which causes the reaction mixture to be homogenized.
  • the viscosity of the solution varies parallel to the optical change and provides information about the degree of substitution (DS).
  • DS degree of substitution
  • cellulose esters are cellulose acetate propionate, cellulose butyrate and cellulose acetate butyrate, which are prepared analogously to the process described above, preferably using the respective acid anhydrides.
  • the cellulose ester is typically dissolved in a solvent, eg THF, acetone, etc., so that the concentration of the cellulose ester is around 1 to 10 mg/mL.
  • a solvent eg THF, acetone, etc.
  • This solution is then precipitated in a non-solvent, such as a mixture of isopropanol and distilled water.
  • the non-solvent can be added to the solution of the cellulose ester.
  • the resulting suspension is typically stirred for 12 to 24 hours to enable solvent exchange between the still swollen particles and the precipitant.
  • the particles settled into the lower quarter of the precipitation mixture and about 4/5 of the solvent mixture are separated off.
  • the resulting suspension is centrifuged and the resulting particle sludge is flushed with water to then be incorporated into coating formulations.
  • the usual yields are between 70 and 80%.
  • the heat-sensitive recording material according to the invention is preferably characterized in that the nanoparticles of the at least one cellulose ester have number-average particle sizes of 50 to 400 nm, preferably 160-200 nm (+/- 40 nm), measured by means of dynamic light scattering (or “dynamic light scattering", DLS).
  • Dynamic light scattering is a method in which the scattered light from a laser is analyzed on a dissolved or suspended sample. It is often used with polymers and biopolymers or nanoparticles of these polymers and biopolymers to determine their average particle size.
  • the number-average particle size was determined in detail as follows: A "Nanophox" from the manufacturer Sympatec was used.
  • This particle size analyzer uses photon cross-correlation spectroscopy (a statistical analysis method based on DLS) to determine particle sizes and distributions.
  • the temperature was kept constant during the measurement with a thermostat, typically at 20 °C. Distilled water is usually used as the fluid medium.
  • a large number of scatter events are detected (typically set at around 300,000 per second over several minutes).
  • the measured values obtained in this way provide information about the Brownian molecular movement of the particles and their diffusion coefficients.
  • the particle diameter is calculated on the basis of this by using the Stokes-Einstein relationship.
  • thermoresponsive layer has a transparency, measured according to DIN 53147:1993-01, of less than 35%, preferably less than 30%, particularly preferably less than 25% and very particularly preferably less than 20%, in particular less than 15% or even less than 10%.
  • Transparency means the ability of matter to let electromagnetic waves through (transmission).
  • Opacity describes the opposite of transparency, i.e. lack of transparency or lack of permeability. Opacity is the reciprocal of transmission.
  • the low transparency preferred according to the invention has the advantage that the black or colored side of the carrier substrate is essentially completely covered and appears at least essentially white to the outside.
  • the heat-sensitive recording material according to the invention is preferably characterized in that the at least one cellulose ester comprises cellulose acetate, cellulose acetate propionate, cellulose butyrate and/or cellulose acetate butyrate, preferably cellulose acetate butyrate.
  • cellulose esters are particularly preferred because they have glass transition temperatures (Tg) and melting temperatures (Tm) which are particularly preferred for use in a heat-sensitive recording material.
  • nanoparticles of cellulose acetate butyrate are particularly preferred. These degrees of substitution (DS) are preferably 0.12 ⁇ 0.1 for acetyl groups and 2.62 ⁇ 0.13 for butyryl groups, the number-average molar mass (Mn) is preferably 30,000 g/mol and the Tm is approximately 141°C
  • the heat-sensitive recording material according to the invention is preferably characterized in that the at least one cellulose ester has a Tg of 45°C to 150°C and/or a Tm of 100°C to 185°C.
  • Tg and Tm are determined according to DIN 53765:1994-03 by means of differential scanning calorimetry (DDK or "differential scanning calorimetry” (DSC)).
  • the heat-sensitive recording material according to the invention is characterized in that the at least one cellulose ester is contained in the thermoresponsive layer in an amount of 35 to 70% by weight, based on the total weight of the thermoresponsive layer.
