EP3957489A1 - Matière d'enregistrement thermosensible sans générateur - Google Patents

Matière d'enregistrement thermosensible sans générateur Download PDF

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Publication number
EP3957489A1
EP3957489A1 EP20191808.3A EP20191808A EP3957489A1 EP 3957489 A1 EP3957489 A1 EP 3957489A1 EP 20191808 A EP20191808 A EP 20191808A EP 3957489 A1 EP3957489 A1 EP 3957489A1
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EP
European Patent Office
Prior art keywords
heat
recording material
sensitive recording
layer
range
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.)
Granted
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EP20191808.3A
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German (de)
English (en)
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EP3957489B1 (fr
Inventor
Claas Boxhammer
Ilyas Kabul
Helga FRAHLING
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
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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 EP20191808.3A priority Critical patent/EP3957489B1/fr
Priority to FIEP20191808.3T priority patent/FI3957489T3/fi
Priority to ES20191808T priority patent/ES2937111T3/es
Priority to EP22204860.5A priority patent/EP4163119A1/fr
Priority to PL20191808.3T priority patent/PL3957489T3/pl
Priority to PT201918083T priority patent/PT3957489T/pt
Priority to CA3128553A priority patent/CA3128553A1/fr
Priority to US17/405,159 priority patent/US20220055389A1/en
Priority to AU2021218068A priority patent/AU2021218068A1/en
Publication of EP3957489A1 publication Critical patent/EP3957489A1/fr
Publication of EP3957489B1 publication Critical patent/EP3957489B1/fr
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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
    • B41M5/363—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 low molecular weight organic compound such as a fatty acid, e.g. for reversible recording
    • 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
    • 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

Definitions

  • the present invention relates to a heat-sensitive recording material comprising or consisting of a) a carrier substrate (preferably paper substrate) and b) a melt layer arranged on one side of the carrier substrate or paper substrate, the melt layer i) an amide wax having a melting point in the range of 60 ° C to 180 ° C, ii) an inorganic pigment and iii) comprises or consists of a polymeric binder.
  • the present invention also relates to a coating composition for producing a corresponding fused layer, a method for producing a heat-sensitive recording material and the use of a heat-sensitive recording material.
  • Heat-sensitive recording materials have been known for many years and are very popular. This popularity is due, among other things, to the fact that their use is associated with the advantage that the typeface is formed solely by the irradiation of heat, and printers without toner and ink cartridges can therefore be used. It is therefore no longer necessary to purchase, store, change or refill toner or color cartridges. As a result, this innovative technology has established itself across the board, especially in public transport and retail.
  • WO 2012/145456 A1 describes a heat-sensitive recording material that does not require (color) developers or color acceptors.
  • Polymer particles having a core-shell structure are arranged in a layer arranged on a substrate, whereby this layer is opaque. Upon exposure to heat, the polymer particles melt and the core-shell structure collapses, revealing the previously opaque layer and revealing the underlying colored substrate.
  • the primary object of the present invention was therefore to provide a heat-sensitive recording material that can be produced without (color) developer and at the same time has a high degree of whiteness according to ISO 2470-1:2016-09 (also referred to as brightness) having.
  • the recording materials described in the prior art or commercially available have a low contrast between the printed and non-printed image. This is because the background, i.e. the non-printed area of the paper, has a low degree of whiteness.
  • the contrast of the image is significantly deteriorated during storage at high temperatures, resulting in a deterioration in readability. For example, when storing heat-sensitive recording materials in a car parked in the sun during the summer months, the interior of the car can heat up to temperatures of up to approx. 65°C. This can lead to heat-sensitive recording materials (e.g. a parking ticket) no longer being readable or only difficult to read.
  • a further object of the present invention was therefore to provide a heat-sensitive recording material that has an improved contrast between the non-printed and printed areas, in particular after storage of the recording material at high temperatures (such as can occur in a car in summer, for example). ).
  • the aim is therefore to provide a recording material which has better readability of the printed image.
  • the recording materials described in the prior art also have the disadvantage that microplastics or nanoplastics are used in the layers. Pollution of the environment by micro- or nanoparticles poses a problem for ecosystems and the latest research results suggest that such particles can pose risks for smaller organisms as well as for humans.
  • a further object of the present invention was therefore to provide a heat-sensitive recording material which can be produced without microplastics or nanoplastics and as a result has excellent environmental compatibility combined with excellent printability.
  • heat-sensitive recording materials according to the invention have a high degree of whiteness (determined according to ISO 2470-1:2016-09).
  • the amide wax is particularly compatible with inorganic pigments due to the hydrophobic hydrocarbon residues and the hydrophilic amide group.
  • Our own investigations have shown that, surprisingly, the amide waxes are not (or not significantly) absorbed by the inorganic pigments during the printing process, but remain in the melt layer or are partially absorbed by the adjacent layers.
  • the amide waxes together with the inorganic pigments form a nearly transparent layer through which the underlying support substrate or other layers can be seen.
  • the amide waxes form a very opaque layer with the inorganic pigments, which covers the colored substrate to a high degree. A high contrast is obtained as a result.
  • the substrate or the colored intermediate layer (4) is black or has a dark shade such as blue or red.
  • Possibilities of coloring the carrier substrate or of (conventionally) printing it, for example, with a colored intermediate layer, for example a printing ink, are known to the person skilled in the art.
  • the carrier substrate can be colored with carbon black (or other dyes). The use of carbon black has the advantage that it has very good temperature resistance and light stability.
  • inorganic pigments in the intermediate layer serves only to be able to adjust the color of the intermediate layer as best as possible.
  • the interlayer does not contain any inorganic pigments. This does not affect the technical effect of the enamel layer.
  • a colored carrier substrate or a colored intermediate layer is not absolutely necessary, although this is preferred.
  • a heat-sensitive recording material can already be obtained if a corresponding melting layer is printed on commercially available white paper (ie not colored) or a transparent film is applied as a carrier substrate. After printing by the selective action of heat, a printed image can also be recognized without a colored carrier substrate or a colored intermediate layer.
  • a possible area of use for this embodiment is security paper, in which the printed image is initially barely visible and only becomes visible when the paper is irradiated with light of a specific wavelength (eg UV light).
