CN111798738B - Dynamic anti-counterfeit label - Google Patents
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- CN111798738B CN111798738B CN202010699838.XA CN202010699838A CN111798738B CN 111798738 B CN111798738 B CN 111798738B CN 202010699838 A CN202010699838 A CN 202010699838A CN 111798738 B CN111798738 B CN 111798738B
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- G—PHYSICS
- G09—EDUCATION; CRYPTOGRAPHY; DISPLAY; ADVERTISING; SEALS
- G09F—DISPLAYING; ADVERTISING; SIGNS; LABELS OR NAME-PLATES; SEALS
- G09F3/00—Labels, tag tickets, or similar identification or indication means; Seals; Postage or like stamps
- G09F3/02—Forms or constructions
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D11/00—Inks
- C09D11/02—Printing inks
- C09D11/03—Printing inks characterised by features other than the chemical nature of the binder
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D11/00—Inks
- C09D11/02—Printing inks
- C09D11/08—Printing inks based on natural resins
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D11/00—Inks
- C09D11/02—Printing inks
- C09D11/10—Printing inks based on artificial resins
- C09D11/106—Printing inks based on artificial resins containing macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
- C09D11/107—Printing inks based on artificial resins containing macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds from unsaturated acids or derivatives thereof
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D11/00—Inks
- C09D11/52—Electrically conductive inks
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Abstract
The invention belongs to the technical field of anti-counterfeit labels, and particularly relates to a dynamic anti-counterfeit label which at least comprises a substrate layer, wherein a low-voltage heating ink layer and a covering layer are sequentially arranged above the substrate layer, the substrate layer is a thermosetting film made of thermosetting materials, and the covering layer is a thermoplastic film made of thermoplastic materials; the low-voltage heating ink layer is connected with a power supply positioned outside the dynamic anti-counterfeiting label, and a lead A and a lead B which are arranged in the dynamic anti-counterfeiting label are more favorable for good transmission of current; the charging power supply or the mobile power supply can be directly connected with the USB interface arranged outside the dynamic anti-counterfeiting label, so that the dynamic label is provided with a power supply, is convenient to use and is not limited by places. The basal layer adopts a thermosetting plastic film, the covering layer is a thermoplastic plastic film, after being heated, the thermoplastic covering layer is bent and deformed, and the thermosetting basal layer is not changed, so that the dynamic anti-counterfeiting label is dynamically deformed, and the purpose of verifying authenticity is achieved.
Description
Technical Field
The invention belongs to the technical field of anti-counterfeit labels, and particularly relates to a dynamic anti-counterfeit label.
Background
The anti-counterfeiting label is a mark which can be stuck, printed and transferred on the surface of an object and has an anti-counterfeiting function. The anti-counterfeiting characteristic and the identification method of the anti-counterfeiting label are the main structures of the anti-counterfeiting label, and the anti-counterfeiting is a preventive measure for the actions of counterfeiting or copying for the purpose of deception and without permission of all persons. At present, the anti-counterfeiting technology diversity generates watermark anti-counterfeiting, digital code anti-counterfeiting, bar code anti-counterfeiting, two-dimensional code anti-counterfeiting and the like, however, the anti-counterfeiting labels are static, the use style is single, and the requirement of dynamic change display cannot be met.
Disclosure of Invention
The invention aims to solve the defects of the prior art and provides a dynamic anti-counterfeiting label.
The technical scheme adopted for achieving the purpose of the invention is as follows: a dynamic anti-counterfeit label at least comprises a substrate layer, wherein a low-voltage heating ink layer and a covering layer are sequentially arranged above the substrate layer, the substrate layer is a thermosetting film made of thermosetting materials, and the covering layer is a thermoplastic film made of thermoplastic materials; and the low-voltage heating ink layer is connected with a power supply positioned outside the dynamic anti-counterfeiting label.
And the power supply is a USB interface or a switch and a battery which can be connected with electricity, and the low-voltage heating ink layer is connected with the power supply through a conducting wire made of conductive ink or conductive metal.
And a first silver paste layer is arranged between the basal layer and the upper part of the low-voltage heating ink layer, and a second silver paste layer is arranged between the low-voltage heating ink layer and the covering layer.
Moreover, the thermosetting material adopts one or a mixture of epoxy resin, polytetrafluoroethylene, nylon and polystyrene in any proportion, and the thermoplastic material adopts one or a mixture of ABS plastic, polyvinyl chloride, polypropylene or polycarbonate in any proportion.
The low-voltage heating ink layer comprises the following components in percentage by mass: 5-10% of water-based acrylic resin, 5-10% of rosin resin, 5-15% of graphite, 3-10% of carbon black, 0-50% of carbon nanotube dispersion liquid, 0.5-1.5% of pH regulator, 1-5% of dispersing agent, 0-1% of xanthan gum, 0.5-1% of defoaming agent and 10-50% of deionized water.
