EP2993055B1 - Web-shaped heat-sensitive recording material with a protective layer - Google Patents
Web-shaped heat-sensitive recording material with a protective layer Download PDFInfo
- Publication number
- EP2993055B1 EP2993055B1 EP14183864.9A EP14183864A EP2993055B1 EP 2993055 B1 EP2993055 B1 EP 2993055B1 EP 14183864 A EP14183864 A EP 14183864A EP 2993055 B1 EP2993055 B1 EP 2993055B1
- Authority
- EP
- European Patent Office
- Prior art keywords
- heat
- layer
- recording material
- ply
- sensitive recording
- 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.)
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- 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
- B41M2205/38—Intermediate layers; Layers between substrate and imaging layer
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
- B41M—PRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
- B41M2205/00—Printing methods or features related to printing methods; Location or type of the layers
- B41M2205/40—Cover layers; Layers separated from substrate by imaging layer; Protective layers; Layers applied before imaging
-
- 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
- B41M5/124—Duplicating or marking methods; Sheet materials for use therein using pressure to make a masked colour visible, e.g. to make a coloured support visible, to create an opaque or transparent pattern, or to form colour by uniting colour-forming components
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
- B41M—PRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
- B41M5/00—Duplicating or marking methods; Sheet materials for use therein
- B41M5/26—Thermography ; Marking by high energetic means, e.g. laser otherwise than by burning, and characterised by the material used
- B41M5/40—Thermography ; Marking by high energetic means, e.g. laser otherwise than by burning, and characterised by the material used characterised by the base backcoat, intermediate, or covering layers, e.g. for thermal transfer dye-donor or dye-receiver sheets; Heat, radiation filtering or absorbing means or layers; combined with other image registration layers or compositions; Special originals for reproduction by thermography
- B41M5/41—Base layers supports or substrates
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
- B41M—PRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
- B41M5/00—Duplicating or marking methods; Sheet materials for use therein
- B41M5/26—Thermography ; Marking by high energetic means, e.g. laser otherwise than by burning, and characterised by the material used
- B41M5/40—Thermography ; Marking by high energetic means, e.g. laser otherwise than by burning, and characterised by the material used characterised by the base backcoat, intermediate, or covering layers, e.g. for thermal transfer dye-donor or dye-receiver sheets; Heat, radiation filtering or absorbing means or layers; combined with other image registration layers or compositions; Special originals for reproduction by thermography
- B41M5/42—Intermediate, backcoat, or covering layers
- B41M5/423—Intermediate, backcoat, or covering layers characterised by non-macromolecular compounds, e.g. waxes
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
- B41M—PRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
- B41M5/00—Duplicating or marking methods; Sheet materials for use therein
- B41M5/26—Thermography ; Marking by high energetic means, e.g. laser otherwise than by burning, and characterised by the material used
- B41M5/40—Thermography ; Marking by high energetic means, e.g. laser otherwise than by burning, and characterised by the material used characterised by the base backcoat, intermediate, or covering layers, e.g. for thermal transfer dye-donor or dye-receiver sheets; Heat, radiation filtering or absorbing means or layers; combined with other image registration layers or compositions; Special originals for reproduction by thermography
- B41M5/42—Intermediate, backcoat, or covering layers
- B41M5/426—Intermediate, backcoat, or covering layers characterised by inorganic compounds, e.g. metals, metal salts, metal complexes
Definitions
- the invention relates to a sheet-like heat-sensitive recording material having at least a first layer and a first layer at least partially covering the second layer, wherein the sheet-like heat-sensitive recording material proposed here additionally comprises a second layer at least partially covering the protective layer.
- the web-shaped heat-sensitive recording material proposed on this page takes environmental-friendly aspects into account to a particular extent.
- the object of the invention is defined in the appended claims.
- Heat-sensitive recording materials have been known for many years and enjoy a generally unbroken popularity, which, among other things, is due to the fact that their use for the ticket and / or purchase document issuing businessman is associated with great advantages. Since the color-forming components are contained in the recording material itself in the known color-reactive recording materials attributable to the heat-sensitive recording method, the toner and color-cartridge-free thermal printers, which in their function no longer need to be regularly monitored by anyone, can be used in large numbers be set up. Thus, this innovative technology has largely prevailed, especially in public transport and retail.
- the inventors considered the EP 0 512 114 A1 which proposes as a recording material for tachographs at least a 2-ply sheet with a colored support on which an opaque layer of an aqueous suspension with polymer particles is applied.
- a sheet of a paper with a black topcoat is disclosed, wherein paper including topcoat together serve as a colored support and onto which an opaque layer of hollow body pigments is spread.
- the layer containing the hollow body pigment is scratched open and the underlying black topcoat becomes visible as a typeface.
- the manipulation of the hollow body pigments to form a typeface their removal which is very easy in their involvement in the top coat due to the low degree of interconnectedness within the top coat having them.
- the protective layer itself can be applied by means of conventional brushing, for which, inter alia, a coating color is usable, as described above and for which a surface-related mass in a range of 1.5 to 4.5 g / m 2 is preferred, or the protective layer may alternatively be printed. Processing technology and in terms of their technological properties are particularly suitable such protective layers which are curable by means of actinic radiation.
- actinic radiation UV or ionizing radiation, such as electron beams to understand.
- a particularly preferred second embodiment alternative to the first embodiment described above for a completely or partially covering the second layer protective layer provides as binder a polyvinyl alcohol, wax as a zinc stearate, as a pigment aluminum hydroxide or alternatively also silica and one or more crosslinkers before, with particularly preferred Quantities for such a protective layer are given in Table 1 below: ⁇ u> Table 1: ⁇ / u> product % By weight [atro] aluminum hydroxide 10 - 25 polyvinyl alcohol 55 - 70 zinc stearate 7 - 9 crosslinkers 6-7
- a coating composition comprising as a binder at least one polyvinyl alcohol and the at least one crosslinking agent. It is preferred if the polyvinyl alcohol of the protective layer according to the third embodiment variant is modified with carboxyl, diacetone or in particular silanol groups. Also mixtures of different Carboxyl-, diacetone- or silanol-modified polyvinyl alcohols are preferably usable.
- the at least one crosslinker for the protective layer according to the third embodiment is preferably selected from the group consisting of boric acid, polyamines, epoxy resins, dialdehydes, formaldehyde oligomers, polyamine epichlorohydrin resin, adipic dihydrazide and melamine formaldehyde. It is also possible to use mixtures of different crosslinkers.
- the weight ratio of the modified polyvinyl alcohol to the crosslinker is in a range from 20: 1 to 5: 1, and more preferably in a range from 12: 1 to 7: 1 Ratio of the modified polyvinyl alcohol to the crosslinker in the range of 100 parts by weight to 8 to 11 parts by weight.
- the at least one inorganic pigment is preferably selected from the group consisting of silicon dioxide bentonite, aluminum hydroxide, calcium carbonate, kaolin and mixtures of said inorganic pigments.
- the protective layer according to this third embodiment with a basis weight in a range of 1.0 g / m 2 to 6 g / m 2 and particularly preferably from 1.2 g / m 2 to 3.8 g / m 2 apply.
- the protective layer is preferably formed in one layer, without being limited in this regard.
- a protective layer-like sheet-like heat-sensitive recording material is equipped as a label with back (self) adhesive layer.
- the usual construction then provides a web-shaped substrate, preferably a paper web, which has a front side and a rear side opposite it. On the reverse side, the sheet-shaped heat-sensitive recording material then has the (self) adhesive layer.
- a first layer, a second layer at least partially covering the first layer and a protective layer at least partially covering the second layer are applied to the substrate in this order.
- the adhesive layer may be covered with a release material such as a silicone-containing release paper or the outer layer formed on the second layer protective layer of the recording material according to the invention is provided with an additional release layer, preferably by means of a so-called five-Walzenêtwerks is applied.
- the release layer in this case has release agents, preferably based on silicone oil.
- the release layer is curable or crosslinkable under the influence of high-energy radiation, such as UV or electron radiation.
- high-energy radiation such as UV or electron radiation.
- the monomers or prepolymers used for the preparation of this layer must contain additives of photoinitiators in a known manner.
- electron beam curing a particularly uniform over its cross-section, that is cured release layer could be achieved.
- the heat-sensitive recording material In order to form the heat-sensitive recording material according to the invention, its first layer with the intensive coloring facing the second layer is first covered with high opacity, that is to say almost opaque, by the second layer with the hollow-body pigments. Because of the opacity of the second layer caused by the hollow-body pigments, no or only little of the coloring of the first layer can be determined.
- heat in the form of any pattern which means in the form of whatever typeface are the hollow body pigments melted the second layer, for example by means of the printhead of a thermal printer, as well as the statements in paragraph [0006] can be seen.
- the fusion or collapse of the hollow body pigments results in an increased light transmission of the second layer.
- the second layer there remain still irregular empty spaces between the molten hollow body pigments and unmelted components which maintain an albeit reduced opacity of this second layer.
- the preferred additional incorporation of at least one fatty acid or a fatty acid amide and / or hydroxymethylated fatty acid amide and / or at least one heat-sensitive sensitizer in the second layer of the effect of reducing a confused light scattering is significantly improved because the at least one fatty acid or fatty acid amide and / or hydroxymethylated fatty acid amide and / or the at least one heat-sensitive sensitizer envelop the unmelted components of the second layer and fill the empty spaces within the second layer.
- fatty acids or fatty acid amides and / or hydroxymethylated fatty acid amides which are preferably provided for incorporation into the second layer
- fatty acid amides and especially hydroxymethylated fatty acid amides are preferred
- fatty acid amides and hydroxymethylated fatty acid amides within the scope of a preferred embodiment of the present invention also in combination, in particular in a wt .-% (atro) in the second layer related mixing ratio of 1: 2 to 2: 1, can be used within the second layer.
- preferred fatty acids include stearic acid and palmitic acid, which can also be used in particular in a combined manner within the second layer.
- fatty acid amides is preferably stearic acid amide
- hydroxymethylated fatty acid amides is preferably Methylolstearinklamid.
- the combination of stearinamide and Methylolstearinamid within the second layer is a preferred embodiment for the design of the second layer.
- the hollow body pigments within the second layer have a wall of plastic, ideally of thermoplastic resin, which melts under high heat input.
- This thermoplastic resin or the hollow body pigment outer wall itself preferably comprises (meth) acrylonitrile copolymer, polyvinyl chloride, polyvinylidene chloride, polystyrene, styrene acrylate, styrene (meth) acrylate copolymer, polyacrylonitrile, polyacrylic acid ester or else the mixture of at least two of the components mentioned ,
- pigment mixtures of different hollow body pigments for the second layer are conceivable.
- so-called "cup-shaped" pigments in particular also apply as hollow-body pigments.
- thermoplastic resin of the hollow body pigment outer wall in a range from 35 ° C to less than or equal to 200 ° C and preferably in a range from 75 ° C to less than or equal to 120 ° C has been found advantageous because below temperatures of 35 ° C, the wall of the hollow body pigments is no longer sufficiently stable at room temperature. Above temperatures of 200 ° C, there are handling problems of over heating the surface of the recording material.
- the preferred temperature range between 75 ° C to less than or equal to 120 ° C provides the simplest conditions in terms of processing quality and speed in the Forming the second layer and in its use to create a typeface by merging the hollow body pigments in the form of this typeface, which is not limited to the purposes of the present invention to the mere reproduction of alphanumeric characters, but just as markings of any kind, such as characters, Icons or monochrome or grayscale images.
- Suitable binders for incorporation in the second layer of the heat-sensitive recording material proposed herein are, for example, water-soluble binders such as starch, hydroxyethylcellulose, methylcellulose, carboxymethylcellulose, gelatin, casein, polyvinyl alcohols, modified polyvinyl alcohols, ethylene-vinyl alcohol copolymers, sodium polyacrylates, acrylamide-acrylate copolymers, acrylamide Acrylate-methacrylate terpolymers and alkali metal salts of styrene-maleic anhydride copolymer or ethylene-maleic anhydride copolymer, which binders can be used alone or in combination with one another; Also water-insoluble latex binders such as styrene-butadiene copolymers, acrylonitrile-butadiene copolymers and methyl acrylate-butadiene copolymers are suitable as binders for incorporation into the second layer.
