Removable covering paint scheme of layers arranged on a heat-sensitive carrier, thermal printer, and method for thermal printing such a carrier
10005307 ยท 2018-06-26
Inventors
- Gyula Langos (Paszto, HU)
- Janosne Kocsardi (Nagykovacsi, HU)
- Laszlo Juhasz (Budapest, HU)
- Peter Juhasz (Budapest, HU)
- Peter Kos (Budapest, HU)
- Zoltan Konya (Tiszasziget, HU)
- Akos Kukovecz (Domaszek, HU)
Cpc classification
A63F3/0665
HUMAN NECESSITIES
B41J11/0015
PERFORMING OPERATIONS; TRANSPORTING
B41M3/005
PERFORMING OPERATIONS; TRANSPORTING
B41M2205/04
PERFORMING OPERATIONS; TRANSPORTING
B41M5/42
PERFORMING OPERATIONS; TRANSPORTING
B41M5/426
PERFORMING OPERATIONS; TRANSPORTING
B41M5/44
PERFORMING OPERATIONS; TRANSPORTING
B41M2205/40
PERFORMING OPERATIONS; TRANSPORTING
B41M5/443
PERFORMING OPERATIONS; TRANSPORTING
B41M2205/38
PERFORMING OPERATIONS; TRANSPORTING
International classification
B41M5/42
PERFORMING OPERATIONS; TRANSPORTING
B41M5/44
PERFORMING OPERATIONS; TRANSPORTING
A63F3/06
HUMAN NECESSITIES
B41J11/00
PERFORMING OPERATIONS; TRANSPORTING
Abstract
This invention relates to a removable multilayered aqueous flexo covering paint scheme of layers arranged on a heat sensitive carrier (1) provided by a heat sensitive layer (2) to be colored by applying heat, and a coat of lacquer (3) containing 70% acrylate oligomer, 22% acrylate monomer, 5% photo-initiator and 3% silicone is arranged on the heat sensitive layer (2); a disperse parting layer (4) containing 20-35% soot paste, 25% aqueous acrylate emulsion, 6% calcined kaolin, 1% antifoam agent and spread improver, 3% c rheological modifier and 45% water is arranged on the coat of lacquer (3); and a covering paint layer (5) containing carbon nanotubes functionalized by hydroxyl, carbonyl and carboxy groups is arranged on the disperse parting layer (4). A method and apparatus for thermal printing of a carrier (1) preprinted by the removable multilayered aqueous flexo covering paint scheme of layers and provided by a heat sensitive layer (2) to be colored by applying heat is also disclosed.
Claims
1. A heat sensitive carrier (1) provided with a heat sensitive layer (2) to be colored by applying heat and a removable aqueous flexo covering paint scheme of layers, characterized in that the paint scheme of layers comprising a coat of lacquer (3) containing 70% acrylate oligomer, 22% acrylate monomer, 5% photo-initiator and 3% silicone is-arranged on the heat sensitive layer (2); a disperse parting layer (4) containing 20% soot paste with 35% of soot, 25% aqueous acrylate emulsion, 6% calcined kaolin, 1% antifoam agent and spread improver, 3% rheological modifier and 45% water arranged on the coat of lacquer (3); and a topcoat paint layer (5) containing carbon nanotubes functionalized by hydroxyl, carbonyl and carboxy groups arranged on the disperse parting layer (4), and wherein measuring field (9) is printed with an ink containing carbon nanotubes directly onto the surface of the heat sensitive layer (2) of the heat sensitive carrier (1).
2. The heat sensitive carrier (1) according to claim 1, characterized in that the length of the carbon nanotubes arranged in the topcoat layer (5) is between 4-20 m.
3. The heat sensitive carrier (1) according to claim 2, characterized in that the topcoat layer (5) is formed by 32% of an aluminum paste containing 70% Al, 3% nanotube paste, 60% aqueous acrylate emulsion, 1% combination of antifoam agent and spread improver, and 4% of water.
4. The heat sensitive carrier (1) according to claim 3, characterized in that the carbon nanotube paste consists of 5% hydrophilized carbon nanotubes having a length of 4-20 m, 20% aqueous acrylate emulsion, and 2% combination of an antifoaming and a spread improver agent, 0.3% pH adjusting additive, 0.2% biocide additive, 3% isopropyl alcohol, and 69.5% of water.