The low-voltage heating ink layer is formed by coating low-voltage heating ink on the substrate layer through a screen printing or coating method.
The pH regulator is one or more of formamide, ethanolamine or ammonia water which are mixed in any proportion.
The dispersant is one of Dispenser W-518 type aqueous wetting dispersant, Dispenser W-920 type aqueous wetting dispersant, NUOSPERSE FX 600 type aqueous wetting dispersant or NUOSPERSE FX 365 type aqueous wetting dispersant or a plurality of the dispersant mixed in any proportion.
The defoaming agent is one or a plurality of types of DefomW-0506 type waterborne defoaming agents, TEGO Foamex 805 type waterborne defoaming agents or SF-809B type standard American silicon fluorine defoaming agents which are mixed in any proportion.
The dynamic anti-counterfeiting label provided by the invention can be powered by a battery, and can be connected with a USB interface of the dynamic anti-counterfeiting label by a charging power supply or a mobile power supply, so that the dynamic anti-counterfeiting label is provided with a power supply, is convenient to use and is not limited by places. The low voltage heating ink layer acts like a heating resistor. The stratum basale adopts thermosetting plastic film, and the overburden is thermoplastic plastic film, and after being heated, the bending deformation takes place for thermoplastic overburden, and thermosetting stratum basale is unchangeable to make this dynamic antifalsification label produce dynamic deformation after charging, reach the purpose of verifying the true and false. The arrangement of the first silver paste layer and the second silver paste layer is more favorable for good transmission of current.
The technical scheme of the invention has the beneficial effects that:
(1) the power supply has two options, namely a USB interface capable of being connected with electricity, and a switch and a battery. When the power supply adopts the combination of a switch and a battery, the switch is closed to provide power for the dynamic label; when the USB interface is adopted, the charging power supply or the mobile power supply can be directly connected with the USB interface arranged outside the dynamic anti-counterfeiting label, so that the dynamic anti-counterfeiting label is convenient to use and is not limited by places.
(2) The stratum basale adopts thermosetting plastic film, and the overburden is thermoplastic plastic film, and after being heated, the bending deformation takes place for thermoplastic overburden, and thermosetting stratum basale is unchangeable to make this dynamic antifalsification label produce dynamic deformation after charging, reach the purpose of verifying the true and false.
(3) And a wire is arranged between each of the first silver paste layer and the second silver paste layer and the low-voltage heating ink layer, so that the current can be well transmitted.
(4) The low-voltage heating ink provided by the invention has the following advantages: 1. biomass materials such as xanthan gum and rosin resin are used as raw materials, so that the effects of energy conservation and environmental protection are achieved; 2. under the combined action of the xanthan gum and the rosin resin, the overall proportion of the acrylic resin in the ink is reduced, so that the proportion of conductive fillers such as carbon black, graphite and carbon nano tubes in a carbon film formed after the prepared low-voltage heating ink is dried is increased, and the conductivity is excellent; 3. the low-voltage heating ink has higher viscosity and better thixotropy, the viscosity of the ink is instantly reduced under the action of shearing force in the printing process to form a thicker carbon film, the viscosity is rapidly improved after the printing is finished, so that the ink is not diffused on a printing stock, the printing adaptability of the ink is improved, and the low-voltage heating ink is suitable for screen printing; 4. the low-voltage heating ink can obtain a better heating effect under a lower working voltage. High heating efficiency and high heating rate.
Drawings
FIG. 1 is a schematic structural diagram of an embodiment of a dynamic security label provided by the present invention;
FIG. 2(a) is a graph showing the operation of 3cm by 3cm low voltage heating ink packs prepared in example 1 of the present invention at different voltages;
FIG. 2(b) is a schematic diagram of the operation of the low-voltage heating ink block in the embodiment 1 under the condition of continuously changing voltage;
FIG. 3 is a graph showing the temperature of the low-voltage heating ink block versus time in this embodiment 1;
FIG. 4 is a graph showing the heating temperature of the low-voltage heating ink block as a function of power density in this example 1;
FIG. 5 is a graph showing the volt-ampere relationship of the low voltage thermal ink stick of this example 1;
FIG. 6 is a graph showing the relationship between the input voltage and the saturation temperature of the low-voltage heating ink block in this embodiment 1;
FIG. 7 is a schematic structural diagram of the dynamic anti-counterfeit label provided by the present invention before power connection;
FIG. 8 is a schematic structural diagram of the dynamic anti-counterfeit label provided by the present invention after being connected with power;
in the figure: 1. the USB interface comprises a substrate layer, 2 parts of a first silver paste layer, 3 parts of a low-voltage heating ink layer, 4 parts of a second silver paste layer, 5 parts of a covering layer, 6 parts of wires A, 7 parts of wires B and 8 parts of a USB interface.
Detailed Description
The invention is further explained by the figures and the examples.