- water-soluble binders such as
- the second layer generally comprises lubricants, which are preferably waxes such as, and most preferably, zinc stearates and paraffin waxes, as well as other additives, including but not limited to wetting agents and defoamers.
- lubricants which are preferably waxes such as, and most preferably, zinc stearates and paraffin waxes, as well as other additives, including but not limited to wetting agents and defoamers.
- the second layer of the proposed heat-sensitive recording material As a base color for the second layer of the proposed heat-sensitive recording material is particularly white, since heat-sensitive recording materials, especially in their intended and preferred use as a receipt and / or label and / or ticket in white appearance usually are desired in the market. Also, the non-fused hollow body pigments, as long as no further coloring components of the second layer are admixed, appear white.
- the sheet-shaped heat-sensitive recording material proposed here can be used without limitation also with a particularly light coloration of the second layer and is therefore considered as one possible form of the proposed heat-sensitive recording material.
- the first layer is a mass-dyed web-shaped substrate, to which the substrate in a preferred embodiment carbon black components and / or dyes are added in such an amount that the substrate has an intense color
- paper is generally considered to be a preferred substrate in the range of 35 to 180 g / m 2 in the range of the basis weight in the sense of the present invention.
- the heat-sensitive recording material proposed here according to the second possible embodiment has a colored intermediate layer as described above, it is possible, but no longer necessary, for the substrate bearing the intermediate layer as the first layer to have a coloration.
- the dyed intermediate layer as the first layer can be applied by printing technology to a substrate acting as the base support, for example in the form of paper or film.
- this colored intermediate layer is preferably applied to a substrate, wherein it is particularly preferred if the colored Intermediate layer is applied with gratis coating devices, as they represent, for example, roller coater, doctor blade or (roll) doctor blade coating.
- the colored intermediate layer can make a positive contribution to the leveling of the substrate surface, which on the one hand reduces the amount of coating material necessarily applied to form the second layer and on the other hand, the function of the second layer is supported.
- a fairly wide range between 2 and 10 g / m 2 and preferably between 2 and 7 g / m 2 has proven to be particularly suitable, especially when applied with a doctor blade between 2 and 4 g / m 2 , while in printing technical order of the colored intermediate layer as a first layer values well below 2 g / m 2 then with layer thicknesses preferably between 0.5 .mu.m and 1.5 .mu.m are possible.
- the smoothness (according to Bekk) of the first layer a range of 200 sec to 500 sec has proven to be suitable, which is why such a range is considered to be preferred in the context of the present invention.
- the particularly preferred higher values between 300 sec and 500 sec are achieved by smoothing the substrate with applied first layer, for example by means of a two-, three- or Mehrwalzenglättwerks or even by means of a calender.
- inorganic oil-absorbing white pigments preferably in a range from 20 to 45% by weight, based on the total weight of the intermediate layer, are added to the dyed intermediate layer , which are of great relevance for the external appearance and for the improvement of the later printability.
- Preferred inorganic inorganic pigments of the intermediate layer have been those selected from the group comprising natural and calcined kaolin, silica, bentonite, calcium carbonate and aluminum hydroxide, in particular boehmite here. Also mixtures of several different types of inorganic white pigments are conceivable.
- the particle size of the inorganic white pigments present in the colored interlayer is preferably in a range of less than 2 ⁇ m. Pigments having a particle size distribution of from 34 to 40% by weight of less than 1 ⁇ m and from 57 to 63% by weight of less than 2 ⁇ m, in each case based on the total amount of white pigments in the intermediate layer, have proved to be advantageous.
- the intermediate layer preferably has carbon black constituents and / or dyes in an appropriate amount, in the case of carbon black pigments preferably in a range from 30 to 40% by weight, based on the total weight of the intermediate layer.
- Carbon black pigments having an average particle size of 50 nm have proved to be advantageous.
- the intermediate layer dyed as the first layer and additionally pigmented contains at least one binder, preferably based on a synthetic polymer, with styrene-butadiene latex, for example, giving particularly good results.
- a synthetic binder with the admixture of at least one natural polymer is a particularly suitable embodiment.
- a binder is highly saponified polyvinyl alcohol.
- Binder total amount of white pigments and carbon black pigments within the pigmented intermediate layer between 1: 3 and 1: 4 is a particularly suitable embodiment.
- the task of the first intermediate layer for the subsequently applied second intermediate layer to ensure a particularly flat surface, so that the basis weight of the second intermediate layer is particularly low, preferably in a range between 1 and 8 g / m 2 and even better between 1 and 5 g / m 2 , especially when applied with a doctor blade very particularly preferably between 1.5 and 3.0 g / m 2 , can be selected.
- the amount of carbon black pigments which can lead to difficulties within the recycling, can be reduced.
- the first intermediate layer according to the third embodiment mainly comprises white pigments as disclosed in paragraph [0042], binders and others also usual additives.
- Decisive is their job with a leveling coating device, such as with a doctor blade or (roller) doctor blade coating with subsequent treatment by means of calender and / or calender.
- FIG. 1 shows the basic structure of the sheet-like heat-sensitive recording material according to the invention here omitting the protective layer (40) according to the invention with a first layer (1) having intense coloration - in this case uniformly black, represented by soot colors, for example - and a second layer covering the first layer (FIG. 2).
- first layer (1) having intense coloration - in this case uniformly black, represented by soot colors, for example -
- second layer covering the first layer FIG. 2
- a different representation of translucent and opaque regions of the second layer (2) is dispensed with.
- the first layer is a mass-dyed web-shaped substrate (11).
- the second layer (2) is applied, for which in principle a range in terms of basis weight between 2 and 10 g / m 2 is considered to be preferred, as very particularly preferred is a range between 4 and 8 g / m 2 .
- a basis weight of the second layer of less than 2 g / m 2
- the coverage of the first layer is often no longer adequately ensured, whereas a second layer with a basis weight of well over 10 g / m 2 for economic reasons does not make sense.
- FIG. 2 shows in this respect, a sheet-like heat-sensitive recording material according to the invention, wherein the recording material is designed in one of its simplest embodiments.
- the second layer (2) whose hollow body pigments are fused by means of the print head of a thermal printer in the form of a typeface, is applied to a substrate (11) formed as a first layer here, for example with carbon black constituents for coloring the substrate.
- the second layer (2) completely covers the subjacent substrate (11).
- the second layer (2) is in turn covered by a protective layer (40).
- FIG. 3 shows such an embodiment of the proposed heat-sensitive recording material, wherein the recording material in this case, a polyolefin-coated paper as a substrate (10) on which a pigmented intermediate layer (21) is applied as a first layer.
- the recording material in this case, a polyolefin-coated paper as a substrate (10) on which a pigmented intermediate layer (21) is applied as a first layer.
- This first layer is covered over the entire area by the second layer (2), whose hollow-chamber pigments are partially fused in the form of a typeface.
- the second layer (2) is in turn covered by a protective layer (40).
- the surface mass,% by weight (% by weight) and parts by weight (parts by weight) given in the specification and claims refer to the "atro" weight, respectively. absolutely dry parts by weight.
- the relevant figures are calculated from the "lutro" weight, i. air-dry parts by weight, less the proportion by weight of water in the interior of the pigments as supplied.
- the thus-finished heat-sensitive recording material is fed to a thermal printer.
- the hollow particles of the second layer are melted together with the stearic acid amide and the heat sensitive sensitizer according to a predetermined check pattern by the printhead of the thermal printer so that areas in the second layer with fused components and filled intermediate areas and areas with unfused components and unfilled intermediate areas ent stand.
- the thus prepared recording material thus has a very well recognizable, sharp-edged typeface on with blackened areas where the hollow body pigments are fused together in the second layer by the heat input of the printhead of the thermal printer.
- the blackened areas originate from the uniform color of the intermediate layer, the color of which can be recognized by the transparent areas of the second layer with the hollow body pigments fused there.
- the whiteness of the heat-sensitive recording material according to the invention is determined once with, once without UV, the measurements being carried out in accordance with the specifications of ISO 2469 / ISO 2470, with the proviso that in the measurements made here D65- Light is used at a viewing angle of 8 °.
- the white measurements are carried out using a device of the type Elrepho 3000 (illuminant D 65/10). The values determined are 56% (with UV content) and 52% (without UV), which largely corresponds to a gray paper, but in view of this coating and functional technology this is considered to be acceptable and salable.
- the respective optical print density is determined before and after the formation of a black-and-white checkered thermo-printout with an Atlantek 400 device from Viex (USA) using a thermal head with a resolution of 300 dpi and an energy per unit area of 16 mJ / mm 2 is used.
- the respectively non-printed area or the respective thermo-printed area is measured at three locations with the Gretag MacBeth Densitometer TYPE D19C NB / U densitometer (Gretag MacBeth, 8105 Regensdorf, Switzerland).
- the unprinted areas have a mean optical density of 0.33 ODU (Optical Density Units), for the thermo-printed areas a mean optical density of 1.22 ODU. With a difference of 0.89 ODU as the contrast between printed and unprinted areas, the present invention proves that a skilled typeface is easy to see, underscoring the value of the present invention.
- ODU Optical Density Units
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- Optics & Photonics (AREA)
- Heat Sensitive Colour Forming Recording (AREA)
Description
Die Erfindung betrifft ein bahnförmiges wärmeempfindliches Aufzeichnungsmaterial mit mindestens einer ersten Lage und einer die erste Lage zumindest teilweise abdeckenden zweiten Lage, wobei das hier vorgeschlagene bahnförmige wärmeempfindliche Aufzeichnungsmaterial zusätzlich eine die zweite Lage zumindest teilweise abdeckende Schutzschicht aufweist. Das diesseits vorgeschlagene bahnförmige wärmeempfindliche Aufzeichnungsmaterial berücksichtigt in einem besonderen Maße umweltschonende Aspekte.
Der Gegenstand der Erfindung ist in den beigefügten Ansprüchen definiert.The invention relates to a sheet-like heat-sensitive recording material having at least a first layer and a first layer at least partially covering the second layer, wherein the sheet-like heat-sensitive recording material proposed here additionally comprises a second layer at least partially covering the protective layer. The web-shaped heat-sensitive recording material proposed on this page takes environmental-friendly aspects into account to a particular extent.
The object of the invention is defined in the appended claims.
Wärmeempfindliche Aufzeichnungsmaterialien sind seit vielen Jahren bekannt und erfreuen sich einer im Grundsatz ungebrochenen Beliebtheit, was unter anderem darauf zurückzuführen ist, dass ihre Verwendung für den Ticket und/oder Kaufbeleg ausgebenden Geschäftsmann mit großen Vorteilen verbunden ist. Weil bei den bekannten, dem wärmeempfindlichen Aufzeichnungsverfahren als üblicher Stand der Technik zuzurechnenden farbreaktiven Aufzeichnungsmaterialien die farbbildenden Komponenten in dem Aufzeichnungsmaterial selbst stecken, können die Toner- und Farbkartuschen-freien Thermodrucker, die in ihrer Funktion von niemandem mehr regelmäßig kontrolliert werden müssen, in großer Zahl aufgestellt werden. So hat sich diese innovative Technologie insbesondere im öffentlichen Personenverkehr und im Einzelhandel weitgehend flächendeckend durchgesetzt.Heat-sensitive recording materials have been known for many years and enjoy a generally unbroken popularity, which, among other things, is due to the fact that their use for the ticket and / or purchase document issuing businessman is associated with great advantages. Since the color-forming components are contained in the recording material itself in the known color-reactive recording materials attributable to the heat-sensitive recording method, the toner and color-cartridge-free thermal printers, which in their function no longer need to be regularly monitored by anyone, can be used in large numbers be set up. Thus, this innovative technology has largely prevailed, especially in public transport and retail.