  • a material that absorbs (invisible) ultraviolet and blue light and emits visible light with longer wavelengths can be used as the carrier substrate or intermediate layer (4), while the melting layer has no fluorescence.
  • the printed image is initially not or hardly visible to the human eye and becomes visible after exposure to light of a specific wavelength, which excites the substrate to fluoresce.
  • the carrier substrate is transparent, a colored layer can also be applied to the back of the carrier substrate, or a contrast can be obtained if the printed recording material is placed on a colored surface.
  • a heat-sensitive recording material in which the carrier substrate has a coloring or in which a colored layer is arranged between the carrier substrate and the melting layer. It is particularly preferred here if the paper substrate or the color layer arranged between the paper substrate and melt layer has an optical density (blackening) of at least 0.50, preferably at least 1.0, more preferably at least 1.20.
  • the term “essentially no microplastics or nanoplastics” means that the melting layer or the heat-sensitive recording material contains less than 0.5% by weight, preferably less than 0.1% by weight, microplastics or nanoplastics has, based on the total weight of the melting layer or the heat-sensitive recording material. No microplastic or nanoplastic is particularly preferably added, so that no microplastic or nanoplastic is present. However, small amounts of microplastics or nanoplastics cannot be ruled out, since they may be contained in some starting materials as impurities, for example in one embodiment in which paper is used as the carrier substrate that has a proportion of recycled fibers.
  • small plastic particles for example made of PET (polyethylene terephthalate), PP (polypropylene), PE (polyethylene) or other plastics, which are smaller than 5 mm, are referred to as microplastics or nanoplastics.
  • Nanoplastic refers to a subgroup of microplastic and differs only in particle size, with nanoplastic having a particle size of less than 1 ⁇ m, while microplastic has a particle size of greater than or equal to 1 ⁇ m and less than 5 mm.
  • the term "essentially no (organic) (color) developers or leuco compounds” means that the melting layer or the heat-sensitive recording material contains less than 0.5% by weight, preferably less than 0.1% by weight. -%, more preferably less than 0.02% by weight of (color) developer and leuco compounds, based on the total weight of the melting layer or the heat-sensitive recording material.
  • no (color) developers and leuco compounds are added to the melting layer, so that no (color) developers and leuco compounds are present.
  • small amounts of (color) developer and leuco compounds cannot be ruled out, since they may be present as impurities in some starting materials.
  • heat-sensitive recording materials according to the invention also have the advantage that they have a high resistance to some chemicals.
  • Our own investigations have shown that the melted layer retains a high level of whiteness in the tape test and the melted layer does not gray, while recording materials from the prior art show graying of the respective recording layer.
  • part of a sample is covered with commercially available adhesive tape and left for 24 let absorb. The sample is then examined. It has been shown that printed parts of the recording materials remain the same black while in comparison samples the unprinted part shows a greyish discoloration of the melting layer after storage at ambient temperature. A recognizable discoloration occurs after 96 hours and is clearly pronounced after 21 days.
  • this effect is even more pronounced in the unprinted part of the comparison samples when the sample is stored or stored for a longer period of time, for example after a period of several days to a few weeks, which is therefore advantageous for longer storage or storage, eg of receipts, proves to be very disadvantageous.
  • the present invention thus provides a significant improvement over the prior art.
  • the melt layer in the unprinted state has an opacity according to ISO 2471 of at least 50%, preferably at least 60%, particularly preferably at least 70%.
  • the melt layers in recording materials according to the invention usually have an opacity of more than 75%, more than 80% or even more than 85%.
  • the opacity of the enamel layer is determined according to ISO 2471, with the isolated layer being measured.
  • a melt layer with the same composition and thickness can be applied to a completely transparent substrate (e.g. quartz glass) and measured.
  • pigments commonly used in papermaking can be used as the inorganic pigment, for example pigment selected from the group consisting of calcined kaolin, natural kaolin, kaolinite, magnesium silicate hydrate, silicon dioxide, bentonite, calcium carbonate, calcium silicate hydrate, calcium aluminate sulfate, aluminum hydroxide, aluminum oxide and boehmite.
  • the enamel layer does not contain any natural kaolin.
  • the melting layer and preferably the entire heat-sensitive recording material does not contain any organic pigments. It is particularly preferred here if the melting layer and preferably the entire heat-sensitive recording material does not contain any hollow sphere pigments (eg core-shell pigments).
  • melt layer does not comprise aluminum trihydrate (ATH), calcium carbonate, polyethylene, polystyrene and/or silicon dioxide.
  • the entire heat-sensitive recording material does not comprise aluminum trihydrate (ATH), polyethylene, polystyrene and/or silicon dioxide.
  • the melting layer preferably the entire recording material
  • the use of aluminum hydroxide and/or aluminum oxide is less preferred, particularly in the case of recording materials that can come into direct contact with the consumer or with food, since the market demands materials that do not contain aluminum compounds due to the controversial effect of aluminum compounds on the human body.
  • the inorganic pigment has a (preferably average) aspect ratio of from 3 to 100, preferably from 5 to 95, particularly preferably from 10 to 90.
  • the (preferably average) aspect ratio of the inorganic pigment is greater than 15.
  • the aspect ratio also called “aspect ratio” or “shape factor” 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 15 means that the diameter of the platelet is 15 times greater than the thickness of the platelet.
  • the form of the inorganic pigments is preferably plate-like or rod-like, with rod-like pigments being particularly preferred.
  • platelet-shaped or rod-shaped pigments leads to particularly advantageous enamel layers. Without wishing to be bound to a specific theory here, it is assumed that corresponding pigments form particularly ordered layers which have a high degree of opacity. Platelet-shaped pigments can overlap in such a way that they form a kind of "scale structure" that is particularly dense. Rod-shaped pigments can also arrange themselves accordingly and form very dense layers. It is therefore surprising and was not foreseeable for the person skilled in the art that in a system according to the invention a transparency of the melt layer can be obtained when this is treated with heat. The person skilled in the art would not have expected that layers with flake or rod-shaped pigments, which form a very opaque layer, would become transparent through the action of heat.