Fig. 1 shows an embodiment of the dynamic anti-counterfeit label provided by the present invention, which includes a substrate layer 1, a first silver paste layer 2, a low voltage heating ink layer 3, a second silver paste layer 4 and a cover layer 5 are sequentially disposed above the substrate layer 1, a wire a6 and a wire B7 are used for connecting the low voltage heating ink layer with a USB interface 8 outside the dynamic anti-counterfeit label, and the specific positions of the wire a and the wire B are set according to the size of the low voltage heating ink layer, and can be set up above and below the low voltage heating ink layer, or at both ends of the low voltage heating ink layer. The first silver paste layer and the second silver paste layer are conductive, and good transmission of current can be facilitated. The conducting wire is made of conducting ink or conducting metal, and the conducting ink can adopt the low-voltage heating ink provided by the scheme and can also be other types of conducting ink. Besides, the power supply adopts a USB interface of a power connection point, and can be replaced by a combination of a switch and a battery. The low voltage heating ink layer acts like a heating resistor. The circuit is simple and easy to realize, and the circuit is formed by connecting a switch, a battery, a lead and a low-voltage heating ink layer into a loop, or two poles of a USB interface are connected with the low-voltage heating ink layer through the lead.
The base layer is a thermosetting film made of a thermosetting material, and the covering layer is a thermoplastic film made of a thermoplastic material. The thermosetting material adopts one or a plurality of materials mixed in any proportion of epoxy resin, polytetrafluoroethylene, nylon and polystyrene, and the thermoplastic material adopts one or a plurality of materials mixed in any proportion of ABS plastic, polyvinyl chloride, polypropylene or polycarbonate. The low-voltage heating ink layer is formed by coating low-voltage heating ink on a substrate layer by a screen printing or coating method, and the substrate layer is made of any material capable of printing ink, such as paper, cloth, cotton and plastic.
Fig. 7 is a schematic structural diagram of the dynamic anti-counterfeit label before power connection, a rated voltage of a wire power supply in the dynamic anti-counterfeit label is DC5V, when the dynamic anti-counterfeit label is verified to be true, only a charging power supply or a mobile power supply needs to be connected with a USB interface to provide a power supply for the dynamic anti-counterfeit label, and because the rated voltage of the wire power supply is low, the mobile power supply can supply power to the dynamic label, so that a use place of the dynamic label is not limited by a fixed power supply, and the dynamic label is more convenient. Fig. 8 is a schematic structural diagram of the dynamic anti-counterfeit label after being powered on, referring to fig. 3, the resistance of the heating ink in the dynamic anti-counterfeit label is 5 Ω, when the dynamic anti-counterfeit label is connected with a power supply, after a circuit is connected, the low-voltage heating ink can be rapidly heated to more than 80 ℃ within 10s, and at the moment, the thermoplastic covering layer is bent and deformed, and the thermosetting base layer is not changed, so that the dynamic anti-counterfeit label is dynamically deformed after being charged, and the purpose of verifying authenticity is achieved.
The technical scheme of the invention has the beneficial effects that:
(1) the power supply has two options, namely a USB interface capable of being connected with electricity, and a switch and a battery. When the power supply adopts the combination of a switch and a battery, the switch is closed to provide power for the dynamic label; when the USB interface is adopted, the charging power supply or the mobile power supply can be directly connected with the USB interface arranged outside the dynamic anti-counterfeiting label, so that the dynamic anti-counterfeiting label is convenient to use and is not limited by places.
(2) The stratum basale adopts thermosetting plastic film, and the overburden is thermoplastic plastic film, and after being heated, the bending deformation takes place for thermoplastic overburden, and thermosetting stratum basale is unchangeable to make this dynamic antifalsification label produce dynamic deformation after charging, reach the purpose of verifying the true and false.
(3) And a wire is arranged between each of the first silver paste layer and the second silver paste layer and the low-voltage heating ink layer, so that the current can be well transmitted.
The low-voltage heating ink in the dynamic anti-counterfeiting label comprises the following components in percentage by mass: 5-10% of water-based acrylic resin, 5-10% of rosin resin, 5-15% of graphite, 3-10% of carbon black, 0-50% of carbon nanotube dispersion liquid, 0.5-1.5% of pH regulator, 1-5% of dispersing agent, 0-1% of xanthan gum, 0.5-1% of defoaming agent and 10-50% of deionized water. The pH regulator is one or more of formamide, ethanolamine or ammonia water which are mixed in any proportion. The dispersant is one of Dispenser W-518 type aqueous wetting dispersant, Dispenser W-920 type aqueous wetting dispersant, NUOSPERSE FX 600 type aqueous wetting dispersant or NUOSPERSE FX 365 type aqueous wetting dispersant or a plurality of the dispersant mixed in any proportion. The defoaming agent is one or a plurality of types of DefomW-0506 type waterborne defoaming agents, TEGO Foamex 805 type waterborne defoaming agents or SF-809B type standard American silicon fluorine defoaming agents which are mixed in any proportion.