In der zurückliegenden näheren Vergangenheit sind jedoch vermehrt Bedenken gegen die Umweltverträglichkeit
- insbesondere von bestimmten (Farb-)Entwicklern, auch als Farbakzeptoren bezeichnet,
- teilweise auch von Farbstoffvorläufern, mit denen die (Farb-)Entwickler bei Wärmezufuhr unter Ausbildung einer visuell erkennbaren Farbe reagieren,
- □ Bisphenol-A, das ist 2,2 bis (4-hydroxyphenyl)-Propan, und
- □ Bisphenol-S, das ist 4,4'-Dihydroxydiphenylsulfon,
- □ Pergafast® 201, das ist N-(p-toluensulphonyl)-N'-3-(p-toluensulphonyl-Oxy-phenyl)-harnstoff, der Firma BASF Corporation, und
- ▪ D8, das ist 4-[(4-(1-methylethoxy)phenyl)sulfonyl]phenol,
- in particular of certain (color) developers, also referred to as color acceptors,
- partially also of dye precursors with which the (color) developers react when supplied with heat to form a visually recognizable color,
- □ bisphenol-A, which is 2,2 bis (4-hydroxyphenyl) propane, and
- □ bisphenol-S, which is 4,4'-dihydroxydiphenyl sulfone,
- Pergafast® 201, which is N- (p-toluenesulphonyl) -N'-3- (p-toluenesulphonyl-oxy-phenyl) -urea, the BASF Corporation, and
- ▪ D8, that is 4 - [(4- (1-methylethoxy) phenyl) sulfonyl] phenol,
In Berücksichtigung dieser in kürzester Zeit völlig veränderten Marktlage erkannte die Erfinderschaft die Notwendigkeit für ein völlig neuartiges wärmeempfindliches Aufzeichnungsmaterial, das in einem besonderen Maße umweltschonende Aspekte berücksichtigt. Als Lösung wird hiermit nun ein bahnförmiges wärmeempfindliches Aufzeichnungsmaterial mit mindestens einer ersten Lage und einer die erste Lage zumindest teilweise abdeckenden zweiten Lage vorgeschlagen, wobei
- die erste Lage zumindest zugewandt zur zweiten Lage eine intensive Färbung aufweist und
- die zweite Lage Hohlkörperpigmente aufweist, die zur Ausbildung eines Schriftbildes manipulierbar sind.
- the first layer at least facing the second layer has an intense coloration and
- the second layer has hollow body pigments that can be manipulated to form a typeface.
Als nächstliegender Stand der Technik betrachtet die Erfinderschaft die
Gegenstand der internationalen Patentanmeldung
Genau diese Eigenschaft der Hohlkörperpigmente enthaltende Schicht wird in der
- der Maskierungsschicht in diesem hervorragend bewährten Aufzeichnungsmaterial gemäß der
EP 1 778 499 B1 - der Hohlkörperpigment enthaltende Schicht gemäß der
WO 2012 / 145 456 A1 - und der zweiten Lage in dem wärmeempfindlichen Aufzeichnungsmaterial gemäß vorliegendem Vorschlag
Über die vorstehend angeführten Dokumente hinaus, sind auch die Dokumente
Dokument
Das Dokument
- the masking layer in this well-established recording material according to the
EP 1 778 499 B1 - the hollow body pigment-containing layer according to the
WO 2012/145 456 A1 - and the second layer in the heat-sensitive recording material according to the present proposal
Beyond the above mentioned documents, there are also the documents
document
The document
Nach intensiven Untersuchungen an gattungsgemäßen wärmeempfindlichen Aufzeichnungsmaterialien, wie sie im oberen Absatz [0004] beschrieben werden, mit mindestens einer ersten Lage und einer die erste Lage zumindest teilweise abdeckenden zweiten Lage, wobei
- die erste Lage zumindest zugewandt zur zweiten Lage eine intensive Färbung aufweist und
- die zweite Lage Hohlkörperpigmente aufweist, die zur Ausbildung eines Schriftbildes manipulierbar sind,
- ▪ die erste Lage zumindest zugewandt zur zweiten Lage eine intensive Färbung aufweist und
- ▪ die zweite Lage Hohlkörperpigmente aufweist, die zur Ausbildung eines Schriftbildes durch lokal begrenzte Wärmebehandlung schmelzbar sind,
- the first layer at least facing the second layer has an intense coloration and
- the second layer has hollow body pigments which can be manipulated to form a typeface,
- The first layer at least facing the second layer has an intensive coloration and
- The second layer has hollow body pigments which can be melted by locally limited heat treatment to form a typeface,
Die eingangs angeforderten umweltschonenden Aspekte des hier vorgeschlagenen bahnförmigen wärmeempfindlichen Aufzeichnungsmaterials ergeben sich dabei aus dem gänzlichen Verzicht auf Farbstoffvorläufern und mit denen reaktionsfähigen (Farb-)Entwicklern.The initially required environmentally friendly aspects of the sheet-like heat-sensitive recording material proposed here result from the complete abandonment of dye precursors and with those reactive (color) developers.
Um den besonderen Anforderungen an eine solche Schutzschicht im Sinne der vorliegenden Erfindung in einem besonders hohen Maße gerecht zu werden, betrachtet es die Erfinderschaft als besonders vorteilhaft, wenn eine solche Schutzschicht mindestens die folgenden Bestandteile aufweist:
- mindestens ein anorganisches Pigment,
- mindestens ein Bindemittel,
- mindestens ein Wachs,
- optische Aufheller
- ganz besonders bevorzugt mindestens einen Vernetzer
- at least one inorganic pigment,
- at least one binder,
- at least one wax,
- optical brighteners
- most preferably at least one crosslinker
Das mindestens eine anorganische Pigment der Schutzschicht ist bevorzugt ausgesucht aus der Liste, umfassend:
- ▪ natürliches oder gefälltes Kalziumkarbonat,
- ▪ Kaolin,
- ▪ Siliziumdioxid und Kieselsäure,
- ▪ Aluminiumhydroxid,
- ▪ Titanoxid,
- ▪ alkalisch aufbereitetes Bentonit.
- ▪ natural or precipitated calcium carbonate,
- ▪ kaolin,
- ▪ silica and silica,
- ▪ aluminum hydroxide,
- ▪ titanium oxide,
- ▪ alkaline bentonite.
Als Bindemittel bietet sich zunächst eine große Auswahl möglicher Vertreter an. So ist das mindestens eine Bindemittel der Schutzschicht bevorzugt ausgesucht aus der Liste, umfassend:
- ▪ selbstvernetzende Bindemittel, ausgewählt aus der Gruppe umfassend Styrol-Acrylsäureester-Copolymerisat, ein Acrylamidgruppen enthaltendes Copolymerisat aus Styrol/Acrylsäureester sowie ganz bevorzugt ein Copolymer auf Basis von Acrylnitril, Methacrylamid und Acrylester,
- ▪ Polyvinylalkohol, bevorzugt modifiziert mit Carboxyl-, Diaceton- oder insbesondere Silanolgruppen
sowie - ▪ Mischungen verschiedener Carboxyl-, Diaceton- oder Silanol-modifizierter Polyvinylalkohole
- ▪ self-crosslinking binder selected from the group comprising styrene-acrylic acid ester copolymer, a copolymer of styrene / acrylic ester containing acrylamide groups, and most preferably a copolymer based on acrylonitrile, methacrylamide and acrylic ester,
- ▪ Polyvinyl alcohol, preferably modified with carboxyl, diacetone or in particular silanol groups
such as - ▪ Mixtures of various carboxyl-, diacetone- or silanol-modified polyvinyl alcohols
Das mindestens eine Wachs der Schutzschicht kann bevorzugt ausgesucht sein aus der Liste, umfassend Paraffinwachs und Zinkstearat. Als Vernetzer bietet sich insbesondere mindestens ein Vertreter an, ausgesucht aus der Liste, umfassend:
- ▪ Borsäure,
- ▪ Polyamine,
- ▪ Epoxyharze,
- ▪ Dialdehyde,
- ▪ Formaldehydoligomere,
- ▪ Adipinsäuredihydrazid
sowie speziell
- ▪ zyklische Harnstoffe,
- ▪ Methylolharnstoff,
- ▪ Amoniumzirkoniumkarbonat und
- ▪ besonders bevorzugt Polyaminepichlorhydrinharz.
- ▪ boric acid,
- ▪ polyamines,
- ▪ epoxy resins,
- ▪ dialdehydes,
- ▪ formaldehyde oligomers,
- ▪ adipic dihydrazide
as well as specifically
- ▪ cyclic ureas,
- ▪ methylolurea,
- Amonium zirconium carbonate and
- Particularly preferably polyamine epichlorohydrin resin.
In einer ersten Ausführungsvariante weist die Schutzschicht, wie sie vorstehend eingeführt ist,
- als das mindestens eine Bindemittel bevorzugt ein oder mehrere wasserunlösliche, selbstvernetzende Acrylpolymere,
- den mindestens einen Vernetzer und
- das mindestens eine Pigment auf,
- as the at least one binder preferably one or more water-insoluble, self-crosslinking acrylic polymers,
- the at least one crosslinker and
- the at least one pigment on,
Als selbstvernetzendes Acrylpolymer innerhalb der Schutzschicht gemäß erster Ausführungsvariante ist ein selbstvernetzendes Bindemittel zu verstehen, ausgewählt aus der Gruppe umfassend
- ▪ ein Styrol-Acrylsäureester-Copolymerisat,
- ▪ ein Acrylamidgruppen enthaltendes Copolymerisat aus Styrol/Acrylsäureester,
- ▪ ein Copolymer auf Basis von Acrylnitril, Methacrylamid und Acrylester.
- ▪ a styrene-acrylic acid ester copolymer,
- An acrylamide-containing copolymer of styrene / acrylic ester,
- ▪ a copolymer based on acrylonitrile, methacrylamide and acrylic ester.
Neben dem alkalisch aufbereiteten Bentonit kann als Pigment auch natürliches oder gefälltes Kalziumkarbonat, Kaolin, Kieselsäure, Aluminiumhydroxid oder Titanoxid in die Schutzschicht eingebunden sein. Hinsichtlich der Vernetzer sind insbesondere solche bevorzugt, die ausgewählt sind aus der Gruppe umfassend
- zyklischen Harnstoff,
- Methylolharnstoff,
- Amoniumzirkoniumkarbonat und
- besonders bevorzugt Polyamidepichlorhydrinharz.
- cyclic urea,
- methylol,
- Amonium zirconium carbonate and
- more preferably polyamide-epichlorohydrin resin.
Durch die Wahl eines wasserunlöslichen, selbstvernetzenden Acrylpolymers als Bindemittel und dessen Verhältnis einerseits zum Pigment in einem Bereich zwischen 7 : 1 und 9 : 1, andererseits und besonders bevorzugt zum Vernetzer größer als 5 : 1 wird schon bei einer Schutzschicht mit relativ geringer flächenbezogener Masse eine hohe Kratzbeständigkeit des hier vorgeschlagen Aufzeichnungsmaterials gegeben.By choosing a water-insoluble, self-crosslinking acrylic polymer as a binder and its ratio on the one hand to the pigment in a range between 7: 1 and 9: 1, on the other hand, and particularly preferably to the crosslinker greater than 5: 1 is already in a protective layer with a relatively small area-related mass one given high scratch resistance of the recording material proposed here.
Die Schutzschicht selbst kann mittels üblicher Streichwerke aufgetragen sein, wofür unter anderem eine Streichfarbe nutzbar ist, wie sie oben beschrieben ist und für die eine flächenbezogene Masse in einem Bereich von 1,5 bis 4,5 g/m2 bevorzugt ist, oder die Schutzschicht kann alternativ auch aufgedruckt sein. Verarbeitungstechnisch und hinsichtlich ihrer technologischen Eigenschaften besonders geeignet sind solche Schutzschichten, die mittels aktinischer Strahlung härtbar sind. Unter dem Begriff "aktinische Strahlung" sind UV- oder ionisierende Strahlungen, wie Elektronenstrahlen, zu verstehen.The protective layer itself can be applied by means of conventional brushing, for which, inter alia, a coating color is usable, as described above and for which a surface-related mass in a range of 1.5 to 4.5 g / m 2 is preferred, or the protective layer may alternatively be printed. Processing technology and in terms of their technological properties are particularly suitable such protective layers which are curable by means of actinic radiation. The term "actinic radiation" UV or ionizing radiation, such as electron beams to understand.
