KR20150142829A - Exothermic element and method for manufacturing the same - Google Patents

Abstract

An exothermic element and a method for manufacturing the same are provided. The exothermic element includes a substrate; a conducive exothermic body which is located on at least one surface of the substrate, has a curved cross section, and is made of one-dimensional conductive wire which is invisible and has a micro width of 1.8 μm or less; and an electrode which is electrically connected to the conducive exothermic body. Therefore, an invisible transparent exothermic device can be provided by using the exothermic body of a micro width. Also, exothermic efficiency can be improved and also transparency can be freely controlled, by controlling a gap or pattern shape of the conductive exothermic body of a fine width.

Description

Exothermic element and method for manufacturing the same

BACKGROUND OF THE INVENTION 1. Field of the Invention [0001] The present invention relates to a heat generating element, and more particularly, to a heat generating element including a conductive heating element of a fine line width which is invisible and a method of manufacturing the same.

In the case of a transparent heater for an automobile glass which is currently in use, an electric resistance wire having a thickness of 500 탆 to 1 mm is printed. In order to ensure a smooth view of the driver, patterning .

In addition, since such a thick hot wire may interfere with the driver's vision, a hot wire pattern is formed only on a localized position on the front and side windows, and there is a limit in removing the frost of the glass in the indoor heating, Causing the driver to feel uncomfortable during driving.

Therefore, there have been studies to replace the conventional thick heat wire, and there have been studies in which transparent heaters are manufactured using ITO transparent electrodes, graphene transparent electrodes, dispersed silver nanowires or carbon nanotubes.

However, these processes have the following problems:

1) ITO transparent heaters use indium-tin-oxide (ITO) transparent conductors, which have indium resource depletion problems and high price problems. In addition, since the vacuum deposition process is used, the process steps and the process cost are expensive, and the transmittance is lowered at a lower wavelength of the visible light.

2) The graphene transparent heater grows the graphene film by chemical vapor deposition (CVD) which forms graphene on the metal catalyst layer. It requires a high temperature of 1000 ℃ or more during the process, and the explosive danger such as hydrogen and methane Materials are used. In addition, graphene grains need to be transferred to a desired substrate after the growth process. In the current technology, it is not easy to transfer a large area graphene to an automobile glass.

3) A method of manufacturing a transparent heater by coating a film on which nanowires or carbon nanotubes are dispersed is a method of coating a glass substrate with a solution in which silver nanowires and carbon nanotubes are uniformly dispersed to form silver nanowires or carbon nanotubes A conductive film is formed by interconnection between the electrodes. This method is also difficult to uniformly coat the dispersion solution on a large-area substrate, and the degree of dispersion of silver nanowires or carbon nanotubes may vary locally on the glass substrate, so that interconnection between silver nanowires or carbon nanotubes A portion that does not occur may occur. Silver nanowires or carbon nanotubes to increase interconnection between the nanowires and the carbon nanotubes has an advantage that the conductivity of the film is improved but the transmittance of light is lowered.

Therefore, it is necessary to study a manufacturing method of a heating element which can solve such a problem.

SUMMARY OF THE INVENTION The present invention has been made to solve the above problems, and it is an object of the present invention to provide a heating element including a conductive heating element of a fine line width of 1.8 탆 or less that is invisible through an electric field robotic nozzle printing method, The purpose is to provide.

According to an aspect of the present invention, there is provided a heating element. Wherein the heating element comprises a substrate, a conductive heating element formed of a one-dimensional conductive wire having a curved cross section located on at least one side of the substrate and having a fine line width of not more than 1.8 탆 which is invisible to the substrate, and a conductive heating element electrically connected to the conductive heating element Electrode.

Since the conductive fine line width heating element of 1.8 μm or less can not be recognized by the human eye, a completely transparent heating element can be manufactured, the Moire interference phenomenon can be overcome, and the haze phenomenon can be very low appear.

The conductive wires constituting the conductive heating element may have a shape aligned from one electrode to the other electrode, and the aligned conductive wires may have a straight line shape, a curved wave form, an aligned zigzag or a twisted shape .

The conductive heating element may be formed of a combination of one or more conductive wires, and the individual conductive wires may be continuously connected from one electrode to the other electrode.