The preparation method of the low-voltage heating ink specifically comprises the following steps:
(1) weighing each component of the low-voltage heating ink according to the mass parts, placing the water-based acrylic resin, the rosin resin, the pH regulator and the deionized water in a stirring kettle, stirring for 5-10 min, after uniformly mixing, sequentially adding the carbon black, the graphite, the carbon nanotube dispersion liquid and the xanthan gum, uniformly stirring, finally adding the dispersing agent and the defoaming agent, and uniformly stirring to form the primary heating ink;
(2) mixing the primary heating ink and the ball-milled beads according to the mass ratio of 3:1, placing the mixture in an electric stirrer, stirring the mixture for 1-3 hours, taking out the mixture, filtering the mixture, and finally placing the primary heating ink in a sand mill, and grinding the mixture until the particle size is below 5 microns to obtain the low-voltage heating ink.
In the preparation process of the low-voltage heating ink, xanthan gum, conductive fillers such as carbon black, graphite and carbon nano tubes and deionized water can form a stable three-dimensional network structure, so that graphene, carbon black and graphite generated in the mechanical grinding process have better dispersion stability; the xanthan gum serving as the biomass hydrogel can form a reversible hydrogel with solvents such as deionized water and the like, free water molecules in the ink are reduced, the viscosity of the ink is improved, the reversible hydrogel enables the viscosity of the prepared low-voltage heating ink to be larger than 10000mPa & s in a standing state, the viscosity of the low-voltage heating ink is reduced to 4000-5000 mPa & s under stirring at a rotating speed of 60r/min, and the viscosity of the low-voltage heating ink is recovered to be more than 10000mPa & s after stirring is stopped.
Example 1:
weighing 7% of water-based acrylic resin, 7% of rosin resin, 6% of graphite, 10% of carbon black, 35% of carbon nanotube dispersion liquid, 0.5% of formamide, 0.5% of ethanolamine, 5% of Disponer W-518 type water-based wetting dispersant, 0.3% of xanthan gum, 0.5% of TEGO Foamex 805 type water-based defoaming agent and 28.2% of deionized water according to parts by mass.
Placing 7% of water-based acrylic resin, 7% of rosin resin, 0.5% of formamide, 0.5% of ethanolamine and 28.2% of deionized water in a stirring kettle, stirring for 5-10 min, after uniformly mixing, sequentially adding 10% of carbon black, 6% of graphite, 35% of carbon nanotube dispersion liquid and 0.3% of xanthan gum, uniformly stirring, finally adding 5% of Disponer W-518 type water-based wetting dispersant and 0.5% of TEGO Foamex 805 type water-based defoaming agent, and uniformly stirring to form primary heating ink; mixing the primary heating ink and the ball-milled beads according to the mass ratio of 3:1, placing the mixture in an electric stirrer to be mixed and dispersed for 2 hours, taking out the mixture to be filtered, and finally placing the primary heating ink in a sand mill to be ground until the particle size is below 5 mu m to obtain the low-voltage heating ink.
The low-voltage heating ink obtained in the embodiment has the viscosity of 9000-11000 mPa & s under stirring at the rotating speed of 12r/min, the viscosity of 4000-5000 mPa & s under stirring at the rotating speed of 60r/min, the thickness of the dried ink layer is 15-18 mu m, the low-voltage heating ink can be used for screen printing of a 200-mesh silk screen printing plate once, and the sheet resistance value of the low-voltage heating ink is 9.6 omega/25 mu m. The saturation temperature of the low-voltage heating ink heating module with the size of 2cm multiplied by 2.5cm under the working voltage of 3V can reach 80 ℃.
The measurement conditions were as follows: 1. square resistance: measurement using a four-probe sheet resistance tester