  • the inorganic pigment has a particle diameter d 50 in the range from 0.8 to 2.0 ⁇ m, preferably in the range from 1.0 to 1.8 ⁇ m, more preferably in the range from 1.2 to 1.6 ⁇ m having.
  • the inorganic pigment has a particle diameter d 97 in the range from 2.0 to 15.0 ⁇ m, preferably from 6.0 to 10.0 ⁇ m, more preferably in the range from 7.0 to 9.0 ⁇ m having.
  • the measurement of the particle diameter can be determined by means of laser granulometry (for example with a Cilas 1064).
  • recording materials according to the invention with the abovementioned inorganic pigments have particularly good properties in terms of high opacity before printing and high transparency after printing. This would not be expected since the particles have a larger particle diameter compared to the wavelength of visible light (400 to 800 nm).
  • the calcium silicate has particularly good properties and leads to heat-sensitive recording materials with particularly good properties (higher White value of unprinted enamel layer with high opacity and very low opacity after printing).
  • the use of calcium silicate, preferably as calcium silicate hydrate, is therefore particularly preferred according to the invention.
  • the inorganic pigment has a pH value determined according to DIN EN ISO 787-9:2019-06 of greater than 7, preferably in the range from greater than or equal to 9 to less than or equal to 14, particularly preferably in the range from greater than or equal to 10, 5 to less than or equal to 12.5.
  • a pH value determined according to DIN EN ISO 787-9:2019-06 of greater than 7, preferably in the range from greater than or equal to 9 to less than or equal to 14, particularly preferably in the range from greater than or equal to 10, 5 to less than or equal to 12.5.
  • biocides are any substance or mixtures as defined in Article 2 of Regulation (EU) No. 528/2012 (Biocide Regulation) of the European Union.
  • a heat-sensitive recording material is particularly preferred according to the invention, in which the melt layer and preferably the entire recording material comprises essentially none of the following compound selected from the group consisting of diphenyl sulfone (DPS), diphenoxyethane (DPE), ethylene glycol m-tolyl ether (EGTE) and beta -Naphthyl benzyl ether (BON).
  • DPS diphenyl sulfone
  • DPE diphenoxyethane
  • EGTE ethylene glycol m-tolyl ether
  • BON beta -Naphthyl benzyl ether
  • the term "essentially none” means in connection with the above-mentioned compounds that the melting layer or the heat-sensitive recording material contains less than 0.5% by weight, preferably less than 0.1% by weight. -% of the above sensitizers, based on the total weight of the melting layer or the heat-sensitive recording material. More preferably none of the above sensitizers are added such that none of the above sensitizers are present.
  • the amide wax used in recording materials according to the invention can be selected, for example, from the group consisting of lauramide ( CAS No. 1120-16-7 ), palmitamide ( CAS No. 629-54-9 ), stearamide ( CAS No. 124-26-5 ), 12-hydroxystearamide ( CAS No. 7059-49-6 ), oleamide ( CAS No. 301-02-0 ), erucamide ( CAS No. 112-84-5 ), N-stearyl stearamide ( CAS No. 13276-08-9 ), N-stearyloleamide ( CAS No. 6592-63-2 ), N-oleyl stearamide ( CAS No.
  • N-stearyl erucamide (10094-45-8), N-methylolstearamide (CAS No. 3370-35-2 ), ethylene bis oleamide ( CAS No. 110-31-6 ), hexamethylenebis oleamide ( CAS No. 6283-37-0 ), N,N'-dioleyl adipamide ( CAS No. 85888-37-5 ), methylenebis stearamide ( CAS No. 109-23-9 ), ethylene bis capramide ( CAS No. 51139-08-3 ), ethylenebis lauramide ( CAS No. 7003-56-7 ), ethylene bis stearamide ( CAS No. 110-30-5 ), ethylenebis 12-hydroxystearamide ( CAS No.
  • ethylene-bis-behenamide CAS No. 7445-68-3
  • hexamethylene-bis-stearamide CAS No. 4112-25-8
  • hexamethylene bis behenamide CAS No. 96548-58-2
  • hexamehylenebis 12-hydroxystearamide CAS No. 55349-01-4
  • N,N'-distearyl adipamide CAS No. 25151-31-9
  • Lauramid CAS No. 1120-16-7
  • palmitamide CAS No. 629-54-9
  • stearamide CAS No. 124-26-5
  • 12-hydroxystearamide CAS No.
  • amide wax is stearamide (octadecanamide, CAS No. 124-26-5 ) or N-methylolstearamide (N-(hydroxymethyl)octadecanamide, CAS No. 3370-35-2 ) is.
  • stearamide leads to the best results and is particularly preferred according to the invention.
  • the amide wax has a melting point that is tailored to the area of use having.
  • Our own investigations have surprisingly shown that heat-sensitive recording materials are particularly preferred when the amide wax has a melting point in the range from 80 to 120.degree. These heat-sensitive recording materials show the best properties in classic printing in a thermal printer.
  • Heat-sensitive recording materials in which the amide wax is a fatty acid monoamide are preferred according to the invention. It is particularly preferred here if the amide wax is a monoamide of a saturated fatty acid whose fatty acid residue has a total number of carbon atoms in the range from ⁇ 14 to ⁇ 20, preferably in the range from ⁇ 16 to ⁇ 18.
  • the amide wax is preferably a synthetically produced wax, which is preferably produced by reacting technical fatty acids, fatty acid esters and/or triacylglycerols with ammonia, monovalent amines, polyvalent amines and/or amino alcohols.
  • a heat-sensitive recording material is preferred according to the invention, the quantitative ratio between i) the one or more amide waxes (total) and ii) the one or more inorganic pigments (total) having a value in the range from 2:8 to 9:1 , preferably from 2.5:7.5 to 7.5:2.5, more preferably from 0.3:0.7 to 0.7:0.3, and most preferably 6.5 ⁇ 0.3:3 .5 ⁇ 0.3.
  • a heat-sensitive recording material is preferred according to the invention, the amide wax being present in a total amount in the range from ⁇ 40 to ⁇ 78 percent by mass, preferably from ⁇ 44 to ⁇ 73 percent by mass, more preferably in the range from 50 to 67 percent by mass, based on the dry mass of the melt layer . If the proportion of amide wax is too high, there is a possibility that parts of the wax will be deposited on the print head, rendering the heat-sensitive recording material unusable. If the amount of the amide wax is too small, there is a possibility that sufficient transparency of the melt layer cannot be obtained during printing.