5. A method for thermal printing of a heat sensitive carrier (1) provided with a heat sensitive layer (2) to be colored by applying heat and preprinted by a removable aqueous flexo covering paint scheme of layers including a topcoat paint layer (5) containing carbon nanotubes functionalized by hydroxyl, carbonyl and carboxy groups, the method comprising the steps of subjecting the heat-sensitive layer (2) of the carrier (1) to heat radiation generated by a thermal printing head (6) characterized in that before applying said thermal radiation, measuring field (9) being formed on the heat-sensitive layer (2) of the carrier (1); determining experimentally a function (Fr) between the electric resistance and temperature as well as relative humidity of environment of the flexo covering paint scheme of layers; then determining a value of relative humidity (RHM) belonging to a maximum of a function (Fs) between thermal conductivity and temperature (T1, T2, T3) as well as relative humidity of environment of the flexo covering paint scheme of layers; measuring electric resistance (R1) of the measuring field (9); determining relative humidity (RH1) of the measuring field (9) by using the value of the resistance (R1) and the function (Fr); and changing the value of relative humidity (RH1) into the value of relative humidity (RHM) in a space surrounding the carrier (1).
6. A method according to claim 5, characterized by forming a measuring field (9) on the heat-sensitive layer (2) of the carrier (1), consisting of a disperse parting layer (4) containing 20% soot paste with 35% of soot, 25% aqueous acrylate emulsion, 6% calcined kaolin, 1% combination of antifoam agent and spread improver, 3% rheological modifier and 45% water, and a topcoat paint layer (5) containing carbon nanotubes functionalized by hydroxyl, carbonyl and carboxy groups arranged on the disperse parting layer (4).
Description
(1) The invention will be described in detail with reference to the accompanying drawings. In the drawings:
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(9)
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(11)
(12) In
(13) The heat-sensitive layer 2 is to be discolored by the effect of the thermal radiation of a thermal printing head 6 to form a visible change 7 of appropriate value of density, that is to be darkened in radiation range of heat penetrating the layer 2. If the visible change 7 should be temporarily hidden, as it is a requirement in the case of scratch-off lottery tickets, a finish coat having adequate thermal conductivity should be arranged, preferably printed, on the top of the heat sensitive layer 2, that makes the otherwise visible change 7 invisible to unauthorized persons for. However, due to the closed surface structure of the heat-sensitive layer 2 of the carrier 1 it is difficult to be printed. Even if it is printable by a given ink, the print usually cannot be removed without any damage of the heat-sensitive layer 2. A complex requirement of having printability and removability for example by scratch-off at the same time requires several layers of paint to be applied, but the paint layers should not form a strong surface bond with each other. Nevertheless, the more the number of layers of paint, the lower the thermal conductivity of the layer scheme, which adversely affects the safe readability of the thermal print.
(14) Therefore, to improve the thermal conductivity of the paint scheme the applicant have developed a thermally conductive, water-based polar solvent flexographic ink according to the invention for thermal papers H, which can be scratched off without any damage of the thermal print, and in which a channel system improving heat conductivity by using multi-walled carbon nanotubes are applied.
(15) Both single-walled and multi-walled carbon nanotubes are extraordinally good conductors of heat, their coefficient of thermal conductivity falls in a range from hundreds to thousands W/mK depending on a degree of purity and the number of their defects. This value is greater by several orders of magnitude than the heat conductivity of polymer resins forming the raw material for paints, which is typically within 1 W/(mK) range. Currently, large-scale production (hundreds of tons/year) of single-walled carbon nanotubes is not running anywhere in the world, so to improve the thermal properties multi-walled carbon nanotubes are used according to the present invention.
(16) Since the thickness of a scratch-off ink multilayer system is generally 2-8 microns, the length of carbon nanotubes used may be between 120 nm-500 microns, depending on the method of its production and after-treatment. Too short tubes do not form continuous thermal duct system in the ink matrix, but too long ones are oriented in the plane of the print in any case and therefore they are not suitable for conducting heat through the layers. We have experimentally determined the optimal length of the nanotubes in the flexo ink, the optimum of which falls between 4 and 20 microns.