  • thermosensitive recording material is preferably characterized in that the thermoresponsive layer further comprises polyvinyl alcohol (PVA).
  • PVA polyvinyl alcohol
  • the polyvinyl alcohol is preferably contained in the thermoresponsive layer in an amount of 5 to 50% by weight based on the total weight of the thermoresponsive layer.
  • Polyvinyl alcohol reduces sample viscosity and results in a more homogeneous coating.
  • polyvinyl alcohol it is also preferred that a small amount, preferably 0.01 to 1% by weight, particularly preferably 0.05 to 0.5% by weight and very particularly preferably about 0 1% by weight of polyvinyl alcohol is added. This has the advantage that the polyvinyl alcohol can already attach to the nanoparticles of cellulose esters as a protective colloid during the precipitation process.
  • thermoresponsive layer also comprises at least one kaolin, alkali metal and/or alkaline earth metal salt.
  • the alkali metal and/or alkaline earth metal salt preferably comprises NaCl, CaCO 3 and/or CaCl 2 .
  • the at least one kaolin, alkali metal and/or alkaline earth metal salt is preferably contained in the thermoresponsive layer in an amount of 0.05 to 10% by weight, based on the total weight of the thermoresponsive layer.
  • the addition of salt is advantageous because the salt can compensate for the surface charges.
  • thermosensitive recording material is preferably characterized in that the thermoresponsive layer further comprises at least one high-molecular polyelectrolyte.
  • the at least one high molecular weight polyelectrolyte preferably comprises a poly(vinylamine-vinylformamide) copolymer, such as is available, for example, under the trade names Lupamin 9010 or Lupamin 4500 from BASF, and/or a cationic polyacrylamide, such as is available, for example, under the trade name Percol 47 from BASF is available.
  • a poly(vinylamine-vinylformamide) copolymer such as is available, for example, under the trade names Lupamin 9010 or Lupamin 4500 from BASF
  • a cationic polyacrylamide such as is available, for example, under the trade name Percol 47 from BASF is available.
  • the at least one high molecular weight polyelectrolyte is preferably present in the thermoresponsive layer in an amount of 5 to 35% by weight based on the total weight of the thermoresponsive layer.
  • thermoresponsive layer comprises at least one kaolin, alkali metal and/or alkaline earth metal salt as defined above and at least one high molecular weight polyelectrolyte as defined above.
  • the heat-sensitive recording material according to the invention is also preferably characterized in that the carrier substrate comprises paper, synthetic paper and/or a plastic film.
  • thermosensitive recording material is preferably characterized in that the thermoresponsive layer comprises at least one silicone oil defoamer, preferably in an amount of 0.05 to 5% by weight based on the total weight of the thermoresponsive layer.
  • thermoresponsive layer contains at least one binder, preferably an acrylate binder, which is available, for example, under the trade name Acronal S 360 D from BASF, preferably in an amount of 0.05 to 5% by weight, based on the total weight of the thermoresponsive layer.
  • binder preferably an acrylate binder, which is available, for example, under the trade name Acronal S 360 D from BASF, preferably in an amount of 0.05 to 5% by weight, based on the total weight of the thermoresponsive layer.
  • thermosensitive recording material of the present invention is preferably characterized in that the pH of the thermoresponsive layer is 6-9.
  • the pH is preferably adjusted by adding HCl or NaOH.
  • the heat-sensitive recording material according to the invention is preferably characterized in that the heat-sensitive color-forming layer contains customary additives, such as stabilizers, release agents, pigments and/or brighteners.
  • the heat-sensitive recording material according to the invention is preferably characterized in that the thermoresponsive layer comprises polyvinyl alcohol, preferably in an amount of 30 to 60 parts by weight, and 100 parts by weight of nanoparticles of cellulose acetate butyrate, these nanoparticles of cellulose acetate butyrate being obtainable by dissolving cellulose acetate butyrate in an organic solvent, preferably in tetrahydrofuran, and precipitating the nanoparticles of cellulose acetate butyrate by adding this solution of cellulose acetate butyrate to a non-solvent, preferably to a mixture of water and isopropanol, preferably in a mixing ratio of 1 to 4, most preferably 1 .2 to 2.8, the non-solvent preferably additionally containing polyvinyl alcohol, preferably in an amount of 0.01 to 1% by weight, particularly preferably about 0.1% by weight, based on the total amount of the non-solvent , includes.