2. Viscosity: measurement using a rotational viscometer
3. Saturation temperature: measured using an infrared camera.
FIG. 2(a) is a graph showing the operation of the 3cm by 3cm low voltage heating ink packs prepared in example 1 of the present invention at different voltages. And respectively switching on heating data of direct current voltages of 1.0v, 1.5v, 2.0v, 2.5v and 3.0v, and testing the temperature response rate of the low-voltage heating ink block and the saturation temperature of the low-voltage heating ink block at each working voltage. The temperature influence speed is fast, the saturation temperature can be reached by switching on the power supply for about 10s, the required voltage is extremely low, the heating efficiency is high, and the heating rate is fast. When 1.0v of voltage is applied to the low-voltage heating ink block, the passing working current is 0.28A, and the saturation temperature which can be reached is about 47 ℃; operation by switching on a voltage of 1.5vThe current is 0.428A, and the saturation temperature is 70 ℃; when 2.0v of voltage is applied, the working current is 0.583A, and the saturation temperature is 100 ℃; when 2.5v of voltage is applied, the working current is 0.749A, and the saturation temperature is 130 ℃; when 3.0v voltage was applied, the operating current was 0.915A, and the saturation temperature reached by the low voltage heat-generating ink block was about 175 ℃. The prepared low-voltage heating ink block has very high electrothermal radiation conversion efficiency, extremely low required working voltage and safer use of the low-voltage heating ink. Fig. 2(b) shows the operation of the low-voltage heating ink block under the condition of continuously changing voltage, the voltage applied to the low-voltage heating ink block is continuously increased from 1.0v to 3.0v at intervals of 0.5v, and it can be seen that the response rate and the heating stability are very stable, and the saturation temperature reached at the same voltage is consistent with that of the graph in fig. 2 (a). According to an electrothermal radiation conversion efficiency formula: β ═ S α (T)r 4-T0 4) P, where β is the electrothermal radiation conversion efficiency of the electrothermal film, S is the heating area of the electrothermal film, and α is the Spander-Boltzmann constant (5.67 × 10)-8In the unit of W/m2K4)，TrIs the saturation temperature, T, at a certain operating voltage0P is the ambient temperature and electric power. According to the formula, the electrothermal radiation conversion efficiency beta of the low-voltage heating ink block under the working voltage of 3v is 74.75 percent, which is about 10 percent higher than that of the traditional electrothermal material.
The carbon material is stable in chemical property, can stably exist in the air, is not suitable for reacting with oxygen, the aqueous acrylic resin used by the low-voltage heating ink block is stable and does not decompose in the air below 250 ℃, and the conductive carbon particles are stable and does not decompose in the air below 400 ℃, so that the prepared low-voltage heating ink block can continuously and stably work at the running temperature below 200 ℃. To further verify that the low voltage heat-generating ink block can continuously and stably operate at high temperature (175 ℃), the low voltage heat-generating ink block is modulated to have higher working voltage (3.0v) and is kept for more than 4h in the operation state at 175 ℃. As shown in fig. 3, the temperature and time variation relationship shows that the saturation temperature remains unchanged in the high temperature state, which indicates that the electrothermal infrared radiation efficiency of the low voltage heat-generating ink block and the composition and performance of the ink are not changed, which is enough to prove that the stability of the low voltage heat-generating ink in the air and in the high temperature state is very outstanding.
Fig. 4 shows a functional relationship between the heating temperature and the power density of the low-voltage heating ink block prepared in this embodiment, and a fitted curve of the temperature and the power density is approximately linear (T ═ 249 × P +37, T is the temperature, and P is the energy density), and as can be seen from the graph, the slope is steep (about 249.53 ℃ c, cm2W-1), which indicates that the saturation temperature that can be reached per unit area under the same power density condition is higher, i.e., the electrothermal infrared radiation efficiency is higher, which indicates that the electrothermal infrared radiation efficiency of the low-voltage heating ink block prepared based on this embodiment is higher, and the energy consumption is lower.
Fig. 5 is a graph of the volt-ampere (V-a) relationship of the low voltage heat-generating ink stick prepared in this example, and it can be seen from the fitted curve that the voltage V applied to the low voltage heat-generating ink stick is almost proportional to the passing current a, which shows that the resistance of the low voltage heat-generating ink stick does not change with the increase of temperature (the saturation temperature is 47 ℃ at 1.0V to 175 ℃ at 3.0V), i.e., the resistance does not change with the change of temperature.
Fig. 6 is a graph of the relationship between the input voltage and the saturation temperature of the low-voltage heat-generating ink block prepared in this example, and it can be seen from the fitted curve in the graph that the saturation temperature reached when the low-voltage heat-generating ink block is powered on is exponential to the voltage applied at both ends: t ═ A1exp(-V/t1)-y0Where T is the saturation temperature of the electrothermal film, V is the voltage at which it is switched on, A1＝39.98±13.40，t1＝-1.91±0.31，y0-14.84 ± 16.71. The exponential relationship between temperature and voltage shows that the conversion efficiency of the low-voltage heat-generating ink block prepared in the embodiment through infrared heat radiation is high.
The low-voltage heating ink block is placed in a room-temperature air environment, the same voltage of 3.0v is applied to the same low-voltage heating ink block for ten days continuously, the temperature response rate and the maximum saturation temperature of the low-voltage heating ink block are almost unchanged, and the stable operation in the air is shown, compared with gold which is easily oxidized in the airThe advantages of the generic electric heating materials (such as silver electric heating materials) are obvious. In addition, in order to verify that the folding resistance test of the flexible electric heating material is carried out for 2500 folds continuously, the resistance of the low-voltage heating ink block is not changed obviously, and the resistance is regular along with the change of the bending angle, which shows that after 2500 folds, the ink on the flexible electric heating film is connected perfectly and is not broken. The pressure resistance of the material is extremely outstanding and is 1x10 when the material is subjected to pressure test by a tablet press5The structure is not destroyed under a pressure below kpa.