  • a heat-sensitive recording material is preferred according to the invention, the binder being present in a total amount in the range from ⁇ 1 to ⁇ 30 percent by mass, preferably from ⁇ 2 to ⁇ 20 percent by mass, more preferably from ⁇ 4 to ⁇ 16 Percentage by mass, based on the dry mass of the enamel layer. Excessive amounts of binder can lead to insufficient opacity of the recording material before printing. With no or too small amounts (often less than 1% by mass) there is a possibility that the adhesion of the melt layer to the substrate will be impaired.
  • a heat-sensitive recording material is preferred according to the invention, the inorganic pigment being present in a total amount in the range from ⁇ 18 to ⁇ 50 percent by mass, preferably from ⁇ 22 to ⁇ 45 percent by mass, particularly preferably in the range from ⁇ 25 to ⁇ 39 percent by mass, based on the Dry mass of the enamel layer.
  • Dry mass in the context of the present invention is preferably understood to mean the water- and moisture-free mass of a sample (here: the melt layer) measured (under laboratory conditions at 23° C. and 50% RH).
  • the dry mass is preferably determined—as is customary in the field—on the sample to be examined (here: the heat-sensitive recording layer according to the invention), which had been dried at 105° C. to constant weight before the determination.
  • the dry mass of a sample (in particular a sample of the enamel layer) can be determined for the purposes of the present invention by holding a sample of defined mass before drying (eg 1.5 g of the sample before drying) for five hours at 105° C. in a drying oven dries and then, after cooling to room temperature (in case of doubt, to 23 °C), check the constancy of weight in a manner known per se (sample, e.g. by heating it up again and determining the mass again), whereby, of course, reabsorption of water during the cooling process must be avoided (desiccator).
  • a sample of defined mass before drying eg 1.5 g of the sample before drying
  • room temperature in case of doubt, to 23 °C
  • the dry mass of a sample in particular a sample of the enamel layer
  • a moisture determination device for example a halogen moisture determination device known per se, under the conditions specified above (105 °C, heating up to to constant weight) are determined.
  • a heat-sensitive recording material is preferred according to the invention, the area-related dry mass of the melt layer being in the range from ⁇ 2 g/m 2 to ⁇ 15 g/m 2 , preferably in the range from ⁇ 3.0 g/m 2 to ⁇ 12 g/m 2 , more preferably in the range from ⁇ 4.0 g/m 2 to ⁇ 10 g/m 2 .
  • a heat-sensitive recording material is preferred according to the invention, the carrier substrate being a paper, synthetic paper or a plastic film.
  • Coating base paper is particularly preferred as the carrier substrate, since it has good recyclability and good environmental compatibility.
  • Coating base paper is understood to be paper that has been treated in a size press or in a coating device. Films made of polypropylene or other polyolefins are preferred as plastic films.
  • the carrier substrate is a paper substrate. It is preferred here if the paper substrate contains a proportion of ⁇ 80 percent by mass of recycled fibers, based on the total mass of the air-dried paper substrate.
  • a heat-sensitive recording material is preferred according to the invention, the paper substrate containing ⁇ 25 percent by mass of fresh fibers, based on the total mass of the air-dried paper substrate.
  • the mass of an "air-dry" paper substrate given above is determined under standard ambient conditions (23°C, 50% RH, 1013 hPa). A water content of the paper substrate of 10 percent by mass is assumed for an air-dried paper substrate--as is customary in the technical field.
  • a high proportion of more than 80 percent by mass of fresh fibers can also be used, or only fresh fibers are used. This has the advantage that the resulting material has fewer impurities and substrates with low grammages (eg less than or equal to 42 or 30 g/m 2 ) can also be used.
  • a heat-sensitive recording material is preferred according to the invention, wherein the one or more polymeric binders are selected from the group consisting of starch and polyvinyl alcohol (PVA).
  • PVA polyvinyl alcohol
  • 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, measured according to DIN 53015 on an aqueous solution with 4% by mass at 20 °C mPas, particularly preferably more than 15 mPas.
  • the wording “substantially no organic or inorganic pigment” means that the further layer (6) has less than 0.5% by weight, preferably less than 0.1% by weight, of organic and inorganic pigments , based on the total weight of the further layer (6). No pigments are particularly preferably added to the further layer (6), so that no pigments are present.
  • a heat-sensitive recording material is preferred according to the invention, with an additional protective layer (5) being arranged on the melting layer.
  • the melting layer is completely or partially covered with a protective layer (5).
  • the arrangement of a protective layer (5) covering the melted layer also shields the melted layer from the outside or from the carrier substrate of the next layer within a roll, so that protection from external influences takes place.
  • Such a protective layer (5) often has the additional positive effect of improving the printability of the heat-sensitive recording material according to the invention, in particular in the indigo to improve offset and flexographic printing.
  • the protective layer (5) of the heat-sensitive recording material according to the invention preferably contains one or more crosslinked or uncrosslinked binders selected from the group consisting of polyvinyl alcohols modified with carboxyl groups, polyvinyl alcohols modified with silanol groups, diacetone-modified polyvinyl alcohols, partially and fully hydrolyzed polyvinyl alcohols, ethylene-acrylic acid copolymer waxes and film-forming acrylic copolymers.
  • the coating composition for forming the protective layer (5) of the heat-sensitive recording material according to the invention preferably contains one or more crosslinking agents for the binder or binders in addition to one or more binders.
  • the crosslinking agent is then preferably selected from the group consisting of boric acid, polyamines, epoxy resins, dialdehydes, formaldehyde oligomers, epichlorohydrin resins, adipic acid dihydrazide, melamine formaldehyde, urea, methylol urea, ammonium zirconium carbonate, polyamide epichlorohydrin resins and dihydroxybis(ammonium lactato)titanium(IV) Tyzor® LA ( CAS no. 65104-06-5 ).