(17) The carbon nanotubes are essentially hydrophobic materials, but paints are polar types (water- or ethanol-based) and therefore nanotubes having even adequate length cannot be dispersed appropriately in a paint without some chemical modification. In this regard, hydroxyl, carbonyl and carboxy groups have been formed by oxidative functionalization on the nanotubes. We have checked on many ways of functionalization, and the following procedure has been found to be optimal:
(18) providing 5 g of carbon nanotubes in 500 cm.sup.3 of HNO3 solution of 65% concentration,
(19) the mixture was boiled reflowing on 300 C. for 6 hours,
(20) the system was allowed to cool to room temperature in 12 hours in unfiltered state,
(21) washed to neutral pH with distilled water,
(22) dried in an air drying box on 80 C. for 4 hours.
(23) As regards the use in a topcoat paint layer 5 it is a critical step to crush the material in a mortar in every 30 minutes during drying. If this step is not done the resulting material can not be sufficiently dispersed into the flexo ink. Laboratory experiments have shown that a paint having a nanotube content of 2-5% cannot be printed directly because of its very high viscosity, thus making the nanotube not directly applicable to make a printing paint. Therefore, a nanotube paste containing 5% of nanotubes was prepared. Measurements made by both the laboratory and industrial scale test prints demonstrated that the nanotube content imparts exceptionally good thermal and electric conductivity to the paint. As regards size compatibility, as mentioned above, application of nanotubes having a size of approx. 4-20 microns is advantageous, from which a paste containing 5% nanotubes may be prepared by bead-grinder, and then can be mixed into a polar type aqueous paint system. According to our analyzes the nanotubes in the internal structure of the ink matrix are located perpendicularly to the plane of the carrier 1, e.g. paper sheet, owing to forces imparting to the matrix during printing, meshing some extent the paint film, and protruding from the top of the paint layer 5 to accept the heat energy to be conveyed.
(24) Preparation of carbon nanotube paste takes place as follows: mixing 5% multi-wall hydrophilized carbon nanotube of 4-20 microns long, with 20% aqueous acrylic emulsion, and 2% antifoam spread improver, 0.3% pH adjustment agent, 0.2% biocide agent (antibacterial and anti-fungal), 3% isopropyl alcohol and 69.5% water and grinding in a bead-grinder for a period of one hour at a rate of 500 revolutions/minute with glass beads of 1 mm in diameter. Nanotube paste thus prepared is used for the preparation of the topcoat paint 5: 32% aluminum paste of 70% Al, 3% nanotube paste, 60% aqueous acrylic emulsion, and antifoam terlsjavt 1%, 4% water, by a simple slow agitation at 500 revolutions/minute.
(25) On the surface of the carrier 1 opposite the heat-sensitive layer 2 a black perturbing print 8 hindering translucence may be formed, which is e.g. a 3 microns thick ink flexo print with standard high carbon black content.
(26) Thermally conductive flexo ink provided by multi-walled carbon nanotubes according to the present invention increases thermal conductivity of the printed ink layer by magnitudes. By using thermally conductive flexo ink provided by multi-walled carbon nanotubes according to the present invention a water based, multilayered flexo ink scheme having appropriate heat conductivity and a layer order as seen e.g. in
(27) Layers 3, 4, 5 may be applied by flexo printing onto the heat sensitive layer 2 for forming the thermal paper H provided by an aqueous, multilayered topcoat flexo ink scheme, in such a way that the heat sensitive layer 2 of a roll of thermal paper H running with a speed of 0.85 m/s is overprinted by an UV light drying lacquer layer 3 having a thickness of 1 m, which layer 3 is hardened sufficiently as exposed to an UV light source with 1.5 kWh/m.sup.2 power after printing. Then, a disperse parting layer 4 having 1 m thickness and a 6-8 m thick, heat conductive topcoat layer 5 containing carbon nanotubes are printed thereon.