Example 2:
weighing 7% of water-based acrylic resin, 7% of rosin resin, 5% of graphite, 10% of carbon black, 35% of carbon nanotube dispersion liquid, 1% of ethanolamine, 5% of Disponer W-920 type water-based wetting dispersant, 0.3% of xanthan gum, 0.5% of DefomW-0506 type water-based defoaming agent and 29.2% of deionized water according to parts by mass.
Placing 7% of water-based acrylic resin, 7% of rosin resin, 1% of ethanolamine and 29.2% of deionized water in a stirring kettle, stirring for 5-10 min, after uniformly mixing, sequentially adding 10% of carbon black, 5% of graphite, 35% of carbon nanotube dispersion liquid and 0.3% of xanthan gum, uniformly stirring, finally adding 5% of Disponer W-920 type water-based wetting dispersant and 0.5% of DefomW-0506 type water-based defoaming agent, and uniformly stirring to form primary heating ink; mixing the primary heating ink and the ball-milled beads according to the mass ratio of 3:1, placing the mixture in an electric stirrer to be mixed and dispersed for 2.5h, taking out and filtering the mixture, and finally placing the primary heating ink in a sand mill to be ground until the particle size is below 5 mu m to obtain the low-voltage heating ink.
The low-voltage heating ink obtained in the embodiment has the viscosity of 9000-11000 mPa & s under stirring at the rotating speed of 12r/min, the viscosity of 4000-5000 mPa & s under stirring at the rotating speed of 60r/min, the thickness of the dried ink layer is 15-18 mu m, the low-voltage heating ink can be used for screen printing of a 200-mesh silk screen printing plate once, and the sheet resistance value of the low-voltage heating ink is 10.6 omega/25 mu m. The saturation temperature of the low-voltage heating ink heating module with the size of 2cm multiplied by 2.5cm under the working voltage of 5V can reach 72 ℃.
Example 3:
respectively weighing 10% of waterborne acrylic resin, 5% of rosin resin, 12% of graphite, 6% of carbon black, 40% of carbon nanotube dispersion liquid, 1.5% of ammonia water, 5% of NUOSPERSE FX 365 type waterborne wetting dispersant, 0.4% of xanthan gum, 1% of SF-809B type standard American silicon fluorine defoaming agent and 19.1% of deionized water according to the mass parts.
Placing 10% of water-based acrylic resin, 5% of rosin resin, 1.5% of ethanolamine and 19.1% of deionized water in a stirring kettle, stirring for 5-10 min, after uniformly mixing, sequentially adding 6% of carbon black, 12% of graphite, 40% of carbon nanotube dispersion and 0.4% of xanthan gum, uniformly stirring, finally adding 5% of NUEROSPSE FX 365 type water-based wetting dispersant and 1% of SF-809B type standard silicon fluorine defoaming agent, and uniformly stirring to form primary heating ink; mixing the primary heating ink and the ball-milled beads according to the mass ratio of 3:1, placing the mixture in an electric stirrer to be mixed and dispersed for 2.5h, taking out and filtering the mixture, and finally placing the primary heating ink in a sand mill to be ground until the particle size is below 5 mu m to obtain the low-voltage heating ink.
The low-voltage heating ink obtained in the embodiment has the viscosity of 15000-20000 mPa & s under stirring at the rotating speed of 12r/min, the thickness of the dried ink layer is 20-22 mu m, the low-voltage heating ink can be used for screen printing of a 200-mesh silk screen plate once, and the sheet resistance value of the low-voltage heating ink is 8.9 omega/25 mu m. The saturation temperature of the low-voltage heating ink heating module with the size of 2cm multiplied by 2.5cm under the working voltage of 5V can reach 76 ℃.
Example 4:
weighing 5% of water-based acrylic resin, 10% of rosin resin, 9% of graphite, 6% of carbon black, 30% of carbon nanotube dispersion liquid, 0.5% of ethanolamine, 4% of a mixture of Disponer W-920 type water-based wetting dispersant and NUOSPERSE FX 600 type water-based wetting dispersant, 0.5% of xanthan gum, 0.5% of TEGO Foamex 805 type water-based defoaming agent and 34.5% of deionized water according to parts by mass.
Placing 5% of water-based acrylic resin, 10% of rosin resin, 0.5% of ethanolamine and 34.5% of deionized water in a stirring kettle, stirring for 5-10 min, after uniformly mixing, sequentially adding 6% of carbon black, 9% of graphite, 30% of carbon nanotube dispersion and 0.5% of xanthan gum, uniformly stirring, finally adding a mixed solution of 4% of Disponer W-920 type water-based wetting dispersant and NUOSPERSE FX 600 type water-based wetting dispersant and 0.5% of TEGO Foamex 805 type water-based defoaming agent, and uniformly stirring to form primary heating ink; mixing the primary heating ink and the ball-milled beads according to the mass ratio of 3:1, placing the mixture in an electric stirrer to be mixed and dispersed for 3 hours, taking out the mixture to be filtered, and finally placing the primary heating ink in a sand mill to be ground until the particle size is below 5 mu m to obtain the low-voltage heating ink.