  • a heat-sensitive recording material according to the invention whose protective layer (5) is formed from such a coating composition containing one or more binders and one or more crosslinking agents for the binder or binders, contains in the protective layer (5) one or more crosslinked by reaction with one or more crosslinking agents Binders, wherein the crosslinking agent or agents are selected from the group consisting of boric acid, polyamines, epoxy resins, dialdehydes, formaldehyde oligomers, epichlorohydrin resins, adipic acid dihydrazide, melamine formaldehyde, urea, methylolurea, ammonium zirconium carbonate, polyamideepichlorohydrin resins and dihydroxybis(ammonium lactato)titanium(IV) Tyzor ® LA ( CAS no. 65104-06-5 ).
  • the crosslinking agent or agents are selected from the group consisting of boric acid, polyamines, epoxy resins, dialdehydes, formal
  • Crosslinked binder is understood to mean the reaction product formed by reacting a binder with one or more crosslinking agents.
  • the protective layer (5) that completely or partially covers the molten layer can be obtained from a coating composition comprising one or more polyvinyl alcohols and one or more crosslinking agents. It is preferred that the polyvinyl alcohol of the protective layer (5) is modified with carboxyl or especially silanol groups. Mixtures of different carboxyl- or silanol-modified polyvinyl alcohols can also be used with preference.
  • a protective layer (5) has a high affinity for the preferably UV-crosslinking printing ink used in the offset printing process. This provides crucial support in meeting the requirement for excellent printability within offset printing.
  • the crosslinking agent or agents for the protective layer (5) are preferably selected from the group consisting of boric acid, polyamines, epoxy resins, dialdehydes, formaldehyde oligomers, polyamine epichlorohydrin resin, adipic acid dihydrazide, melamine formaldehyde and dihydroxybis(ammonium lactato)titanium(IV) Tyzor® LA ( CAS no. 65104-06-5 ). Mixtures of different crosslinking agents are also possible.
  • the weight ratio of the modified polyvinyl alcohol to the crosslinking agent is preferably in a range from 20:1 to 5:1 and particularly preferably in a range from 12:1 to 7:1 preferred is a ratio of the modified polyvinyl alcohol to the crosslinking agent in the range of 100 parts by weight to 8 to 11 parts by weight.
  • the protective layer (5) according to this embodiment variant additionally contains an inorganic pigment.
  • the inorganic pigment is preferably selected from the group consisting of silicon dioxide, bentonite, aluminum hydroxide, calcium carbonate, kaolin and mixtures of the inorganic pigments mentioned.
  • silicon dioxide and aluminum hydroxide is less preferred in some embodiments.
  • the protective layer (5) has a mass per unit area in a range from 0.5 g/m 2 to 6 g/m 2 and is particularly preferred from 0.75 g/m 2 to 3.8 g/m 2 , more preferably in the range from 0.95 to 2.0 g/m 2 .
  • the protective layer (5) is preferably formed in one layer.
  • the coating composition for forming the protective layer (5) comprises a water-insoluble, self-crosslinking acrylic polymer as a binder, a crosslinking agent and a pigment component
  • the pigment component of the protective layer (5) consisting of one or more inorganic pigments and at least 80% by weight are formed from a highly purified alkaline processed bentonite
  • the binder of the protective layer (5) consists of one or more water-insoluble, self-crosslinking acrylic polymers and the binder/pigment ratio is in a range from 7:1 to 9:1.
  • a self-crosslinking acrylic polymer within the protective layer (5) according to the second variant described here is preferably selected from the group consisting of styrene-acrylic acid ester copolymers, acrylamide-containing copolymers of styrene and acrylic acid ester and copolymers based on acrylonitrile, methacrylamide and acrylic ester. The latter are preferred.
  • Alkaline bentonite, natural or precipitated calcium carbonate, kaolin, silicic acid or aluminum hydroxide (the last two pigments are less preferred) can be incorporated into the protective layer (5) as a pigment.
  • Preferred crosslinking agents are selected from the group consisting of cyclic urea, methylol urea, ammonium zirconium carbonate and polyamide epichlorohydrin resins.
  • the protective layer (5) itself can be applied using conventional coating units, for which a coating color can be used, among other things, preferably with a mass per unit area in the range from 0.5 to 4.5 g/m 2 , more preferably in the range from 0.75 up to 3 g/m 2 .
  • the protective layer (5) is printed on.
  • Such are particularly suitable for processing and with regard to their technological properties
  • Protective layer (5)s which can be cured by means of actinic radiation.
  • actinic radiation means UV or ionizing radiation such as electron beams.
  • the appearance of the protective layer (5) is decisively determined by the type of smoothing and the roll surfaces influencing the friction in the calender and calender and their materials.
  • a roughness (Parker Print Surf roughness) of the protective layer (5) of less than 1.5 ⁇ m (determined in accordance with ISO standard 8791, part 4) is considered preferable.
  • the use of calenders in which NipcoFlex TM or zone-controlled Nipco-P TM rolls are used has particularly proven itself in the context of the experimental work preceding this invention; however, the invention is not limited to this.
  • the melting layer can be arranged on both sides of the paper substrate. This makes it possible to produce recording materials that can be printed on both sides. If the paper substrate is colored, both melt layers can be applied directly to the paper substrate. Otherwise, a colored intermediate layer can be arranged between the paper substrate and each melting layer.
  • the heat-sensitive recording material according to the invention is equipped as a label with a (self-)adhesive layer on the back.
  • the usual structure then provides a carrier substrate, preferably a paper substrate, which has a front side and a back side opposite it.
  • the heat-sensitive recording material then has the (self-)adhesive layer on the back.
  • the enamel layer and optionally a protective layer (5) partially or completely covering the enamel layer can then be applied on the front side.
  • a colored layer can also be applied between the carrier substrate and the melting layer, for example if the carrier substrate itself is not colored.
  • the adhesive layer can be covered with a release material such as a release paper containing silicone, or the protective layer (5) formed on the outer melt layer of the recording material according to the invention is provided with an additional release layer (7), which is preferably applied using a so-called five-roller applicator .
  • the release layer has release agents, preferably based on silicone oil or silicones.
  • the release layer can be cured or crosslinked under the influence of high-energy radiation, for example UV or electron beams. If the release layer is to be cured by means of UV rays, the monomers or prepolymers used to produce this layer must contain additions of photoinitiators in a known manner. Electron beam curing made it possible to achieve a release layer that was particularly uniform over its cross section, that is to say a cured release layer.