(28) After testing at laboratory scale, the examination of the flexo ink layer 5 scheme containing multiwalled carbon nanotubes in aqueous matrix has been repeated at industrial conditions. Proof impressions made by a stud at laboratory scale with different layer thickness as well as machine printing has been prepared. For commensurating the dimensions of prints produced at laboratory scale with those at industrial conditions a determination of cell depth of the anilox roll has been calculated according to the expression 3 n+n/3, where n is the dry layer thickness required. In
(29) Increase of the electric conductivity can be seen in the form of a percentage increase relating to the base electric conductivity of the paint+paper system fully dried and kept in an exsiccator having 0 RH % humidity inside. It can be discerned that the increase of the electric conductivity may be considered as being linear throughout the whole RH % scale in a range of ambient temperature expected at typical operational circumstances of thermal printing. An increase of the slope of characteristic curve depending on the ambient temperature is caused probably by a greater mobility of secunder carriers of charge.
(30) In
(31) According to the correlations presented in
(32) Variation of optical blackening (gradation or density) of thermo paper provided by flexographic covering paint scheme of layers containing carbon nanotubes and conventional topcoat layer, respectively, is shown as a function of the thickness of layer scheme in
(33) We have found that the alteration Q (decrease) of an amount of heat Q transmitted by a printing head 6 while transiting layers 5,4,3 for obtaining a change 7 having adequate density value in the layer 2 of the thermal paper H is not more than 10%, but in order to obtain less heat loss a further improvement of heat conductivity of the aqueous flexo topcoat print layers containing nanotubes would be required, which can be achieved by means of a heat printer according to the invention described later.
(34) Density (or gradation) of the thermal paper H provided by flexographic covering paint scheme of layers containing carbon nanotubes is shown as a function of energy imparted, where one can observe that an area T delimited by the boundary of thermal deformation of covering paint scheme of layers and by the level of secure optical reading is explicitly narrow (0.2 mJ/mm.sup.2) as it is seen in
(35) By using a method according to the invention a relative humidity RH accordant with the actual ambient temperature of thermal printing is determined by means of measuring fields 9 printed with an ink containing carbon nanotubes directly onto the surface of heat sensitive carrier 1 (that is omitting the lacquer layer 3), preferably spaced apart by moving units h, as it is seen in
(36) Measuring fields 9 are printed directly onto the thermal paper H, that is the lacquer layer 3 is omitted, since as we have found at studying the flexo ink containing carbon nanotubes the electric conductivity, therefore heat conductivity of the system consisting of heat paper H provided by heat sensitive layer 2 and flexo ink with multi-walled carbon nanotubes applied directly thereon changes as a function of relative humidity and temperature of ambient air.
(37) Measuring the electric resistance of a measuring field 9 by means of a measuring element 13 depicted in
(38) Consequently, by measuring, according to the invention, the electric resistance and temperature of a thermal paper H provided by a topcoat ink layer system containing carbon nanotubes to be heat printed by means of a preprinted measuring field 9 and a measuring element 13 immediately before thermal printing, its value of humidity RH1 according to the calibration curve shown in
(39) If the moisture content is higher or lower than an RHM value equivalent to a maximum relating to the thermal conductivity of a given thermal paper provided by a flexo topcoat ink layer system containing carbon nanotubes, a relationship similar as shown in
(40) Subsequently, the thermal printing is performed by making the thermal printing head 6 to operate and transmitting thermal energy in the range T shown in
(41) Increasing or decreasing the humidity in the close vicinity of thermal printing and transmitting thermal energy required to form the print 7 is implemented by a thermal printer apparatus according to the present invention.
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(43) Hence it follows that the electric conductivity, and as a consequence heat conductivity of the system can be finely controlled by adjusting overall humidity of a combined thermal paper H+flexographic topcoat ink layer system containing carbon nanotubes. Moreover, as the humidity of the sample material and the surrounding air are in dynamic equilibrium with each other, this type of control can be implemented in practice by precisely controlling the relative humidity of the air in the microenvironment of the printing operation carried out by a thermal printer 10 according to the present invention.