Eine alternativ zur oben beschriebenen ersten Ausführungsvariante ganz besonders bevorzugte zweite Ausführungsvariante für eine die zweite Lage ganz oder teilweise abdeckenden Schutzschicht sieht als Bindemittel einen Polyvinylalkohol, als Wachs ein Zinkstearat, als Pigment Aluminiumhydroxid oder alternativ auch Siliziumdioxid sowie einen oder mehrere Vernetzer vor, wobei besonders bevorzugte Mengen für eine solche Schutzschicht in der nachfolgenden Tabelle 1 wiedergegeben sind:
In einer dritten Ausführungsvariante für eine die zweite Lage ganz oder teilweise abdeckenden Schutzschicht ist diese erhältlich aus einer Beschichtungsmasse umfassend als Bindemittel mindestens einen Polyvinylalkohol und den mindestens einen Vernetzer. Dabei ist es bevorzugt, wenn der Polyvinylalkohol der Schutzschicht gemäß dritter Ausführungsvariante mit Carboxyl-, Diaceton- oder insbesondere Silanolgruppen modifiziert ist. Auch Mischungen verschiedener Carboxyl-, Diaceton- oder Silanol-modifizierter Polyvinylalkohole sind bevorzugt einsetzbar.In a third embodiment for a second layer completely or partially covering the protective layer is available from a coating composition comprising as a binder at least one polyvinyl alcohol and the at least one crosslinking agent. It is preferred if the polyvinyl alcohol of the protective layer according to the third embodiment variant is modified with carboxyl, diacetone or in particular silanol groups. Also mixtures of different Carboxyl-, diacetone- or silanol-modified polyvinyl alcohols are preferably usable.
Der mindestens eine Vernetzer für die Schutzschicht gemäß dritter Ausführungsvariante ist vorzugsweise ausgewählt aus der Gruppe bestehend aus Borsäure, Polyaminen, Epoxyharzen, Dialdehyden, Formaldehydoligomeren, Polyaminepichlorhydrinharz, Adipinsäuredihydrazid und Melaminformaldehyd. Auch Mischungen verschiedener Vernetzer sind möglich.The at least one crosslinker for the protective layer according to the third embodiment is preferably selected from the group consisting of boric acid, polyamines, epoxy resins, dialdehydes, formaldehyde oligomers, polyamine epichlorohydrin resin, adipic dihydrazide and melamine formaldehyde. It is also possible to use mixtures of different crosslinkers.
Bevorzugt liegt in der Beschichtungsmasse zur Ausbildung der Schutzschicht gemäß dritter Ausführungsvariante das Gewichtsverhältnis des modifizierten Polyvinylalkohols zu dem Vernetzer in einem Bereich von 20 : 1 bis 5 : 1 und besonders bevorzugt in einem Bereich von 12 : 1 bis 7 : 1. Besonders bevorzugt ist ein Verhältnis des modifizierten Polyvinylalkohols zum Vernetzer im Bereich von 100 Gewichtsteilen zu 8 bis 11 Gewichtsteilen.Preferably, in the coating composition for forming the protective layer according to the third embodiment, the weight ratio of the modified polyvinyl alcohol to the crosslinker is in a range from 20: 1 to 5: 1, and more preferably in a range from 12: 1 to 7: 1 Ratio of the modified polyvinyl alcohol to the crosslinker in the range of 100 parts by weight to 8 to 11 parts by weight.
Das mindestens eine anorganische Pigment ist vorzugsweise ausgewählt aus der Gruppe bestehend aus Siliziumdioxid Bentonit, Aluminiumhydroxid, Kalziumkarbonat, Kaolin und Mischungen aus den genannten anorganischen Pigmenten.The at least one inorganic pigment is preferably selected from the group consisting of silicon dioxide bentonite, aluminum hydroxide, calcium carbonate, kaolin and mixtures of said inorganic pigments.
Es ist bevorzugt, die Schutzschicht gemäß dieser dritten Ausführungsvariante mit einer flächenbezogenen Masse in einem Bereich von 1,0 g/m2 bis 6 g/m2 und besonders bevorzugt von 1,2 g/m2 bis 3,8 g/m2 aufzutragen. Dabei wird die Schutzschicht bevorzugt einlagig ausgebildet, ohne diesbezüglich eingeschränkt zu sein.It is preferred that the protective layer according to this third embodiment with a basis weight in a range of 1.0 g / m 2 to 6 g / m 2 and particularly preferably from 1.2 g / m 2 to 3.8 g / m 2 apply. In this case, the protective layer is preferably formed in one layer, without being limited in this regard.
In einer besonderen Ausführungsform ist das erfindungsgemäße, eine Schutzschicht aufweisende bahnförmige wärmeempfindliche Aufzeichnungsmaterial als Etikett mit rückseitiger (Selbst)Klebeschicht ausgerüstet. Der übliche Aufbau sieht dann ein bahnförmiges Substrat, bevorzugt eine Papierbahn, vor, die eine Vorderseite und eine ihr gegenüberliegende Rückseite aufweist. Rückseitig weist dann das bahnförmige wärmeempfindliche Aufzeichnungsmaterial die (Selbst)Klebeschicht auf. Vorderseitig sind auf das Substrat in dieser Reihenfolge eine erste Lage, eine die erste Lage zumindest teilweise abdeckende zweite Lage sowie eine die zweite Lage zumindest teilweise abdeckende Schutzschicht aufgetragen.In a particular embodiment, the present invention, a protective layer-like sheet-like heat-sensitive recording material according to the invention is equipped as a label with back (self) adhesive layer. The usual construction then provides a web-shaped substrate, preferably a paper web, which has a front side and a rear side opposite it. On the reverse side, the sheet-shaped heat-sensitive recording material then has the (self) adhesive layer. On the front side, a first layer, a second layer at least partially covering the first layer and a protective layer at least partially covering the second layer are applied to the substrate in this order.
Je nach Bedarf kann die Klebeschicht mit einem Releasematerial wie beispielsweise einem silikonhaltigen Releasepapier abgedeckt sein oder die äußere auf der zweiten Lage ausgebildete Schutzschicht des erfindungsgemäßen Aufzeichnungsmaterials wird mit einer zusätzlichen Releaseschicht versehen, die bevorzugt mittels eines sogenannten Fünf-Walzen-Auftragswerks aufgebracht ist. Die Releaseschicht weist dabei Trennmittel bevorzugt auf Basis von Silikonöl auf. Durch die Ausführung der Releaseschicht mit Silikonöl kann das vorgeschlagene Aufzeichnungsmaterial mit rückseitiger Selbstklebeschicht ohne Releasepapier in einer Rolle aufgewickelt werden, so dass in der Rolle die Selbstklebeschicht und die Releaseschicht in Kontakt kommen, ohne dass es zu einer dauerhaften Verklebung kommt.Depending on requirements, the adhesive layer may be covered with a release material such as a silicone-containing release paper or the outer layer formed on the second layer protective layer of the recording material according to the invention is provided with an additional release layer, preferably by means of a so-called five-Walzenauftragwerks is applied. The release layer in this case has release agents, preferably based on silicone oil. By carrying out the release layer with silicone oil, the proposed recording material having a self-adhesive backing without release paper can be wound up in a roll so that the self-adhesive layer and the release layer come into contact in the roll without permanent bonding.
In einer besonders bevorzugten Ausführungsform ist die Releaseschicht unter dem Einfluss von energiereicher Strahlung, wie beispielsweise UV- oder Elektronenstrahlung, härt- bzw. vernetzbar. Sofern die Releaseschicht mittels UV-Strahlen gehärtet werden soll, müssen die zur Herstellung dieser Schicht verwendeten Monomere bzw. Prepolymere in bekannter Weise Zusätze von Photoinitiatoren enthalten. Durch Elektronenstrahlhärtung konnte eine über ihren Querschnitt besonders gleichmäßig ausgebildete, das bedeutet ausgehärtete Releaseschicht erzielt werden.In a particularly preferred embodiment, the release layer is curable or crosslinkable under the influence of high-energy radiation, such as UV or electron radiation. If the release layer is to be cured by means of UV rays, the monomers or prepolymers used for the preparation of this layer must contain additives of photoinitiators in a known manner. By electron beam curing, a particularly uniform over its cross-section, that is cured release layer could be achieved.
Wie vorstehend bereits ausgeführt, kann nach Zufuhr von ein Schriftbild erzeugender Hitze, letztere beispielsweise abgegeben durch einen Thermodruckkopf, der optische Unterschied zwischen Schriftbild und Hintergrundweiße, zu bemessen in der optischen Druckdichte vor und nach der Schriftbildausbildung, aus Sicht der Erfinderschaft als zu gering angesehen werden. Zur Verbesserung dieses Kontrasts zwischen Schriftbild und Hintergrundweiße weist die zweite Lage des hier vorgeschlagenen bahnförmigen wärmeempfindlichen Aufzeichnungsmaterials neben den Hohlkörperpigmenten bevorzugt auch
- ▪ mindestens eine Fettsäure oder ein Fettsäureamid und/oder hydroxymethyliertes Fettsäureamid
- ▪ mindestens einen wärmeempfindlichen Sensibilisator
- ▪ mindestens eine Fettsäure oder ein Fettsäureamid und/oder hydroxymethyliertes Fettsäureamid und mindestens einen wärmeempfindlichen Sensibilisator
- ▪ at least one fatty acid or fatty acid amide and / or hydroxymethylated fatty acid amide
- ▪ at least one heat-sensitive sensitizer
- ▪ at least one fatty acid or fatty acid amide and / or hydroxymethylated fatty acid amide and at least one thermosensitive sensitizer
Zur Ausbildung des erfindungsgemäßen wärmeempfindlichen Aufzeichnungsmaterials wird dessen erste Lage mit der zur zweiten Lage zugewandten intensiven Färbung zunächst mit hoher Opazität, das heißt nahezu undurchsichtig abgedeckt durch die zweite Lage mit den Hohlkörperpigmenten. Wegen der durch die Hohlkörperpigmente verursachten Opazität der zweiten Lage lässt sich somit keinerlei oder nur wenig der Färbung der ersten Lage feststellen. Durch lokal, bevorzugt scharf begrenzte, Wärmezufuhr in Form eines beliebigen Musters, das bedeutet in Form eines wie auch immer gestalteten Schriftbildes werden die Hohlkörperpigmente der zweiten Lage beispielsweise mittels des Druckkopfes eines Thermodruckers geschmolzen, so wie es auch den Ausführungen in Absatz [0006] zu entnehmen ist. Durch die Verschmelzung bzw. das Kollabieren der Hohlkörperpigmente entsteht infolgedessen eine erhöhte Lichtdurchlässigkeit der zweiten Lage. Jedoch verbleiben in der zweiten Lage noch unregelmäßige leere Zwischenräume zwischen den geschmolzenen Hohlkörperpigmenten und nicht geschmolzenen Komponenten, die eine wenn auch reduzierte Opazität dieser zweiten Lage aufrechterhalten. Durch die bevorzugte zusätzliche Aufnahme von mindestens einer Fettsäure oder eines Fettsäureamids und/oder hydroxymethylierten Fettsäureamids und/oder von mindestens einem wärmeempfindlichen Sensibilisator in die zweite Lage wird der Effekt der Reduzierung einer konfusen Lichtstreuung deutlich verbessert, weil die mindestens eine Fettsäure oder Fettsäureamid und/oder hydroxymethyliertes Fettsäureamid und/oder der mindestens eine wärmeempfindliche Sensibilisator die nicht geschmolzenen Komponenten der zweiten Lage umhüllen und die leeren Räume innerhalb der zweiten Lage ausfüllen. Im Ergebnis kommt es zu einer signifikanten Steigerung innerhalb des optischen Unterschieds zwischen dem durch extern zugeführter Hitze, beispielsweise eines Thermokopfes, bewirktem Schriftbild und der Hintergrundweiße. Diese Steigerung innerhalb des optischen Unterschieds zwischen Schriftbild und Hintergrundweiße fällt besonders intensiv aus, wenn in die zweite Lage sowohl mindestens eine Fettsäure oder Fettsäureamid und/oder hydroxymethyliertes Fettsäureamid wie auch mindestens ein wärmeempfindlicher Sensibilisator eingebunden sind, was als ganz besonders bevorzugt seitens der Erfinderschaft angesehen wird.In order to form the heat-sensitive recording material according to the invention, its first layer with the intensive coloring facing the second layer is first covered with high opacity, that is to say almost opaque, by the second layer with the hollow-body pigments. Because of the opacity of the second layer caused by the hollow-body pigments, no or only little of the coloring of the first layer can be determined. By local, preferably sharply limited, heat in the form of any pattern, which means in the form of whatever typeface are the hollow body pigments melted the second layer, for example by means of the printhead of a thermal printer, as well as the statements in paragraph [0006] can be seen. As a result, the fusion or collapse of the hollow body pigments results in an increased light transmission of the second layer. However, in the second layer, there remain still irregular empty spaces between the molten hollow body pigments and unmelted components which maintain an albeit reduced opacity of this second layer. The preferred additional incorporation of at least one fatty acid or a fatty acid amide and / or hydroxymethylated fatty acid amide and / or at least one heat-sensitive sensitizer in the second layer of the effect of reducing a confused light scattering is significantly improved because the at least one fatty acid or fatty acid amide and / or hydroxymethylated fatty acid amide and / or the at least one heat-sensitive sensitizer envelop the unmelted components of the second layer and fill the empty spaces within the second layer. As a result, there is a significant increase in the optical difference between externally applied heat such as a thermal head, a typeface caused, and background whiteness. This increase within the optical difference between typeface and background whiteness is particularly intense when both at least one fatty acid or fatty acid amide and / or hydroxymethylated fatty acid amide and at least one thermosensitive sensitizer are included in the second layer, which is considered to be particularly preferred by the inventors ,
Unter den zur Einbindung in die zweite Lage bevorzugt vorgesehenen Fettsäuren oder Fettsäureamiden und/oder hydroxymethylierten Fettsäureamiden gelten Fettsäureamide und hier insbesondere hydroxymethylierte Fettsäureamide als bevorzugt, wobei Fettsäureamide und hydroxymethylierte Fettsäureamide im Rahmen einer bevorzugten Ausführung der vorliegenden Erfindung auch in Kombination, insbesondere in einem auf Gew.-% (atro) in der zweiten Lage bezogenen Mischungsverhältnis von 1:2 bis 2:1, innerhalb der zweiten Lage eingesetzt werden können. Als Beispiele für als bevorzugt angesehene Fettsäuren gelten Stearinsäure und Palmitinsäure, die auch insbesondere kombiniert innerhalb der zweiten Lage eingesetzt werden können. Als Beispiel für die Fettsäureamide gilt bevorzugt Stearinsäureamid, als Beispiel für hydroxymethylierte Fettsäureamide gilt bevorzugt Methylolstearinsäureamid. Auch dabei stellt die Kombination von Stearinamid und Methylolstearinamid innerhalb der zweiten Lage eine bevorzugte Ausführung zur Ausgestaltung der zweiten Lage dar.Among the fatty acids or fatty acid amides and / or hydroxymethylated fatty acid amides which are preferably provided for incorporation into the second layer, fatty acid amides and especially hydroxymethylated fatty acid amides are preferred, fatty acid amides and hydroxymethylated fatty acid amides within the scope of a preferred embodiment of the present invention also in combination, in particular in a wt .-% (atro) in the second layer related mixing ratio of 1: 2 to 2: 1, can be used within the second layer. Examples of preferred fatty acids include stearic acid and palmitic acid, which can also be used in particular in a combined manner within the second layer. As an example of the fatty acid amides is preferably stearic acid amide, as an example of hydroxymethylated fatty acid amides is preferably Methylolstearinsäureamid. Again, the combination of stearinamide and Methylolstearinamid within the second layer is a preferred embodiment for the design of the second layer.