The low-voltage heating ink obtained in the example has viscosity of 12000mPa & s under stirring at a rotating speed of 12r/min, the thickness of the dried ink layer is 19 μm, the low-voltage heating ink can be used for screen printing of a 200-mesh screen printing plate once, and the sheet resistance value of the low-voltage heating ink is 9.6 omega/25 μm. The saturation temperature of the low-voltage heating ink heating module with the size of 2cm multiplied by 2.5cm under the working voltage of 5V can reach 70 ℃.
Example 5:
respectively weighing 10% of water-based acrylic resin, 10% of rosin resin, 15% of graphite, 10% of carbon black, 1.5% of ethanolamine, 5% of NUOSPERSE FX 365 type water-based wetting dispersant, 1% of DefomW-0506 type water-based defoaming agent and 47.5% of deionized water according to parts by weight.
Placing 10% of water-based acrylic resin, 10% of rosin resin, 1.5% of ethanolamine and 47.5% of deionized water in a stirring kettle, stirring for 5-10 min, after uniformly mixing, sequentially adding 10% of carbon black and 15% of graphite, uniformly stirring, finally adding 5% of NUOSPERSE FX 365 type water-based wetting dispersant and 1% of DefomW-0506 type water-based defoaming agent, and uniformly stirring to form primary heating ink; mixing the primary heating ink and the ball-milled beads according to the mass ratio of 3:1, placing the mixture in an electric stirrer to be mixed and dispersed for 3 hours, taking out the mixture to be filtered, and finally placing the primary heating ink in a sand mill to be ground until the particle size is below 5 mu m to obtain the low-voltage heating ink.
The low-voltage heating ink obtained in the example has a viscosity of 18000mPa · s under stirring at a rotation speed of 12r/min, has a thickness of 23 μm after drying, can be used for screen printing of a 200-mesh screen printing plate once, and has a sheet resistance value of 12.8 Ω/25 μm. The saturation temperature of the low-voltage heating ink heating module with the size of 2cm multiplied by 2.5cm under the working voltage of 5V can reach 68 ℃.
Example 6:
weighing 7.5% of water-based acrylic resin, 7.5% of rosin resin, 5% of graphite, 8% of carbon black, 50% of carbon nanotube dispersion liquid, 0.8% of ammonia water, 1% of Disponer W-920 type water-based wetting dispersant, 1% of xanthan gum, 0.3% of mixed liquid of TEGO Foamex 805 type water-based defoamer and SF-809B type standard silicon fluorine defoamer and 18.9% of deionized water according to parts by weight.
Placing 7.5% of water-based acrylic resin, 7.5% of rosin resin, 0.8% of ammonia water and 18.9% of deionized water in a stirring kettle, stirring for 5-10 min, after uniformly mixing, sequentially adding 8% of carbon black and 5% of graphite, uniformly stirring, finally adding a mixed solution of 1% of Disponer W-920 type water-based wetting dispersant, 0.3% of TEGO Foamex 805 type water-based defoaming agent and SF-809B type standard silicon fluorine defoaming agent, and uniformly stirring to form primary heating ink; mixing the primary heating ink and the ball-milled beads according to the mass ratio of 3:1, placing the mixture in an electric stirrer to be mixed and dispersed for 1h, taking out the mixture to be filtered, and finally placing the primary heating ink in a sand mill to be ground until the particle size is below 5 mu m to obtain the low-voltage heating ink.
The low-voltage heating ink obtained in the embodiment has the viscosity of 11000mPa & s under the stirring at the rotating speed of 12r/min, the thickness of the dried ink layer is 18 mu m, the low-voltage heating ink can be used for screen printing of a 200-mesh screen printing plate once, and the sheet resistance value of the low-voltage heating ink is 9.0 omega/25 mu m. The saturation temperature of the low-voltage heating ink heating module with the size of 2cm multiplied by 2.5cm under the working voltage of 5V can reach 76 ℃.
Example 7:
weighing 8% of water-based acrylic resin, 5% of rosin resin, 12% of graphite, 3% of carbon black, 40% of carbon nanotube dispersion liquid, 0.5% of formamide, 0.5% of ethanolamine, 3% of NUOSPERSE FX 365 type water-based wetting dispersant, 0.3% of xanthan gum, 0.6% of DefomW-0506 type water-based defoaming agent and 27.1% of deionized water according to parts by mass.