  • the non-solvent preferably additionally containing polyvinyl
  • this heat-sensitive recording material further contains 2 to 10 parts by weight of a binder, 10 to 20 parts by weight of a viscosity regulator and 1 to 5 parts by weight of NaOH.
  • the coating weight of the (dry) heat-sensitive layer is preferably about 1 to about 10 g/m 2 , preferably about 3 to about 6 g/m 2 .
  • the nanoparticles of at least one cellulose ester can be produced by known methods.
  • the method is preferably characterized in that the cellulose ester comprises cellulose acetate, cellulose acetate propionate and/or cellulose acetate butyrate, preferably cellulose acetate butyrate.
  • the method is further preferably characterized in that the non-solvent is water or a mixture of water and at least one organic solvent, preferably in a mixing ratio of 1 to 4, particularly preferably 1.2 to 2.8, the at least one organic solvent is preferably isopropanol thereof.
  • the method is also preferably characterized in that the non-solvent additionally contains polyvinyl alcohol, preferably in an amount of 0.01 to 1% by weight, preferably about 0.1% by weight, based on the total amount of the non-solvent includes.
  • the nanoparticles of at least one cellulose ester obtained in this way usually have an average particle diameter of about 160 to 200 nm with a standard deviation of about 40 nm (measured using DLS, as described above).
  • the heat-sensitive recording material of the present invention can be produced by the usual methods.
  • the heat-sensitive recording material according to the invention is preferably produced by a method in which an aqueous suspension containing the starting materials of the thermoresponsive layer and having a solids content of from about 15 to about 60% by weight is applied to at least one black or colored side of the carrier substrate, and the aqueous suspension is applied and dried by coating processes which produce a contour coating (curtain coater) or a leveling coating (blade coater, squeegee).
  • This method is particularly advantageous from an economic point of view.
  • the heat-sensitive recording material according to the invention by means of a process in which the aqueous application suspension is applied using the curtain coating method, preferably at an operating speed of the coater of at least about 400 m/min.
  • the so-called curtain coating process is known to those skilled in the art and is characterized by the following criteria: In the curtain coating process, a freely falling curtain of a coating dispersion is formed. The coating dispersion, in the form of a thin film (curtain), is "poured" onto a substrate by free fall to apply the coating dispersion to the substrate.
  • the DE 10196052 T1 discloses the use of the curtain coating process in the production of information recording materials, including heat-sensitive recording materials.
  • Adjusting the operating speed of the coater to at least about 400 m/min has both economic and technical advantages. More preferably, the line speed is at least about 750 m/min, more preferably at least about 1000 m/min, and most preferably at least about 1500 m/min. It was particularly surprising that even at the latter speed, the heat-sensitive recording material obtained is in no way impaired and that the operation is optimal even at this high speed.
  • the aqueous, deaerated application suspension has a viscosity of about 150 to about 800 mPas (Brookfield, 100 rpm, 20° C.). If the value falls below about 150 mPas or the value of about 800 mPas is exceeded, this leads to to poor runnability of the coating material on the coating unit.
  • the viscosity of the aqueous, deaerated application suspension is particularly preferably about 200 to about 500 mPas.
  • the surface tension of the aqueous application suspension can be increased to 25 to 60 mN/m, preferably to about 35 to about 50 mN/m (measured according to the static ring method according to Du Noüy, DIN 53914, 1997-07), to be set.
  • the dried thermoresponsive layer is subjected to a smoothing operation. It is advantageous here to adjust the Bekk smoothness, measured according to DIN 53107 (2000), to about 100 to about 1200 seconds, preferably to about 300 to about 700 seconds. Bekk smoothness of 100 to 300 seconds are measured according to method A of DIN 53107 (2000) and Bekk smoothness of more than 300 according to method B of DIN 53107 (2000).