The conductive wire constituting the conductive heating element is manufactured by an electric field assisted robot nozzle printing method. Such an electric field assisted robot nozzle printing method has a drawback in that it is difficult to implement by a conventional drop-on-demand type printing system such as inkjet printing or electrohydrohynamic jet printing, Can be easily produced.

The conductive heating element may have a curved cross section of the heating element. More specifically, the conductive heating element may be formed of a wire having a circular, elliptical, semicircular, arcuate, crushed round, crushed semicircular, squalene or crushed arcuate cross- An open hollow, an empty hollow elliptical, a hollow semicircular or hollow hollow arcuate tube shape.

The cross-section of the conductive heating element may include an aspect ratio of 10 or less, and more preferably, the cross-sectional aspect ratio is 5 or less. The length of the conductive heating element may be 1 mm or more.

Also, the conductive heating element may include a spiral shape.

The conductive heating element on the substrate is characterized in that the vertical direction between the electrodes and the horizontal patterns between the electrodes and the electrodes are aligned with each other.

In addition, the substrate may include at least one selected from the group consisting of a transparent substrate, a translucent substrate, an opaque substrate, a metal substrate, a conductive substrate, an insulating substrate, a carbon substrate, and a composite substrate of a conductor and an insulating film.

The electrode may be formed of a metal such as gold, silver, copper, titanium, platinum, aluminum, cobalt, chromium, magnesium, silicon, tungsten, stainless steel, nickel, ITO, graphene, carbon nanotube, silver nanowire, Polyaniline (PANI) and derivatives thereof, poly (3-hexylthiophene) (P3HT) and derivatives thereof, polyphenyl (PPY) and derivatives thereof, polythiophene (PT) and derivatives thereof, polyphenylene sulfide (PPS) and derivatives thereof, polyaluminum chloride (PAC) and derivatives thereof, and polyphenylene vinylene A derivative thereof, and a derivative thereof.

Also, the conductive heating element may include a metal, a metal oxide, or a conductive polymer. The metal may include at least one selected from the group consisting of gold, silver, copper, titanium, platinum, aluminum, cobalt, chromium, magnesium, silicon, tungsten, stainless steel and nickel. The metal oxide may include at least one selected from the group consisting of indium tin oxide, indium zinc oxide, indium gallium zinc oxide, tin oxide, zinc oxide, gallium zinc oxide, nickel oxide, copper oxide and aluminum oxide have. The conductive polymer may be at least one selected from the group consisting of poly (3,4-ethylenedioxythiophene) (PEDOT) and derivatives thereof, polyaniline (PANI) and derivatives thereof, poly (3-hexylthiophene) (PPY) and derivatives thereof, polythiophene (PT) and derivatives thereof, polyphenylene sulfide (PPS) and derivatives thereof, polyaluminum chloride (PAC) and derivatives thereof, and polyphenylene vinylene A derivative thereof, and a derivative thereof.

Meanwhile, it may further include a protective layer disposed on the conductive heating element. At this time, the protective layer may include at least one selected from the group consisting of a transparent material, a translucent material, an opaque material, a metal material, a conductive material, an insulating material, a carbon material, and a composite material of a conductor and an insulating film.

According to another aspect of the present invention, there is provided a method of manufacturing a heating element. The method includes the steps of: preparing a substrate; forming a conductive heating element made of a one-dimensional conductive wire having a curvilinear cross section and having a fine line width of not more than 1.8 mu m invisible on the substrate; And forming an electrode electrically connected to the electrode.

The step of forming the conductive heating element is performed by an electric field assisted robot nozzle printer, and the electric field assisted robotic nozzle printer includes:

i) a solution storage device for containing a printing solution;

ii) a nozzle device for discharging the solution supplied from the solution storage device;

iii) a voltage applying device for applying a voltage to the nozzle;

iv) a collector for fixing the substrate;

v) a voltage application device for applying a voltage to the substrate;

vi) a robot stage for moving the collector in a horizontal direction;

vii) a micro distance adjuster for moving the collector in a vertical direction; And

viii) a lithotripter supporting the collector.