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(45) A blower system 19 arranged in the thermal printing apparatus 10 controls the air temperature prevailing in the house 11. A photocell sensor 20 is for detecting spacing units h, such that it detects any signal M printed on the back side of the thermal paper H roll according to a correct position of measuring field 9 arranged on the other side, as shown in
(46) Reservoir 21 containing air of 0% relative humidity RH content is provided for absorbing moisture content in excess of RHM. An evaporative heating element 22 is for providing a moisture content difference being necessary to reach an adequate relative humidity RHM by evaporating water sprayed onto the heating element 22. Thermal printing takes place by operation of the printer head 6, and then thermal paper H tape leaves the house 11 by passing behind transparent e.g. plexiglass windows 24, 25. Owing to an adequate infrared-absorbing capacity of windows 23.24 thermally printed information protected by flexo topcoat layers cannot be read in seconds after printing either by an infrared camera.
(47) A reservoir 23 of 100% relative humidity RH containing water is provided in the house 11 of the thermal printing apparatus 10, which may spray an amount of water determined by the control electronics, for example. 10 picoliter, onto the evaporative heating element 22 in order to provide further moisture content inside the housing 11 of the printer apparatus 10 if it is required, as determined by the control electronics. The 0% relative humidity RH reservoir 21, which consists preferably of a metal container provided by electric resistance heating, decreases the relative humidity RH of the air passing through it, so that the excess moisture content can be absorbed. In an alternative embodiment a closed metal container is arranged before the reservoir 21, in which a zeolite cartridge was placed, which is suitable for decreasing the absolute humidity of the air by adsorption (not shown). The zeolite may be a disposable cartridge, or automatically regenerated by the apparatus 10.
(48) The blower system 19, not shown in Figures, is suitable for delivering air onto the thermal paper H before the printing head 6 through reservoirs 21, 23 by means of fans, solenoid valves and nozzles not shown but well known in the art, according to a target humidity RHM.
(49) The measuring element 13 sensing electric resistance monitors the electric resistance of the measuring fields 9 permanently or cyclically as needed and the apparatus 10 controls the operation of reservoir 23, temperature of evaporative heating element 22 and the valves both of blower system 19 and reservoir 21 based on the measured values.
(50) A thermal printing cycle begins with printing a print on a surface area of the heat sensitive layer 2 covered and uncovered by ink layer system, and then, in a fixed state of the thermal paper H, the shortest time period of which is 15 sec passing up to the next printing cycle, a measuring cycle takes place on the next measuring field 9 in a time of 1-4 sec. The series of measurements are evaluated by the electronics by means of an algorithm developed for this purpose and controls the temperature and humidity control devices of the apparatus 10.
(51) While regulating in the practice the humidity RH in the interior of the housing 11 of thermal printer apparatus 10, the humidity-electric resistance correlation is exploited in both directions by controlling evaporating, absorbing, heating and cooling processes described above. The apparatus 10 measures of all time or as needed in specified cycles 9 the electric resistance of the measuring fields 9, on the basis of that measured value a calibrated controller counts the actual relative humidity RH1 prevailing inside the house 11 of the apparatus 10. This value is corrected by the apparatus 10 to an optimum value of relative humidity RHM predetermined individually for each thermal paper H by operating the blower system 19, the reservoir 21 containing air of 0% relative humidity RH, the evaporating heating element 22 and reservoir 23.
(52) Therefore, the main advantage of the aqueous flexo topcoat ink layer system containing carbon nanotubes arranged on a heat sensitive carrier 1 heat printable by the apparatus 10 and method according to the invention against solution of the art is that on the one hand that the heat transmitting covering paint scheme has improved heat transmitting properties and it is removable without damaging the heat sensitive layer, but its heat conductivity and, therefore, the quality of a print to be formed thereunder are far better than that of removable topcoat ink layers belonging to the state of the art. On the other hand, by the use of the thermal printer and thermal printing process according to the invention the thermal conductivity of a topcoat ink system with improved thermal conductivity according to the present invention can be optimized directly during printing without the need of the coated carrier should have a pre-printing moisture content necessarily exceeding the optimum moisture content, immediately before printing. Therefore, the heat energy level required to form the print may be lower resulting in a reduced power consumption and thermal load of the printing head 6since the resolution of the printer is determined by the size of heat developing resistors, the possibility of miniaturization of which is limited, but the size is inversely proportional to the physical resistance of the resistor against its thermal load that is its lifetimeand the thermal deformation of the topcoat layer system can be avoided as well.