  • the present invention also relates to a heat-sensitive recording material obtainable by the above process.
  • figure 1 shows optical micrographs of a printed heat-sensitive recording material according to the invention.
  • figure 2 shows an illustration of the opacities. These are the gray values of a horizontal line. The laser power was 70%.
  • the gray value is a value between 0 and 255, where 255 represents an all-black pixel and 0 represents an all-white pixel.
  • An aqueous application suspension was prepared by mixing 100 parts of cellulose acetate butyrate nanoparticles with an average particle diameter of about 170 nm ( ⁇ 40 nm) in the presence of 0.1% polyvinyl alcohol, THF as solvent and a water/isopropanol mixture in a ratio of 1, 2 to 2.8 precipitated as non-solvent as described above, mixed with 40 parts polyvinyl alcohol, 5 parts Styronal D 517 as binder, 15 parts Sterocoll as viscosity regulator and 3 parts 1M NaOH.
  • a ratio of 11.75% by weight solids/liquid was chosen for the coating formulation. This value was chosen because the particles are in the form of ⁇ 15% by weight suspension after manufacture.
  • the solids content of the additives and coatings were determined using a dry balance.
  • the polyvinyl alcohol used is 84% saponified polyvinyl acetate (Mn 100,000 g/mol).
  • the sample vials were filled with 100 mg nanoparticles of cellulose acetate butyrate, the respective additives were added and the solids content (FS) was adjusted to 11.75% by weight with distilled water.
  • the formulation is then homogenized using a vortex shaker and an ultrasonic bath.
  • the coating was applied using an automatic film applicator from BYK Additives & Instruments to a Hostaphan film type RNK 50.0 2600 that had been precoated for line application.
  • the feed rate selected was 100 mm min -1 and the doctor blade gap 90 ⁇ m.
  • Heat-sensitive recording materials were prepared with the coating amount of the thermoresponsive layer being 2.5, 4 and 6 g/m 2 .
  • the coated substrates were cut in half with scissors. Half of a substrate was heated in a drying cabinet at 70 °C for 30 min to simulate simple drying conditions. Both samples were then "printed" with a 30-watt CO 2 laser (parameters in Table 1).
  • a light microscope in transmitted light mode was used to analyze the prints.
  • the paper coatings of formulation 1 showed promising results, which are shown in figure 1 are shown.
  • the patterns are macroscopically very homogeneous. With a laser power of 70%, sharp line profiles could already be seen. Increasing the laser power to 80% reduces the distance between the individual lines.
  • figure 2 serves to illustrate the opacities. These are the gray values of a horizontal line. The relative opacity of the PVA coatings reached a maximum of 95%. The thermal treatment showed no negative influence.

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  • Physics & Mathematics (AREA)
  • Optics & Photonics (AREA)
  • Heat Sensitive Colour Forming Recording (AREA)
  • Chemical & Material Sciences (AREA)
  • Inorganic Chemistry (AREA)
  • Thermal Transfer Or Thermal Recording In General (AREA)
  • Paper (AREA)

Claims (11)

  1. Matériau de revêtement thermosensible comprenant un substrat porteur noir ou coloré sur au moins un côté et une couche thermoréactive sur l'au moins un côté noir ou coloré du substrat porteur, dans lequel la couche thermoréactive comporte des nanoparticules au moins d'un ester de cellulose.
  2. Matériau de revêtement thermosensible selon la revendication 1, caractérisé en ce que les nanoparticules d'au moins un ester de cellulose présentent une grandeur de particules moyenne en nombre de 50 à 400, mesurée au moyen de la diffusion de lumière dynamique (DLS).
  3. Matériau de revêtement thermosensible selon l'une quelconque des revendications précédentes, caractérisé en ce que la couche thermoréactive présente une transparence, mesurée selon DIN 53147:1993-01, de moins de 35 %.
  4. Matériau de revêtement thermosensible selon l'une quelconque des revendications précédentes, caractérisé en ce que l'au moins un ester de cellulose comporte de l'acétate de cellulose, de l'acétopropionate de cellulose, du butyrate de cellulose et/ou du butyrate d'acétate de cellulose, de préférence du butyrate d'acétate de cellulose.