Hinsichtlich der wärmeempfindlichen Sensibilisatoren gelten als bevorzugt solche, ausgesucht aus der Liste:
- Benzyl-p-benzyloxy-benzoat,
- 2-(2H-benzotriazol-2-yl)-p-cresol,
- p-Benzylbiphenyl,
- 1,2-Di(phenoxy)-ethan, auch EGPE genannt,
- 1,2-Di(m-methylphenoxy)ethan,
- 2-(2H-benzotriazol-2-yl)-p-cresol, auch bekannt als Tinuvin® der Firma CIBA Speciality Chemicals Inc.,
- Dibenzyloxalat,
- Benzylnaphthylether, auch BNE genannt,
- Dimethylterephthalat,
- Diphenylsulfon,
- Benzyl-p-benzyloxy benzoate,
- 2- (2H-benzotriazol-2-yl) -p-cresol,
- p-benzylbiphenyl,
- 1,2-di (phenoxy) ethane, also called EGPE,
- 1,2-di (m-methylphenoxy) ethane,
- 2- (2H-benzotriazol-2-yl) -p-cresol, also known as Tinuvin® from CIBA Specialty Chemicals Inc.,
- dibenzyl,
- Benzylnaphthyl ether, also called BNE,
- dimethyl terephthalate,
- diphenyl sulfone,
In zahlreichen Untersuchungsreihen, die dieser Schrift zu Grunde liegen, erkannte die Erfinderschaft schließlich, dass ein auf Gew.-% (atro) in der zweiten Lage bezogenes Verhältnis von
- Fettsäuren oder Fettsäureamiden und/oder hydroxymethylierten Fettsäureamiden zu wärmeempfindlichen Sensibilisatoren,
- Fettsäureamiden und/oder hydroxymethylierten Fettsäureamiden zu wärmeempfindlichen Sensibilisatoren,
- Fettsäureamiden und/oder hydroxymethylierten Fettsäureamiden zu wärmeempfindlichen Sensibilisatoren, bevorzugt ausgesucht aus der Liste umfassend Benzylnaphthylether und insbesondere 1,2-Di(phenoxy)-ethan
- 1 : 2 bis 2 : 1
- 1,0 : 1,5
bis 1,5 : 1,0
- Fatty acids or fatty acid amides and / or hydroxymethylated fatty acid amides to heat-sensitive sensitizers,
- Fatty acid amides and / or hydroxymethylated fatty acid amides to heat-sensitive sensitizers,
- Fatty acid amides and / or hydroxymethylated fatty acid amides to heat-sensitive sensitizers, preferably selected from the list comprising benzyl naphthyl ether and in particular 1,2-di (phenoxy) ethane
- 1: 2 to 2: 1
- 1.0: 1.5 to 1.5: 1.0
Ferner erkannte die Erfinderschaft, dass ein auf Gew.-% (atro) in der zweiten Lage bezogenes Verhältnis von der Gesamtmenge an Hohlkörperpigmenten zur Gesamtmenge aus Fettsäuren oder Fettsäureamiden und/oder hydroxymethylierten Fettsäureamiden und wärmeempfindlichen Sensibilisatoren, beide insbesondere ausgesucht nach allen hier offenbarten bevorzugten Ausführungen,
in einem Bereich von
- 1,0 : 2,5 bis 1 : 4,5
- 1,0 : 2,5
bis 1,0 : 3,5
in a range of
- 1.0: 2.5 to 1: 4.5
- 1.0: 2.5 to 1.0: 3.5
Die Hohlkörperpigmente innerhalb der zweiten Lage weisen eine unter starker Wärmezufuhr schmelzende Wandung aus Kunststoff, idealerweise aus thermoplastischem Harz auf. Dieser thermoplastische Harz bzw. die Hohlkörperpigment-Außenwandung selbst weist bevorzugt (Meth)Acrylnitril-Copolymer, Polyvinylchlorid, Polyvinylidenchlorid, Polystyrol, Styrolacrylat, Styrol-(meth)Acrylat-Copolymer, Polyacrylnitril, Polyacrylsäureester oder auch die Mischung aus mindestens zwei der genannten Komponenten auf. Genauso sind auch Pigmentmischungen aus unterschiedlichen Hohlkörperpigmenten für die zweite Lage vorstellbar. Im Sinne der vorliegenden Erfindung gelten auch insbesondere so genannte "Cup-shaped"-Pigmente als Hohlkörperpigmente. Im Gegensatz zu den klassischen Hohlkörperpigmenten, bei denen ein innerer Kern aus Gas, gewöhnlich aus Luft, vollständig umschlossen wird von einer Hülle aus organischen, gewöhnlich thermoplastischen Bestandteilen, weisen die "Cup-shaped"-Pigmente keine geschlossene Hülle auf und umgeben den inneren Kern nur in Form einer - möglichst weit geschlossenen - Schale bzw. Tasse (= "cup").The hollow body pigments within the second layer have a wall of plastic, ideally of thermoplastic resin, which melts under high heat input. This thermoplastic resin or the hollow body pigment outer wall itself preferably comprises (meth) acrylonitrile copolymer, polyvinyl chloride, polyvinylidene chloride, polystyrene, styrene acrylate, styrene (meth) acrylate copolymer, polyacrylonitrile, polyacrylic acid ester or else the mixture of at least two of the components mentioned , Similarly, pigment mixtures of different hollow body pigments for the second layer are conceivable. For the purposes of the present invention, so-called "cup-shaped" pigments in particular also apply as hollow-body pigments. Unlike the classic hollow body pigments in which an inner core of gas, usually air, is completely enclosed by a shell of organic, usually thermoplastic, components, the "cup-shaped" pigments do not have a closed shell and surround the inner core only in the form of a - as far as possible closed - cup or cup (= "cup").
Eine Glasübergangstemperatur für den thermoplastischen Harz der Hohlkörperpigment-Außenwandung in einem Bereich von 35 °C bis kleiner oder gleich 200 °C und bevorzugt in einem Bereich von 75 °C bis kleiner oder gleich 120 °C wurde als vorteilhaft erkannt, weil unterhalb von Temperaturen von 35 °C die Wandung der Hohlkörperpigmente bei Zimmertemperatur nicht mehr ausreichend stabil ist. Oberhalb von Temperaturen von 200 °C gibt es Handhabungsprobleme hinsichtlich einer zu starken Aufheizung der Oberfläche des Aufzeichnungsmaterials. Der bevorzugte Temperaturbereich zwischen 75 °C bis kleiner oder gleich 120 °C liefert die einfachsten Bedingungen hinsichtlich Verarbeitungsqualität und -geschwindigkeit bei der Ausbildung der zweiten Lage und bei seiner Nutzung zur Schaffung eines Schriftbildes durch Verschmelzung der Hohlkörperpigmente in Form dieses Schriftbildes, was im Sinne der vorliegenden Erfindung nicht beschränkt zu verstehen ist auf die bloße Wiedergabe von alphanumerischen Zeichen, sondern genauso von Markierungen jedweder Art, wie Zeichen, Symbole oder einfarbiger bzw. Grauton-Bilder.A glass transition temperature for the thermoplastic resin of the hollow body pigment outer wall in a range from 35 ° C to less than or equal to 200 ° C and preferably in a range from 75 ° C to less than or equal to 120 ° C has been found advantageous because below temperatures of 35 ° C, the wall of the hollow body pigments is no longer sufficiently stable at room temperature. Above temperatures of 200 ° C, there are handling problems of over heating the surface of the recording material. The preferred temperature range between 75 ° C to less than or equal to 120 ° C provides the simplest conditions in terms of processing quality and speed in the Forming the second layer and in its use to create a typeface by merging the hollow body pigments in the form of this typeface, which is not limited to the purposes of the present invention to the mere reproduction of alphanumeric characters, but just as markings of any kind, such as characters, Icons or monochrome or grayscale images.
Geeignete Bindemittel zur Einbindung in die zweite Lage des diesseits vorgeschlagenen wärmeempfindlichen Aufzeichnungsmaterials sind beispielsweise wasserlösliche Bindemittel wie Stärke, Hydroxyethylzellulose, Methylzellulose, Carboxymethylzellulose, Gelatine, Kasein, Polyvinylalkohole, modifizierte Polyvinylalkohole, Ethylen-Vinylalkohol-Coplymere, Natriumpolyacrylate, Acrylamid-Acrylat-Copolymere, Acrylamid-Acrylat-Methacrylat-Terpolymere sowie Alkalisalze von Styrol-Maleinsäureanhydrid-Copolymer oder Ethylen-Maleinsäureanhydrid-Copolymer, wobei die Bindemittel allein oder in Kombination untereinander eingesetzt werden können; auch wasserunlösliche Latexbinder wie Styrol-Butadiene-Copolymere, AcrylnitrilButadien-Copolymere und Methyl-Acrylat-Butadien-Copolymere bieten sich als Bindemittel zur Einbindung in die zweite Lage an. Im Sinne der vorliegenden Erfindung gilt Polyvinylalkohol als besonders bevorzugtes Bindemittel, das, bezogen auf das Gesamtgewicht der zweiten Lage, in einem Bereich von 12 bis 18 Gew.-% in die zweite Lage des diesseits vorgeschlagenen wärmeempfindlichen Aufzeichnungsmaterials eingebunden ist.Suitable binders for incorporation in the second layer of the heat-sensitive recording material proposed herein are, for example, water-soluble binders such as starch, hydroxyethylcellulose, methylcellulose, carboxymethylcellulose, gelatin, casein, polyvinyl alcohols, modified polyvinyl alcohols, ethylene-vinyl alcohol copolymers, sodium polyacrylates, acrylamide-acrylate copolymers, acrylamide Acrylate-methacrylate terpolymers and alkali metal salts of styrene-maleic anhydride copolymer or ethylene-maleic anhydride copolymer, which binders can be used alone or in combination with one another; Also water-insoluble latex binders such as styrene-butadiene copolymers, acrylonitrile-butadiene copolymers and methyl acrylate-butadiene copolymers are suitable as binders for incorporation into the second layer. For the purposes of the present invention is polyvinyl alcohol as a particularly preferred binder, based on the total weight of the second layer, in a range of 12 to 18 wt .-% is involved in the second layer of this proposed heat-sensitive recording material.