Placing 8% of water-based acrylic resin, 5% of rosin resin, 0.5% of formamide, 0.5% of ethanolamine and 27.1% of deionized water in a stirring kettle, stirring for 5-10 min, after uniformly mixing, sequentially adding 3% of carbon black and 12% of graphite, uniformly stirring, finally adding 3% of NUOSPERSE FX 365 type water-based wetting dispersant and 0.6% of DefomoW-0506 type water-based defoaming agent, and uniformly stirring to form primary heating ink; mixing the primary heating ink and the ball-milled beads according to the mass ratio of 3:1, placing the mixture in an electric stirrer to be mixed and dispersed for 2.5h, taking out and filtering the mixture, and finally placing the primary heating ink in a sand mill to be ground until the particle size is below 5 mu m to obtain the low-voltage heating ink.
The low-voltage heat-generating ink obtained in the example has a viscosity of 13000mPa · s under stirring at a rotation speed of 12r/min, has a thickness of 21 μm after drying, can be used for screen printing of a 200-mesh screen printing plate once, and has a sheet resistance value of 10.9 Ω/25 μm. The saturation temperature of the low-voltage heating ink heating module with the size of 2cm multiplied by 2.5cm under the working voltage of 5V can reach 71 ℃.
The low-voltage heating ink provided by the invention can obtain a better heating effect under a lower working voltage; the low-voltage heating ink has high viscosity and high thixotropy, the viscosity of the ink is instantly reduced under the action of shearing force in the printing process to form a thick carbon film, the viscosity is rapidly improved after the printing is finished, the ink is prevented from diffusing on a printing stock, the printing adaptability of the ink is improved, and the low-voltage heating ink is suitable for screen printing. The xanthan gum in the components can play a role in dispersing graphene, carbon black and graphite, can replace part of acrylic resin, and the addition of a small amount of rosin resin can make up the poor adhesive force and mechanical property of the xanthan gum; under the combined action of the xanthan gum and the rosin resin, the overall proportion of acrylic resin in the ink is reduced, the xanthan gum and the rosin resin are both biomass materials, the energy-saving and environment-friendly effects can be achieved, and in addition, the addition of the xanthan gum and the rosin resin enables the proportion of conductive fillers such as carbon black, graphite and carbon nano tubes in a carbon film formed after the prepared low-voltage heating ink is dried to be increased, and the conductivity is excellent.
Claims (9)
1. A dynamic anti-counterfeiting label at least comprises a substrate layer, and is characterized in that: a low-voltage heating ink layer and a covering layer are sequentially arranged above the substrate layer, the substrate layer is a thermosetting film made of a thermosetting material, and the covering layer is a thermoplastic film made of a thermoplastic material; and the low-voltage heating ink layer is connected with a power supply positioned outside the dynamic anti-counterfeiting label.
2. The dynamic security label of claim 1, wherein: the power supply is a USB interface or a switch and a battery which can be connected with electricity, and the low-voltage heating ink layer is connected with the power supply through a conducting wire made of conductive ink or conductive metal.
3. The dynamic security label of claim 1, wherein: and a first silver paste layer is arranged between the basal layer and the upper part of the low-voltage heating ink layer, and a second silver paste layer is arranged between the low-voltage heating ink layer and the covering layer.
4. The dynamic security label of claim 1, wherein: the thermosetting material adopts one or a plurality of epoxy resin, polytetrafluoroethylene, nylon and polystyrene mixed in any proportion, and the thermoplastic material adopts one or a plurality of ABS plastic, polyvinyl chloride, polypropylene or polycarbonate mixed in any proportion.
5. The dynamic security label of claim 1, wherein: the low-voltage heating ink layer comprises the following components in percentage by mass: 5-10% of water-based acrylic resin, 5-10% of rosin resin, 5-15% of graphite, 3-10% of carbon black, 0-50% of carbon nanotube dispersion liquid, 0.5-1.5% of pH regulator, 1-5% of dispersing agent, 0-1% of xanthan gum, 0.5-1% of defoaming agent and 10-50% of deionized water.
6. The dynamic security label of claim 5, wherein: the low-voltage heating ink layer is formed by coating low-voltage heating ink on the substrate layer through a screen printing or coating method.
7. The dynamic security label of claim 5, wherein: the pH regulator is one or more of formamide, ethanolamine or ammonia water mixed in any proportion.
8. The dynamic security label of claim 5, wherein: the dispersant is one of Dispenser W-518 type aqueous wetting dispersant, Dispenser W-920 type aqueous wetting dispersant, NUOSPERSE FX 600 type aqueous wetting dispersant or NUOSPERSE FX 365 type aqueous wetting dispersant or a mixture of the two in any proportion.
9. The dynamic security label of claim 5, wherein: the defoaming agent is one or more of a DefomW-0506 type waterborne defoaming agent, a TEGO Foamex 805 type waterborne defoaming agent or a SF-809B type standard silicon fluoride defoaming agent which is mixed in any proportion.
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