  5. Matériau de revêtement thermosensible selon l'une quelconque des revendications précédentes, caractérisé en ce que l'au moins un ester de cellulose présente une température de transition Tg de 45 °C à 150 °C et/ou une température de fusion Tm de 100 °C à 185 °C, respectivement déterminée selon DIN 53765:1994-03.
  6. Matériau de revêtement thermosensible selon l'une quelconque des revendications précédentes, caractérisé en ce que l'au moins un ester de cellulose est contenu dans la couche thermoréactive dans une quantité de 35 à 70 % en poids, par rapport au poids total de la couche thermoréactive.
  7. Matériau de revêtement thermosensible selon l'une quelconque des revendications précédentes, caractérisé en ce que la couche thermoréactive comporte en outre de l'alcool de polyvinyle, de préférence dans une quantité de 5 à 50 % en poids, par rapport au poids total de la couche thermoréactive.
  8. Matériau de revêtement thermosensible selon l'une quelconque des revendications précédentes, caractérisé en ce que la couche thermoréactive comporte en outre au moins un kaolin, un sel alcalin et/ou alcalino-terreux, en particulier NaCl, CaCO3 et/ou CaCl2, de préférence dans une quantité de 0,05 à 10 % en poids, par rapport au poids total de la couche thermoréactive.
  9. Matériau de revêtement thermosensible selon l'une quelconque des revendications précédentes, caractérisé en ce que la couche thermoréactive comporte en outre au moins un polyélectrolyte de poids moléculaire élevé, en particulier un copolymère de poly(vinylamine-vinylformamide), de préférence dans une quantité de 5 à 35 % en poids, par rapport au poids total de la couche thermoréactive.
  10. Matériau de revêtement thermosensible selon l'une quelconque des revendications précédentes, caractérisé en ce que le substrat porteur comporte du papier, du papier synthétique et/ou un film de matière plastique.
  11. Procédé de fabrication d'un matériau de revêtement thermosensible selon l'une quelconque des revendications précédentes, caractérisé en ce que sur l'au moins un côté noir ou coloré du substrat porteur, une suspension aqueuse contenant les matériaux de base de la couche thermoréactive qui présente une teneur en matières solides de 15 à 65 % en poids, et dans lequel la suspension aqueuse est appliquée et séchée après des procédés de revêtement qui génèrent un revêtement de contour, au moyen d'une encolleuse à rideau, ou un revêtement de nivellement, au moyen d'une encolleuse à lame, ou au moyen de racles.
EP19722558.4A 2018-05-14 2019-05-02 Revêtements en papier thermoréactifs à base de dérivés de cellulose Active EP3765303B1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE102018111495.8A DE102018111495B4 (de) 2018-05-14 2018-05-14 Thermoresponsive Papierbeschichtungen auf Basis von Cellulosederivaten
PCT/EP2019/061187 WO2019219391A1 (fr) 2018-05-14 2019-05-02 Revêtements en papier thermoréactifs à base de dérivés de cellulose

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EP3765303A1 EP3765303A1 (fr) 2021-01-20
EP3765303B1 true EP3765303B1 (fr) 2023-06-21

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US (1) US11975553B2 (fr)
EP (1) EP3765303B1 (fr)
CN (1) CN112004687B (fr)
DE (1) DE102018111495B4 (fr)
ES (1) ES2954503T3 (fr)
FI (1) FI3765303T3 (fr)
WO (1) WO2019219391A1 (fr)

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DE102021115909A1 (de) * 2021-06-18 2022-12-22 Koehler Innovation & Technology Gmbh Wärmeempfindliche Aufzeichnungsmaterialien
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DE102018111495A1 (de) 2019-11-14
ES2954503T3 (es) 2023-11-22
DE102018111495B4 (de) 2020-04-09
FI3765303T3 (fi) 2023-09-12
US11975553B2 (en) 2024-05-07
CN112004687B (zh) 2023-04-28
US20210213769A1 (en) 2021-07-15
CN112004687A (zh) 2020-11-27
EP3765303A1 (fr) 2021-01-20

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