Neben Hohlkörperpigmenten, Fettsäuren oder Fettsäureamiden und/oder hydroxymethylierten Fettsäureamiden und wärmeempfindlichen Sensibilisatoren umfasst die zweite Lage in der Regel Gleitmittel, das sind bevorzugt Wachse wie beispielsweise und ganz besonders bevorzugt Zinkstearate und Paraffinwachse, sowie weitere Additive, worunter unter anderem Netzmittel und Entschäumer zählen.In addition to hollow body pigments, fatty acids or fatty acid amides and / or hydroxymethylated fatty acid amides and heat-sensitive sensitizers, the second layer generally comprises lubricants, which are preferably waxes such as, and most preferably, zinc stearates and paraffin waxes, as well as other additives, including but not limited to wetting agents and defoamers.
Als Grundfarbe für die zweite Lage des vorgeschlagenen wärmeempfindlichen Aufzeichnungsmaterials bietet sich insbesondere weiß an, da wärmeempfindliche Aufzeichnungsmaterialien insbesondere in ihrer angedachten und bevorzugten Verwendung als Quittung und/oder Label und/oder Fahrschein in weißer Erscheinungsform üblicherweise im Markt gewünscht sind. Auch erscheinen die nicht verschmolzenen Hohlkörperpigmente, solange keine weiteren Färbungskomponenten der zweiten Lage beigemischt sind, weiß. Das hier vorgeschlagene bahnförmige wärmeempfindliche Aufzeichnungsmaterial ist jedoch ohne Einschränkung auch mit einer insbesondere hellen Einfärbung der zweiten Lage einsetzbar und gilt infolgedessen als eine mögliche Form des vorgeschlagenen wärmeempfindlichen Aufzeichnungsmaterials.As a base color for the second layer of the proposed heat-sensitive recording material is particularly white, since heat-sensitive recording materials, especially in their intended and preferred use as a receipt and / or label and / or ticket in white appearance usually are desired in the market. Also, the non-fused hollow body pigments, as long as no further coloring components of the second layer are admixed, appear white. However, the sheet-shaped heat-sensitive recording material proposed here can be used without limitation also with a particularly light coloration of the second layer and is therefore considered as one possible form of the proposed heat-sensitive recording material.
In einer ersten möglichen, besonders einfach und kostengünstig umzusetzenden Ausführungsform der vorliegenden Erfindung ist die erste Lage ein in der Masse gefärbtes bahnförmiges Substrat, wozu dem Substrat in bevorzugter Ausführung Rußbestandteile und/oder Farbstoffe in solcher Menge beigefügt werden, dass das Substrat eine intensive Färbung aufweist. Auch wenn nicht auf Papier als bahnförmiges Substrat der vorliegenden Erfindung beschränkt, gilt grundsätzlich Papier insbesondere in einem Bereich für die flächenbezogene Masse zwischen 35 und 180 g/m2 als bevorzugtes Substrat im Sinne der vorliegenden Erfindung.In a first possible, particularly simple and cost-effective embodiment of the present invention, the first layer is a mass-dyed web-shaped substrate, to which the substrate in a preferred embodiment carbon black components and / or dyes are added in such an amount that the substrate has an intense color , Although not limited to paper as a sheet-like substrate of the present invention, paper is generally considered to be a preferred substrate in the range of 35 to 180 g / m 2 in the range of the basis weight in the sense of the present invention.
In einer zweiten möglichen Ausführungsform der vorliegenden Erfindung in all seinen in dieser Schrift beschriebenen Ausführungsformen - unter anderem hinsichtlich der Ausgestaltung von Schutzschicht, erster Lage und zweiter Lage sowie hinsichtlich aller verwendeten Komponenten und Komponentenkombinationen - wird ein bahnförmiges wärmeempfindliches Aufzeichnungsmaterial mit
- mindestens einer ersten Lage,
- einer die erste Lage zumindest teilweise abdeckenden zweiten Lage
- und mindestens eine die zweite Lage zumindest teilweise abdeckenden Schutzschicht
- ▪ ein bahnförmiges Substrat, hier besonders bevorzugt Papier,
- ▪ mindestens eine gefärbte Zwischenschicht als erste Lage,
- ▪ eine die gefärbte Zwischenschicht als erste Lage zumindest teilweise abdeckende zweite Lage
- ▪ und mindestens eine die zweite Lage zumindest teilweise abdeckende Schutzschicht
- at least one first location,
- a first layer at least partially covering the second layer
- and at least one protective layer at least partially covering the second layer
- ▪ a web-shaped substrate, here particularly preferably paper,
- ▪ at least one colored intermediate layer as first layer,
- A second layer which at least partially covers the colored intermediate layer as the first layer
- And at least one protective layer at least partially covering the second layer
Weist das hier vorgeschlagene wärmeempfindliche Aufzeichnungsmaterial gemäß zweiter möglicher Ausführungsform, wie vorstehend beschrieben, eine gefärbte Zwischenschicht auf, ist es möglich, aber nunmehr nicht mehr nötig, dass das die Zwischenschicht als erste Lage tragende Substrat eine Färbung aufweist. Die gefärbte Zwischenschicht als erste Lage kann drucktechnisch auf ein als Basisträger fungierendes Substrat beispielsweise in Form von Papier oder Folie aufgetragen sein. Bevorzugt ist diese gefärbte Zwischenschicht jedoch auf ein Substrat aufgestrichen, wobei es dann als besonders bevorzugt gilt, wenn die gefärbte Zwischenschicht mit egalisierenden Beschichtungsvorrichtungen aufgetragen ist, wie sie beispielsweise Walzenstreichwerke, Streichmesser- oder (Roll-) Rakelstreichwerke darstellen. Dann kann die gefärbte Zwischenschicht einen positiven Beitrag zur Egalisierung der Substratoberfläche leisten, womit sich einerseits die Menge an notwendigerweise aufzubringender Beschichtungsmasse zur Ausbildung der zweiten Lage reduziert und womit andererseits die Funktion der zweiten Lage unterstützt wird. Für die flächenbezogene Masse der gefärbten Zwischenschicht als erste Lage innerhalb des erfindungsgemäßen wärmeempfindlichen Aufzeichnungsmaterials hat sich ein recht weiter Bereich zwischen 2 und 10 g/m2 und bevorzugt zwischen 2 und 7 g/m2 bewährt, insbesondere bei Auftrag mit einem Streichmesser ganz besonders bevorzugt zwischen 2 und 4 g/m2, während bei drucktechnischem Auftrag der gefärbten Zwischenschicht als erste Lage auch Werte deutlich unter 2 g/m2 dann mit Schichtdicken bevorzugt zwischen 0,5 µm und 1,5 µm möglich sind. Für die Glätte (nach Bekk) der ersten Lage hat sich ein Bereich von 200 sec bis 500 sec als geeignet erwiesen, weshalb ein derartiger Bereich als bevorzugt im Sinne der vorliegenden Erfindung gilt. Insbesondere die besonders bevorzugten höheren Werte zwischen 300 sec und 500 sec werden erreicht durch Glättung des Substrats mit aufgebrachter erster Lage beispielsweise mittels eines Zwei-, Drei- oder Mehrwalzenglättwerks oder gar mittels eines Kalanders.If the heat-sensitive recording material proposed here according to the second possible embodiment has a colored intermediate layer as described above, it is possible, but no longer necessary, for the substrate bearing the intermediate layer as the first layer to have a coloration. The dyed intermediate layer as the first layer can be applied by printing technology to a substrate acting as the base support, for example in the form of paper or film. However, this colored intermediate layer is preferably applied to a substrate, wherein it is particularly preferred if the colored Intermediate layer is applied with egalisierenden coating devices, as they represent, for example, roller coater, doctor blade or (roll) doctor blade coating. Then, the colored intermediate layer can make a positive contribution to the leveling of the substrate surface, which on the one hand reduces the amount of coating material necessarily applied to form the second layer and on the other hand, the function of the second layer is supported. For the basis weight of the colored intermediate layer as the first layer within the heat-sensitive recording material according to the invention, a fairly wide range between 2 and 10 g / m 2 and preferably between 2 and 7 g / m 2 has proven to be particularly suitable, especially when applied with a doctor blade between 2 and 4 g / m 2 , while in printing technical order of the colored intermediate layer as a first layer values well below 2 g / m 2 then with layer thicknesses preferably between 0.5 .mu.m and 1.5 .mu.m are possible. For the smoothness (according to Bekk) of the first layer, a range of 200 sec to 500 sec has proven to be suitable, which is why such a range is considered to be preferred in the context of the present invention. In particular, the particularly preferred higher values between 300 sec and 500 sec are achieved by smoothing the substrate with applied first layer, for example by means of a two-, three- or Mehrwalzenglättwerks or even by means of a calender.
Gleichgültig, ob die gefärbte Zwischenschicht als erste Lage aufgedruckt oder bevorzugt aufgestrichen ist, in beiden Fällen gilt es als bevorzugt, wenn in die gefärbte Zwischenschicht anorganische ölabsorbierende Weißpigmente, bevorzugt in einem Bereich von 20 bis 45 Gew.%, bezogen auf das Gesamtgewicht der Zwischenschicht, eingebunden sind, welche für das äußere Erscheinungsbild und zur Verbesserung der späteren Bedruckbarkeit von großer Relevanz sind. Als anorganische Weißpigmente der Zwischenschicht haben sich bevorzugt solche bewährt, ausgewählt aus der Gruppe, umfassend natürliches wie kalziniertes Kaolin, Siliziumoxid, Bentonit, Kalziumkarbonat sowie Aluminiumhydroxid und hier besonders Böhmit. Auch Mischungen aus mehreren verschiedenartigen anorganischen Weißpigmenten sind vorstellbar.Regardless of whether the dyed intermediate layer is printed or preferably painted on as the first layer, in both cases it is preferred if inorganic oil-absorbing white pigments, preferably in a range from 20 to 45% by weight, based on the total weight of the intermediate layer, are added to the dyed intermediate layer , which are of great relevance for the external appearance and for the improvement of the later printability. Preferred inorganic inorganic pigments of the intermediate layer have been those selected from the group comprising natural and calcined kaolin, silica, bentonite, calcium carbonate and aluminum hydroxide, in particular boehmite here. Also mixtures of several different types of inorganic white pigments are conceivable.
Die als D50-Wert bestimmte Teilchengröße der in der gefärbten Zwischenschicht vorliegenden anorganischen Weißpigmente liegen bevorzugt in einem Bereich von kleiner 2 µm. Als vorteilhaft haben sich Pigmente erwiesen, bei denen eine Teilchengrößenverteilung von 34 bis 40 Gew.-% kleiner 1 µm und 57 bis 63 Gew.-% kleiner 2 µm, jeweils bezogen auf die Gesamtmenge an Weißpigmenten in der Zwischenschicht, vorliegt.The particle size of the inorganic white pigments present in the colored interlayer, determined as the D50 value, is preferably in a range of less than 2 μm. Pigments having a particle size distribution of from 34 to 40% by weight of less than 1 μm and from 57 to 63% by weight of less than 2 μm, in each case based on the total amount of white pigments in the intermediate layer, have proved to be advantageous.
Zur Erzielung einer intensiven Färbung der Zwischenschicht als erste Lage weist diese bevorzugt Rußbestandteile und/oder Farbstoffe in entsprechender Menge, im Fall von Rußpigmenten bevorzugt in einem Bereich von 30 bis 40 Gew.%, bezogen auf das Gesamtgewicht der Zwischenschicht, auf. Als vorteilhaft haben sich dabei Rußpigmente mit einer durchschnittlichen Teilchengröße von 50 nm erwiesen.To achieve intensive coloring of the intermediate layer as the first layer, it preferably has carbon black constituents and / or dyes in an appropriate amount, in the case of carbon black pigments preferably in a range from 30 to 40% by weight, based on the total weight of the intermediate layer. Carbon black pigments having an average particle size of 50 nm have proved to be advantageous.