  • a recording material according to the invention additionally comprising one or more processing aids in the melt layer, preferably selected from the group consisting of defoamers, dispersants and wetting agents, preferably in a total amount of ⁇ 5 percent by mass, particularly preferably in a total amount in the range of ⁇ 0.1 to ⁇ 3% by mass, and more preferably in the range of ⁇ 0.1 to ⁇ 2% by mass, based on the dry mass of the heat-sensitive recording layer.
  • processing aids in the melt layer preferably selected from the group consisting of defoamers, dispersants and wetting agents, preferably in a total amount of ⁇ 5 percent by mass, particularly preferably in a total amount in the range of ⁇ 0.1 to ⁇ 3% by mass, and more preferably in the range of ⁇ 0.1 to ⁇ 2% by mass, based on the dry mass of the heat-sensitive recording layer.
  • biocides are contained in the enamel layer, which is less preferred according to the invention.
  • the use of biocides can be
  • the one or more processing aids preferably serve to facilitate or enable the processing of a coating composition according to the invention for the production of a melted layer in the industrial manufacturing process, in particular in the industrial process of paper manufacture.
  • an above-mentioned heat-sensitive recording material according to the invention which additionally comprises one or more optical brighteners may be preferred.
  • the optical brighteners can be contained in the melting layer, in the carrier substrate or in the protective layer (5). If a heat-sensitive recording material according to the invention additionally comprises one or more optical brighteners, it is preferred if the heat-sensitive recording material according to the invention contains this one or more optical brighteners in a total amount of ⁇ 1 percent by mass, more preferably in a total amount of ⁇ 0.75 percent by mass , related to the dry mass of the respective layer.
  • the above-mentioned heat-sensitive recording material according to the invention particularly preferably contains no optical brighteners.
  • temperature indicators are suitable for monitoring and documenting the temperature of a product. This can provide evidence of whether products or devices have been heated above a certain temperature.
  • the temperature indicators are distinguished by the fact that they are irreversible and—in contrast to temperature indicators known in the prior art—a printed image can be displayed.
  • the printed image can be a warning (as text, code or pictogram) that indicates that the temperature has been exceeded.
  • the temperature indicators known in the prior art are characterized by discoloration, so that an area printed with the thermochromic is discolored.
  • the temperature indicator can be adjusted to a desired transition or triggering temperature.
  • temperature indicators with a transition temperature in the range from 60 to 180° C. can be produced.
  • a further aspect of the present invention relates to the use of the heat-sensitive recording material as a temperature indicator.
  • a further aspect of the present invention relates to a coating composition for producing a melt layer of a heat-sensitive recording material (preferably a recording material according to the invention) comprising the components i) to iii) as defined above.
  • a further aspect of the present invention relates to the use of a coating composition according to the invention as a printing ink. It has surprisingly turned out that coating compositions according to the invention can also be used as a printing ink. It is thus possible to print a print image (e.g. text or images). This printed image is preferably printed on a colored substrate and initially appears white after printing. If heat acts on the printed image, it becomes transparent and the printed image disappears or is no longer visible.
  • a print image e.g. text or images
  • the coating composition for producing a protective layer (5) can have the same configuration as described above for the heat-sensitive recording material.
  • Steps i are performed after step a and before step b.
  • the coating composition for producing a melt layer in step c is not applied to the carrier substrate but to the colored intermediate layer.
  • the colored intermediate layer can be applied completely or only partially to the carrier substrate.
  • a further aspect of the present invention relates to the use of a heat-sensitive recording material according to the invention as an admission ticket, receipt, self-adhesive label, ticket, TITO ticket (ticket-in, ticket-out), flight, train, ship or bus ticket, parking ticket, label , gambling receipt, sales receipt, bank statement, medical and/or technical chart paper, fax paper or security paper.
  • a heat-sensitive recording material as an admission ticket, receipt, self-adhesive label, ticket, TITO ticket (ticket-in, ticket-out), flight, train, ship or bus ticket, parking ticket, label , gambling receipt, sales receipt, bank statement, medical and/or technical chart paper, fax paper or security paper.
  • FIG 1 shows a heat-sensitive recording material (1) that comprises a carrier substrate 2) and a melting layer (3) arranged on one side of the carrier substrate.
  • the supporting substrate consists of a carbon black colored paper while the melt layer comprises i) stearamide as an amide wax, ii) calcium silicate hydrate as an inorganic pigment and iii) a PVA as a polymeric binder.
  • the carrier substrate can also be a foil, a transparent foil or white paper.
  • FIG. 1 shows a heat-sensitive recording material (1) comprising a supporting substrate 2), a colored intermediate layer (4) arranged on one side of the supporting substrate, and a melting layer (3) arranged on the colored intermediate layer (4).
  • the carrier substrate consists of paper.
  • a colored intermediate layer is arranged on the carrier substrate, the PVA as a binder, carbon black as a colorant and kaolin as an inorganic pigment.
  • the melt layer disposed on the colored intermediate layer comprises i) stearamide as an amide wax, ii) calcium silicate hydrate as an inorganic pigment, and iii) a PVA as a polymeric binder.
  • the carrier substrate can also be a film or a transparent film.
  • figure 3 shows a heat-sensitive recording material (1) according to figure 1 in which a protective layer (5) is arranged on the melting layer (3).
  • figure 4 shows a heat-sensitive recording material (1) according to figure 2 in which a protective layer (5) is arranged on the melting layer (3).
  • figure 5 shows a heat-sensitive recording material (1) according to figure 3 in which the colored intermediate layer (4) is not completely applied to the carrier substrate 2 and as a result a typeface (here text) is formed.
  • This is a print (8).
  • the melting layer 3 By heating the melting layer 3 to a specific temperature, it becomes transparent and the typeface becomes visible from the outside.
  • the melting layer can lie directly on the carrier substrate 2 (not shown here).
  • An adhesive layer (9, not shown here) can optionally be arranged on the rear side of the carrier substrate 2 .
  • the in figure 6 Imaged recording material to a temperature indicator, which - if an adhesive layer 9 is present - can be lived on surfaces.