Neben den anorganischen Weißpigmenten und den Rußpigmenten enthält die als erste Lage gefärbte und zudem pigmentierte Zwischenschicht mindestens ein Bindemittel bevorzugt auf Basis eines synthetischen Polymers, wobei beispielsweise Styrol-Butadien-Latex besonders gute Ergebnisse liefert. Die Verwendung eines synthetischen Bindermittels unter Beimischung mindestens eines natürlichen Polymers stellt eine besonders geeignete Ausführungsform dar. Ebenfalls ganz besonders bevorzugt als Bindemittel ist hochverseifter Polyvinylalkohol. Im Rahmen von Versuchen wurde ferner festgestellt, dass mit einem Verhältnis
Bindemittel : Gesamtmenge aus Weißpigmenten und Rußpigmenten
innerhalb der pigmentierten Zwischenschicht zwischen 1:3 und 1:4 eine besonders geeignete Ausführungsform vorliegt.In addition to the inorganic white pigments and the carbon black pigments, the intermediate layer dyed as the first layer and additionally pigmented contains at least one binder, preferably based on a synthetic polymer, with styrene-butadiene latex, for example, giving particularly good results. The use of a synthetic binder with the admixture of at least one natural polymer is a particularly suitable embodiment. Also very particularly preferred as a binder is highly saponified polyvinyl alcohol. In the context of experiments it was further found that with a ratio
Binder: total amount of white pigments and carbon black pigments
within the pigmented intermediate layer between 1: 3 and 1: 4 is a particularly suitable embodiment.
In einer dritten möglichen Ausführungsform der vorliegenden Erfindung in all seinen in dieser Schrift beschriebenen Ausführungsformen - unter anderem hinsichtlich der Ausgestaltung von Schutzschicht, erster Lage und zweiter Lage sowie hinsichtlich aller verwendeten Komponenten und Komponentenkombinationen - wird ein bahnförmiges wärmeempfindliches Aufzeichnungsmaterial mit
- mindestens einer ersten Lage,
- einer die erste Lage zumindest teilweise abdeckenden zweiten Lage
- und mindestens eine die zweite Lage zumindest teilweise abdeckenden Schutzschicht
- ▪ ein bahnförmiges Substrat, hier besonders bevorzugt Papier,
- ▪ eine erste Zwischenschicht mit zur zweiten Zwischenschicht eingeebneter Oberfläche,
- ▪ eine zweite Zwischenschicht mit intensiver Färbung als erste Lage,
- ▪ eine die gefärbte Zwischenschicht als erste Lage zumindest teilweise abdeckende zweite Lage
- ▪ und mindestens eine die zweite Lage zumindest teilweise abdeckende Schutzschicht
- at least one first location,
- a first layer at least partially covering the second layer
- and at least one protective layer at least partially covering the second layer
- ▪ a web-shaped substrate, here particularly preferably paper,
- A first intermediate layer with a surface leveled to the second intermediate layer,
- ▪ a second intermediate layer with intensive coloring as the first layer,
- A second layer which at least partially covers the colored intermediate layer as the first layer
- And at least one protective layer at least partially covering the second layer
In dieser zuletzt offenbarten dritten Ausführungsform ist es die Aufgabe der ersten Zwischenschicht, für die anschließend aufzutragende zweite Zwischenschicht eine besonders ebene Oberfläche zu gewährleisten, damit die flächenbezogene Masse der zweiten Zwischenschicht besonders niedrig, bevorzugt in einem Bereich zwischen 1 und 8 g/m2 und noch besser zwischen 1 und 5 g/m2, insbesondere bei Auftrag mit einem Streichmesser ganz besonders bevorzugt zwischen 1,5 und 3,0 g/m2, gewählt werden kann. Auf diese Weise kann die Menge an Rußpigmenten, die innerhalb des Recyclings zu Schwierigkeiten führen kann, reduziert werden. Während Aufbau und Inhaltstoffe der zweiten Zwischenschicht gemäß dritter Ausführungsform des hier vorgeschlagenen Aufzeichnungsmaterials identisch gewählt werden können zu Aufbau und Inhaltstoffen der Zwischenschicht gemäß zweiter Ausführungsform, weist die erste Zwischenschicht gemäß dritter Ausführungsform hauptsächlich Weißpigmente, wie offenbart in Absatz [0042], Bindemittel und die sonst auch üblichen Additive auf. Entscheidend ist ihr Auftrag mit einer egalisierenden Beschichtungsvorrichtung, wie beispielsweise mit einem Streichmesser- oder (Roll-) Rakelstreichwerk mit anschließender Behandlung mittels Glättwerk und/oder Kalander.In this last disclosed third embodiment, it is the task of the first intermediate layer, for the subsequently applied second intermediate layer to ensure a particularly flat surface, so that the basis weight of the second intermediate layer is particularly low, preferably in a range between 1 and 8 g / m 2 and even better between 1 and 5 g / m 2 , especially when applied with a doctor blade very particularly preferably between 1.5 and 3.0 g / m 2 , can be selected. In this way, the amount of carbon black pigments, which can lead to difficulties within the recycling, can be reduced. While the constitution and ingredients of the second intermediate layer according to the third embodiment of the recording material proposed here can be selected identically to the structure and ingredients of the intermediate layer according to the second embodiment, the first intermediate layer according to the third embodiment mainly comprises white pigments as disclosed in paragraph [0042], binders and others also usual additives. Decisive is their job with a leveling coating device, such as with a doctor blade or (roller) doctor blade coating with subsequent treatment by means of calender and / or calender.
In einer ersten, sehr einfachen Ausführungsform der Erfindung ist die erste Lage ein in der Masse gefärbtes bahnförmiges Substrat (11). Auf das Substrat (11) ist dann die zweite Lage (2) aufgetragen, für die grundsätzlich ein Bereich hinsichtlich der flächenbezogenen Masse zwischen 2 und 10 g/m2 als bevorzugt gilt, als ganz besonders bevorzugt ist ein Bereich zwischen 4 und 8 g/m2 zu betrachten. In verschiedenen Untersuchungsreihen wurde erkannt, dass bei einer flächenbezogenen Masse der zweiten Lage von unter 2 g/m2 die Abdeckung der ersten Lage oft nicht mehr ausreichend zu gewährleisten ist, während eine Ausbildung der zweiten Lage mit einer flächenbezogenen Masse von weit mehr als 10 g/m2 aus wirtschaftlichen Gründen nicht sinnvoll ist.In a first, very simple embodiment of the invention, the first layer is a mass-dyed web-shaped substrate (11). On the substrate (11) then the second layer (2) is applied, for which in principle a range in terms of basis weight between 2 and 10 g / m 2 is considered to be preferred, as very particularly preferred is a range between 4 and 8 g / m 2 . In various series of tests, it was recognized that with a basis weight of the second layer of less than 2 g / m 2, the coverage of the first layer is often no longer adequately ensured, whereas a second layer with a basis weight of well over 10 g / m 2 for economic reasons does not make sense.
Sollen in das Substrat gewöhnlich aus produktionstechnischen Überlegungen keine färbenden Bestandteile eingearbeitet sein, gilt es - wie in der Beschreibung weiter vorne ausführlich erläutert - als bevorzugt, auf das dann auch ungefärbt ausführbare bahnförmige Substrat eine pigmentierte Zwischenschicht als erste Lage auszubilden.
Die in Beschreibung und Patentansprüchen gemachten Angaben zur flächenbezogenen Masse, zu Gew.-% (Gewichts-%) und zu Gew.-Teilen (Gewichts-Teilen) beziehen sich jeweils auf das "atro"-Gewicht, d.h. absolut trockene Gewichtsteile. In den Ausführungen zu den Hohlkörperpigmenten der zweiten Lage sind die diesbezüglichen Zahlenangaben berechnet aus dem "lutro"-Gewicht, d.h. lufttrockene Gewichtsteile, abzüglich des Gewichtsanteils von Wasser im Inneren der Pigmente in ihrer Lieferform.The surface mass,% by weight (% by weight) and parts by weight (parts by weight) given in the specification and claims refer to the "atro" weight, respectively. absolutely dry parts by weight. In the comments on the hollow body pigments of the second layer, the relevant figures are calculated from the "lutro" weight, i. air-dry parts by weight, less the proportion by weight of water in the interior of the pigments as supplied.
Die Erfindung soll anhand des folgenden Beispiels weiter verdeutlicht werden.The invention will be further clarified by the following example.
Auf einer Langsieb-Papiermaschine wird als Substrat eine Papierbahn aus gebleichten und gemahlenen Laub- und Nadelholzzellstoffen mit einer flächenbezogenen Masse von 67 g/m2 unter Zusatz üblicher Zuschlagstoffe in üblichen Mengen hergestellt. Auf die eine Seite des Substrates wird mit einem Streichmesser eine
- zu 36,4 Gew.-% Aluminiumhydroxid als Weißpigment,
- zu 36,4 Gew.-% Rußpigment,
- und zu 20,3 Gew.-% hochverseifter Polyvinylalkohol als Bindemittel
- to 36.4% by weight of aluminum hydroxide as white pigment,
- to 36.4% by weight carbon black pigment,
- and to 20.3 wt .-% highly saponified polyvinyl alcohol as a binder
Auf die Zwischenschicht wird eine zweite Lage unter Nutzung eines Rollrakelstreichwerks aufgetragen und getrocknet mit
- 15,3 Gew.-% (atro) hochverseifter Polyvinylalkohol als Bindemittel,
- 19,8 Gew.-% Hohlkörperpigmente,
- 29,8 Gew.% Stearinsäureamid,
- 29,8 Gew.-% 1,2-Di(phenoxy)-ethan als wärmeempfindlichen Sensibilisator und
- zusammen 4,4 Gew.-% Zinkstearate und Paraffinwachse als Gleitmittel.
- 15.3% by weight (atro) highly saponified polyvinyl alcohol as binder,
- 19.8% by weight of hollow body pigments,
- 29.8% by weight stearic acid amide,
- 29.8 wt .-% 1,2-di (phenoxy) ethane as a heat-sensitive sensitizer and
- together 4.4% by weight of zinc stearates and paraffin waxes as lubricants.
Für die Herstellung der Schutzschicht wird eine Beschichtungsmasse umfassend
- Kaolin als anorganisches Pigment (40 Gewichtsteile),
- ein Diaceton-modifizierter Polyvinylalkohol als Bindemittel (100 Gewichtsteile),
- Zinkstearat als Wachs (26,5 Gewichtsteile)
- und Adipinsäuredihydrazid als Vernetzer (10 Gewichtsteile)
- Kaolin as an inorganic pigment (40 parts by weight),
- a diacetone-modified polyvinyl alcohol as a binder (100 parts by weight),
- Zinc stearate as wax (26.5 parts by weight)
- and adipic dihydrazide as crosslinker (10 parts by weight)
Das so fertig gestellte wärmeempfindliche Aufzeichnungsmaterial wird einem Thermodrucker zugeführt. Die Hohlkörperpigmente der zweiten Lage werden zusammen mit dem Stearinsäureamid und dem wärmeempfindlichen Sensibilisator gemäß eines vorbestimmten Karomusters durch den Druckkopf des Thermodruckers zum Schmelzen gebracht, so dass Bereiche in der zweiten Lage mit verschmolzenen Komponenten und ausgefüllten Zwischenbereichen und Bereiche mit unverschmolzenen Komponenten und unausgefüllten Zwischenbereichen ent stehen. Das so hergestellte Aufzeichnungsmaterial weist somit ein sehr gut erkennbares, scharfkantiges Schriftbild auf mit geschwärzten Bereichen dort, wo die Hohlkörperpigmente in der zweiten Lage durch die Wärmezufuhr des Druckkopfes des Thermodruckers miteinander verschmolzen sind. Die geschwärzten Bereiche entstammen der einheitlichen Färbung der Zwischenschicht, deren Färbung durch die transparenten Bereiche der zweiten Lage mit den dort verschmolzenen Hohlkörperpigmenten zu erkennen sind.The thus-finished heat-sensitive recording material is fed to a thermal printer. The hollow particles of the second layer are melted together with the stearic acid amide and the heat sensitive sensitizer according to a predetermined check pattern by the printhead of the thermal printer so that areas in the second layer with fused components and filled intermediate areas and areas with unfused components and unfilled intermediate areas ent stand. The thus prepared recording material thus has a very well recognizable, sharp-edged typeface on with blackened areas where the hollow body pigments are fused together in the second layer by the heat input of the printhead of the thermal printer. The blackened areas originate from the uniform color of the intermediate layer, the color of which can be recognized by the transparent areas of the second layer with the hollow body pigments fused there.
Proben des so hergestellten erfindungsgemäßen wärmeempfindlichen Aufzeichnungsmaterials werden nunmehr einer weiteren messtechnischen Untersuchung zugeführt. Zu diesem Zweck wird die Weiße des erfindungsgemäßen wärmeempfindlichen Aufzeichnungsmaterials bei Verwendung von Licht einmal mit, einmal ohne UV-Anteil bestimmt, wobei die Messungen durchgeführt werden entsprechend den Vorgaben der ISO 2469 / ISO 2470 mit der Maßgabe, dass bei den hier vorgenommenen Messungen D65-Licht verwendet wird bei einem Betrachtungswinkel von 8°. Die Weißemessungen erfolgen dabei unter Verwendung eines Gerätes der Type Elrepho 3000 (Lichtart D 65/10). Die ermittelten Werte liegen bei 56 % (mit UV-Anteil) bzw. bei 52 % (ohne UV), was weitestgehend zwar einem grauen Papier entspricht, angesichts dieser Beschichtungs- und Funktionstechnologie aber diesseits als akzeptabel und verkaufsfähig angesehen wird.Samples of the heat-sensitive recording material according to the invention thus produced are now subjected to a further metrological examination. For this purpose, the whiteness of the heat-sensitive recording material according to the invention is determined once with, once without UV, the measurements being carried out in accordance with the specifications of ISO 2469 / ISO 2470, with the proviso that in the measurements made here D65- Light is used at a viewing angle of 8 °. The white measurements are carried out using a device of the type Elrepho 3000 (illuminant D 65/10). The values determined are 56% (with UV content) and 52% (without UV), which largely corresponds to a gray paper, but in view of this coating and functional technology this is considered to be acceptable and salable.
Zur messtechnischen Erfassung des optischen Unterschieds zwischen Schriftbild und Hintergrundweiße wird die jeweilige optischen Druckdichte vor und nach der Ausbildung eines schwarz/weiß kariert-gestalteten Thermoprobeausdrucks mit einem Gerät der Type Atlantek 400 der Firma Printrex (USA) ermittelt, wobei ein Thermokopf mit Auflösung von 300 dpi und einer Energie pro Flächeneinheit von 16 mJ/mm2 zum Einsatz kommt. Für jede Einzelbestimmung wird der jeweils nicht bedruckte bzw. wird der jeweils Thermo-bedruckte Bereich an drei Stellen mit dem Densitometer Gretag MacBeth TYPE D19C NB/U gemessen (Firma Gretag MacBeth, 8105 Regensdorf, Schweiz). Für die unbedruckten Bereiche ergibt sich eine mittlere optische Dichte von 0,33 ODU (Optical Density Units), für die Thermo-bedruckten Bereiche eine mittlere optische Dichte von 1,22 ODU. Mit einer Differenz von 0,89 ODU als Kontrast zwischen bedruckten und unbedruckten Bereichen beweist die vorliegende Erfindung, dass ein ausgebildetes Schriftbild gut zu erkennen ist, was den Wert der vorliegenden Erfindung unterstreicht.To measure the optical difference between the typeface and the background white, the respective optical print density is determined before and after the formation of a black-and-white checkered thermo-printout with an Atlantek 400 device from Printrex (USA) using a thermal head with a resolution of 300 dpi and an energy per unit area of 16 mJ / mm 2 is used. For each individual determination, the respectively non-printed area or the respective thermo-printed area is measured at three locations with the Gretag MacBeth Densitometer TYPE D19C NB / U densitometer (Gretag MacBeth, 8105 Regensdorf, Switzerland). The unprinted areas have a mean optical density of 0.33 ODU (Optical Density Units), for the thermo-printed areas a mean optical density of 1.22 ODU. With a difference of 0.89 ODU as the contrast between printed and unprinted areas, the present invention proves that a skilled typeface is easy to see, underscoring the value of the present invention.
- (1)(1)
- erste Lage, aufweisend eine intensive Färbungfirst layer, having an intense coloration
- (2)(2)
- zweite Lagesecond location
- (2-1)(2-1)
- durchscheinende Bereiche der zweiten Lagetranslucent areas of the second layer
- (2-2)(2-2)
- undurchsichtige Bereiche der zweiten Lageopaque areas of the second layer
- (10)(10)
- Substratsubstratum
- (11)(11)
- Substrat als erste LageSubstrate as a first layer
- (21)(21)
- Zwischenschicht als erste LageInterlayer as the first layer
- (40)(40)
- Schutzschichtprotective layer
Claims (11)
- Heat-sensitive recording material in web form, having at least one first ply and a second ply at least partly concealing the first ply, whereo the first ply, at least facing the second ply, has an intensive coloration ando the second ply comprises hollow-body pigments which can be melted to form a script by locally confined heat treatment,characterized in that the first ply is concealed virtually opaquely by the second ply and in that the recording material has at least one protective layer at least partly concealing the second ply, and where the at least one protective layer at least partly concealing the second ply comprises as constituents at least:- at least one inorganic pigment,- at least one binder,- at least one wax.
- Heat-sensitive recording material in web form according to Claim 1, characterized in that the hollow-body pigments of the second ply are fused in the form of a script by means of locally confined heat treatment.
- Heat-sensitive recording material in web form according to either of Claims 1 and 2, characterized in that the at least one protective layer at least partly concealing the second ply additionally comprises at least:- optical brighteners,- at least one crosslinker.
- Heat-sensitive recording material in web form according to any of Claims 1 to 3, characterized in that the at least one binder of the protective layer is selected from the list encompassing:• self-crosslinking binders selected from the group encompassing styrene-acrylic ester copolymer, a styrene/acrylic ester copolymer containing acrylamide groups, and, very preferably, a copolymer based on acrylonitrile, methacrylamide and acrylate,• polyvinyl alcohol,• polyvinyl alcohol modified with carboxyl, diacetone or silanol groups,• mixtures of different carboxyl-, diacetone- or silanol-modified polyvinyl alcohols.
- Heat-sensitive recording material in web form according to Claim 4, characterized in that the at least one binder of the protective layer is selected from the list encompassing:• polyvinyl alcohol,• polyvinyl alcohol modified with carboxyl, diacetone or silanol groups,• mixtures of different carboxyl-, diacetone- or silanol-modified polyvinyl alcohols.
- Heat-sensitive recording material in web form according to any of Claims 1 to 5, characterized in that the at least one wax is a zinc stearate.
- Heat-sensitive recording material in web form according to any of Claims 3 to 6, characterized in that the at least one crosslinker of the protective layer is selected from the list encompassing:▪ cyclic ureas,▪ methylolurea,▪ ammonium zirconium carbonate,▪ polyamine-epichlorohydrin resin.
- Heat-sensitive recording material in web form according to any of Claims 1 to 7, characterized in that the heat-sensitive recording material in web form comprises in its second ply, besides the hollow-body pigments, also▪ at least one fatty acid amide and/or hydroxymethylated fatty acid amide
or▪ at least one heat-sensitive sensitizeror▪ at least a) a fatty acid amide and/or hydroxymethylated fatty acid amide and b) at least one heat-sensitive sensitizer, and where the heat-sensitive sensitizers are selected from the list encompassing:
benzyl p-benzyloxybenzoate, 2-(2H-benzotriazol-2-yl)-p-cresol, p-benzylbiphenyl, 1,2-di(phenoxy)-ethane, 1,2-di(m-methylphenoxy)ethane, 2-(2H-benzotriazol-2-yl)-p-cresol, dibenzyl oxalate, benzyl naphthyl ether, dimethyl terephthalate, diphenyl sulfone. - Heat-sensitive recording material in web form according to Claim 8, characterized in that a ratio, based on wt% in the second ply, of fatty acid amides and/or hydroxymethylated fatty acid amides to heat-sensitive sensitizers, preferably selected from the list encompassing benzyl naphthyl ether and 1,2-di(phenoxy) ethane, is in a range from 1:2 to 2:1, where the figure for wt% is based on absolutely dry parts by weight.
- Heat-sensitive recording material in web form according to either of Claims 8 and 9, characterized in that a ratio, based on wt% in the second ply, of the total amount of hollow-body pigments to the total amount of fatty acid amides and/or hydroxymethylated fatty acid amides and heat-sensitive sensitizers is in a range from 1.0:2.5 to 1:4.5, where the figure for wt% is based on absolutely dry parts by weight.
- Heat-sensitive recording material in web form according to any of Claims 1 to 10, characterized in that the recording material, as a label, has an adhesive layer or self-adhesive layer on the reverse side.
Priority Applications (3)
Application Number | Priority Date | Filing Date | Title |
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EP14183864.9A EP2993055B1 (en) | 2014-09-06 | 2014-09-06 | Web-shaped heat-sensitive recording material with a protective layer |
ES14183864T ES2731553T3 (en) | 2014-09-06 | 2014-09-06 | Heat-sensitive band-shaped recording material with protective layer |
EP19156809.6A EP3517309A1 (en) | 2014-09-06 | 2014-09-06 | Web-shaped heat-sensitive recording material |
Applications Claiming Priority (1)
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EP14183864.9A EP2993055B1 (en) | 2014-09-06 | 2014-09-06 | Web-shaped heat-sensitive recording material with a protective layer |
Related Child Applications (2)
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EP19156809.6A Division-Into EP3517309A1 (en) | 2014-09-06 | 2014-09-06 | Web-shaped heat-sensitive recording material |
EP19156809.6A Division EP3517309A1 (en) | 2014-09-06 | 2014-09-06 | Web-shaped heat-sensitive recording material |
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EP2993055A1 EP2993055A1 (en) | 2016-03-09 |
EP2993055B1 true EP2993055B1 (en) | 2019-04-03 |
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EP14183864.9A Active EP2993055B1 (en) | 2014-09-06 | 2014-09-06 | Web-shaped heat-sensitive recording material with a protective layer |
EP19156809.6A Pending EP3517309A1 (en) | 2014-09-06 | 2014-09-06 | Web-shaped heat-sensitive recording material |
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EP19156809.6A Pending EP3517309A1 (en) | 2014-09-06 | 2014-09-06 | Web-shaped heat-sensitive recording material |
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ES (1) | ES2731553T3 (en) |
Families Citing this family (8)
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DE102017131276A1 (en) | 2017-12-22 | 2019-06-27 | Mitsubishi Hitec Paper Europe Gmbh | Recyclable release substrate |
DE102017131277A1 (en) | 2017-12-22 | 2019-06-27 | Mitsubishi Hitec Paper Europe Gmbh | Recyclable barrier paper |
DE102018111495B4 (en) | 2018-05-14 | 2020-04-09 | Papierfabrik August Koehler Se | Thermoresponsive paper coatings based on cellulose derivatives |
US20220127478A1 (en) * | 2019-03-20 | 2022-04-28 | Matsumoto Yushi-Seiyaku Co., Ltd. | Hollow resin particles for thermosensitive recording media |
ES2937111T3 (en) | 2020-08-19 | 2023-03-24 | Mitsubishi Hitec Paper Europe Gmbh | Developer-free heat sensitive recording material |
DE102021115909A1 (en) | 2021-06-18 | 2022-12-22 | Koehler Innovation & Technology Gmbh | Heat-sensitive recording materials |
WO2023017127A2 (en) * | 2021-08-11 | 2023-02-16 | Koehler Innovation & Technology Gmbh | Heat-sensitive recording material |
DE102021133333A1 (en) | 2021-12-15 | 2023-06-15 | Koehler Innovation & Technology Gmbh | Heat-sensitive recording material in sheet form |
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ES2731553T3 (en) | 2019-11-15 |
EP3517309A1 (en) | 2019-07-31 |
EP2993055A1 (en) | 2016-03-09 |
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