  • figure 6 shows a heat-sensitive recording material (1) that comprises a carrier substrate 2) and a melting layer (3) arranged on one side of the carrier substrate.
  • the carrier substrate consists of a transparent film while the melt layer comprises i) stearamide as an amide wax, ii) calcium silicate hydrate as an inorganic pigment, and ii) a PVA as a polymeric binder.
  • a print 8 is arranged on the rear side of the carrier substrate.
  • the printout 8 (here text) is preferably printed mirror-inverted. After the melting layer 3 has been heated, it becomes transparent and the printed image can be seen from above because of the transparent film.
  • An adhesive layer (9, not shown here) can optionally be arranged on the print 8 .
  • the in figure 6 Imaged recording material to a temperature indicator, which - if an adhesive layer 9 is present - can be lived on surfaces.
  • figure 7 shows a heat-sensitive recording material (1) according to figure 2 in which an adhesive layer 9 is arranged on the back of the carrier material.
  • figure 8 shows a heat-sensitive recording material (1) according to figure 4 in which an adhesive layer 9 is arranged on the back of the carrier material and a release layer 7 is arranged on the protective layer 5 .
  • FIG 9 shows images of the in during the determination of the plasticizer resistance (tape test) of Example 17 ( Figure 9a ) and Comparative Example 7 ( Figure 9b ) and Comparative Example 8 ( Figure 9c ).
  • samples are printed, covered with a strip of transparent adhesive tape and left to stand for 24 hours at 50% RH and 23°C and for an additional 20 days at ambient conditions.
  • the recording material according to the invention Figure 9a
  • the glued-on strip of tape is barely visible.
  • the components of the adhesive tape plasticizers
  • FIG 10 shows images of in during the determination of the temperature resistance of Example 17 ( Figure 10a ) and Comparative Example 7 ( Figure 10b ) and Comparative Example 8 ( Figure 10c ).
  • samples are printed and stored at 60°C for 24 hours. It can be seen that the samples from Comparative Examples 7 ( Figure 10b ) and Comparative Example 8 ( Figure 10c ) are significantly darker than the sample according to the invention from Example 17 ( Figure 10a ).
  • FIG 11 shows images of in during the determination of the temperature resistance of Example 17 ( Figure 11a ) and Comparative Example 7 ( Figure 11b ) and Comparative Example 8 ( Figure 11c ).
  • samples are printed and stored at 90 °C for 21 hours. It can be seen that the samples from Comparative Examples 7 ( Figure 11b ) and Comparative Example 8 ( Figure 11c ) are significantly darker than the sample according to the invention from Example 17 ( Figure 11a ).
  • figure 12 shows the reproduction of the dynamic print density of the recording materials from Example 17 and Comparative Examples 7 and 8 as a diagram.
  • figure 13 shows the reproduction of the dynamic sensitivity of the recording materials from Example 17 and Comparative Examples 7 and 8 as a diagram.
  • FIG 14 shows a photograph of a recording material according to the invention that is irradiated with black light (UV light).
  • the recording material was produced by coating a conventionally available white writing paper with a melt layer described in Example 17. This was followed by a test print in a conventional thermal printer. The printed recording material obtained was then exposed to black light.
  • the writing paper used as the carrier substrate shows a high level of fluorescence, which is only visible in the printed areas. Without the effect of black light, the printed area is difficult or impossible to see.
  • Examples 1 to 3 and Comparative Examples 1 and 2 Production of a recording material and variation of the ratio between amide wax and inorganic pigment:
  • a paper web made from bleached and ground hardwood and softwood pulps with a mass per unit area of 42 g/m 2 is produced as the carrier substrate on a fourdrinier paper machine with the addition of customary additives in customary amounts and carbon black.
  • the paper substrate produced was jet black.
  • a coating composition for producing a molten layer with a mass per unit area of 5.0 g/m 2 is applied to the felt side of the paper web produced (paper substrate) by means of a doctor blade and dried conventionally after application.
  • the heat-sensitive recording materials according to Comparative Example 1 were not printable. From the data given in Table 4 above, it can be seen that the heat-sensitive recording materials of the present invention (Examples 1 to 3) have good dynamic sensitivity. Recording materials according to Comparative Example 2 also showed good dynamic sensitivity, but there were heavy deposits on the thermal print head, so that this recording material cannot be used.
  • the heat-sensitive recording materials according to Comparative Examples 3 and 5 were not printable. From the data presented in Tables 5 and 6 above, it can be seen that the heat-sensitive recording materials of the present invention (Examples 4 to 9) have good dynamic sensitivity. Best printing results could be obtained with a ratio between wax amide and inorganic pigment of 7:3 with a melt layer mass per unit area of 7 g/m 2 . Also in Comparative Examples 4 and 6, the deposits on the thermal print head were excessive, so that this recording material cannot be used. For example, in Example 9, an excellent contrast of 1.13 could be obtained.
  • Example 9 was repeated, but the proportion of binder was varied.
  • the pigment to amide wax ratio was kept constant at 3:7.
  • Example 10 4%
  • Example 11 8th%
  • Example 12 12%
  • Example 13 16%
  • Example 14 20%
  • Example 15 24%
  • Particularly good properties can be achieved with a binder content of between 4 and 16%. Below 4%, the whiteness of the fusible layer can be improved, but the adhesion of the fusible layer to the paper substrate deteriorates. With a binder content of more than 20%, the opacity of the enamel layer is reduced.
  • a paper web made from bleached and ground hardwood and softwood pulps with a mass per unit area of 42 g/m 2 is produced as the carrier substrate on a fourdrinier paper machine with the addition of customary additives in customary amounts and carbon black.
  • the paper substrate produced was jet black.
  • a coating composition with the composition given in Table 9 was prepared to produce a coating composition required for the production of the hot-melt layer.
  • Table 9 ⁇ /u> Composition of the dispersion Coating composition: component Otro amount [%] water - calcium silicate hydrate 28.0 stearamide 60.0 PVA 12.0 total 100.0
  • a coating composition for producing a molten layer with a mass per unit area of 7.0 g/m 2 is applied to the felt side of the paper web produced (paper substrate) by means of a doctor blade and dried conventionally after application.
  • Example 17 was repeated in several runs using amounts of ingredients within the range given in Table 9a.
  • the recording materials produced showed good properties with regard to sensitivity, dynamic print density, contrast, plasticizer stability (tape test) and optical appearance (whiteness).
  • a commercially available product with hollow body pigments in the enamel layer was used.
  • the recording material from Comparative Example 7 has a green-grey appearance on the printable side.
  • the material of Comparative Example 8 has a blue-grey appearance on the printable side.
  • the recording material according to the invention from Example 17 has a white-grey appearance.
  • the print density was determined in three places each on the black colored areas and the uncolored areas of the thermal printout using a Techkon SpectroDens Advanced densitometer. The mean value was formed from the respective measured values of the black-colored areas and the uncolored areas.
  • a thermal printout was hung in a heating cabinet at 60°C. After 24 hours, the thermal paper printout was removed, cooled to room temperature and the print density was again determined at three points each on the black colored areas and the uncolored areas of the thermal test printout using a Techkon SpectroDens Advanced densitometer. The mean value was formed from the respective measured values for the black-colored areas and the uncolored areas.
  • the permanence of the printed image in % corresponds to the quotient of the mean value of the print density of the colored areas before and after storage in the climatic cabinet multiplied by 100.
  • the print density was determined in three places each on the black colored areas and the uncolored areas of the thermal printout using a Techkon SpectroDens Advanced densitometer. The mean value was formed from the respective measured values of the black-colored areas and the uncolored areas.
  • a thermal printout was hung in a heating cabinet at 90°C. After one hour, the thermal paper printout was removed, cooled to room temperature and the print density was again determined at three points each on the black colored areas and the uncolored areas of the thermal test printout using a Techkon SpectroDens Advanced densitometer. The mean value was formed from the respective measured values for the black-colored areas and the uncolored areas.
  • the permanence of the printed image in % corresponds to the quotient of the mean value of the print density of the colored areas before and after storage in the climatic cabinet multiplied by 100.
  • the print density was determined in three places each on the black colored areas and the uncolored areas of the thermal printout using a Techkon SpectroDens Advanced densitometer. The mean value was formed from the respective measured values of the black-colored areas and the uncolored areas.
  • a thermal printout was hung in a climatic cabinet at 40° C. and a relative humidity of 90%. After 24 hours, the thermal paper printout was removed, cooled to room temperature and the print density was again determined at three points each on the black colored areas and the uncolored areas of the thermal test printout using a Techkon SpectroDens Advanced densitometer. The mean value was formed from the respective measured values for the black-colored areas and the uncolored areas.
  • the permanence of the printed image in % corresponds to the quotient of the mean value of the print density of the colored areas before and after storage in the climatic cabinet multiplied by 100.
  • thermo printout For the metrological determination of the plasticizer resistance (tape test) of a thermal printout on the heat-sensitive recording materials of Example 17 according to the invention and Comparative Examples 7 and 8, black and white checkered thermal printouts were made on the heat-sensitive recording materials to be tested using an Atlantek 400 device from the company Viex (USA) using a thermal head with a resolution of 300 dpi and an energy per unit area of 16 mJ/mm 2 .
  • the print density was determined in three places each on the black colored areas and the uncolored areas of the thermal printout using a Techkon SpectroDens Advanced densitometer. The mean value was formed from the respective measured values of the black-colored areas and the uncolored areas.
  • a strip of commercially available adhesive tape was stuck to part of the print area.
  • the thermal test print with adhesive tape was hung in a climatic cabinet at 23° C. and a relative humidity of 50%. After 24 hours, the thermal paper printout was removed and the print density was again determined at three points each on the black colored areas and the uncolored areas of the thermal test printout, using a Techkon SpectroDens Advanced densitometer. The mean value was formed from the respective measured values for the black-colored areas and the uncolored areas.
  • the permanence of the printed image in % corresponds to the quotient of the mean value of the print density of the colored areas before and after storage in the climatic cabinet multiplied by 100.

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  • Physics & Mathematics (AREA)
  • Optics & Photonics (AREA)
  • Chemical & Material Sciences (AREA)
  • Inorganic Chemistry (AREA)
  • Heat Sensitive Colour Forming Recording (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
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EP20191808.3A EP3957489B1 (fr) 2020-08-19 2020-08-19 Matière d'enregistrement thermosensible sans générateur
FIEP20191808.3T FI3957489T3 (fi) 2020-08-19 2020-08-19 Kehitteetön lämpöherkkä tallennusmateriaali
ES20191808T ES2937111T3 (es) 2020-08-19 2020-08-19 Material de registro sensible al calor sin revelador
EP22204860.5A EP4163119A1 (fr) 2020-08-19 2020-08-19 Matériau d'enregistrement thermosensible sans révélateur
PL20191808.3T PL3957489T3 (pl) 2020-08-19 2020-08-19 Niezawierający wywoływaczy, termoczuły materiał do zapisu
PT201918083T PT3957489T (pt) 2020-08-19 2020-08-19 Material de gravação termossensível sem revelador
CA3128553A CA3128553A1 (fr) 2020-08-19 2021-08-17 Materiau d'enregistrement sensible a la chaleur sans developpeur
US17/405,159 US20220055389A1 (en) 2020-08-19 2021-08-18 Developer-Free Heat-Sensitive Recording Material
AU2021218068A AU2021218068A1 (en) 2020-08-19 2021-08-18 Developer-free heat-sensitive recording material

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Publication number Priority date Publication date Assignee Title
EP2993055B1 (fr) 2014-09-06 2019-04-03 Mitsubishi HiTec Paper Europe GmbH Matériel d'enregistrement sensible à la chaleur en forme de bande doté d'une couche de protection
WO2022262908A2 (fr) 2021-06-18 2022-12-22 Koehler Innovation & Technology Gmbh Matériaux d'impression thermosensibles

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PT3957489T (pt) 2022-12-06
EP3957489B1 (fr) 2022-11-02
CA3128553A1 (fr) 2022-02-19
FI3957489T3 (fi) 2023-01-31
ES2937111T3 (es) 2023-03-24
AU2021218068A1 (en) 2022-03-10
PL3957489T3 (pl) 2023-03-20
US20220055389A1 (en) 2022-02-24

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