The step of forming the conductive heating element includes the steps of preparing a printing solution by mixing the conductive heating material production material into distilled water or an organic solvent, injecting the printing solution into a nozzle of the electric field assisted robotic nozzle printer, The printing solution may be ejected from the nozzle to the substrate in accordance with the method described above, and the printing solution discharged onto the substrate may form a fine line width conductive heating element on the substrate.

The conductive heating element may include a metal, a metal oxide, or a conductive polymer. The metal may include at least one selected from the group consisting of gold, silver, copper, titanium, platinum, aluminum, cobalt, chromium, magnesium, silicon, tungsten, stainless steel and nickel. The metal oxide may include at least one selected from the group consisting of indium tin oxide, indium zinc oxide, indium gallium zinc oxide, tin oxide, zinc oxide, gallium zinc oxide, nickel oxide, copper oxide and aluminum oxide have. The conductive polymer may include at least one selected from the group consisting of PEDOT, PANI, P3HT, PPY, PT, PPS, PAC, PPV and derivatives thereof.

The organic solvent may also be selected from the group consisting of dimethylformamide (DMF), dimethylsulfoxide (DMSO), isopropyl alcohol (IPA), tetrahydrofuran (THF), chloroform (CF), chlorobenzene (CB), trichlorethylene And at least one selected from the group consisting of TCE, ethanol, methanol, acetone, toluene, acetic acid, and nitric acid.

Meanwhile, in the step of preparing the printing solution, the printing solution may include at least one of polyvinyl alcohol (PVA), polyvinyl acetate (PVAc), polyvinyl pyrrolidone (PVP), polymethyl methacrylate (PMMA), polyethylene oxide ), Polyvinylcarbazole (PVK), polystyrene (PS), and poly (vinylidene fluoride) (PVDF).

The externally applied electric field is an electric field formed by applying a voltage of -30 kV to 30 kV to the nozzle or the substrate at a voltage of -30 kV to 30 kV at the same time.

And the distance between the nozzle and the substrate is adjusted to be 10 to 300 mm vertically. Preferably 1 mm to 10 mm.

The conductive wire constituting the conductive heating element may be in the form of a wire having a circular cross section, an elliptical cross section, an arcuate cross section, a distorted circular cross section, a distorted round cross section, a distorted elliptical cross section or a distorted arcuate cross section, or a round hollow, hollow hollow, semi- Wherein the aspect ratio of the cross section of the conductive heating element is 5 or less and the length of the conductive heating element is adjusted to 1 mm or more.

The method may further include a heat treatment step, a vacuum drying step, or a light irradiation step to improve the conductivity and the heat generation property between the step of forming the conductive heating element and the step of forming the electrode or after the step of forming the electrode .

The heat treatment is performed in a gas atmosphere containing at least one selected from the group consisting of air, oxygen, nitrogen, hydrogen, and argon. The heat treatment step is characterized in that the heat treatment is performed at a temperature range of 40 ° C to 900 ° C for 1 minute to 5 hours.

The light irradiation step at this time is characterized in that light is irradiated using an excimer laser, an infrared laser, or a UV laser. The light irradiation step is characterized by irradiating light in a wavelength range of 150 nm to 500 탆 for 0.001 second to 5 hours.

In the step of forming the conductive heating element by the electric field assisted robotic nozzle printing method, the conductive heating element may be printed unlimitedly regardless of the length. Roll-to-roll process, and is capable of mass-producing a large-area heating element with very fast and high productivity.

According to another aspect of the present invention, there is provided a transparent heating glass. Such a transparent heat-generating glass is a transparent glass substrate; And the above-described heating element formed on the transparent glass substrate or the heating element manufactured by the above-described method for manufacturing a heating element.

According to another aspect of the present invention, there is provided a heating mirror. Such a heating mirror may include the above-described heating element or a heating element manufactured by the above-described method of manufacturing a heating element.

INDUSTRIAL APPLICABILITY According to the present invention, it is possible to provide a transparent heating element in which a heating element is invisible by using a conductive heating element composed of a one-dimensional wire having a fine line width of 1.8 m or less.

Further, by controlling the pattern shape or the interval of the conductive heating element of the fine line width, it is possible to provide a heating element which can increase the heating efficiency and freely adjust the transparency.

In addition, by using the electric field assisted robotic nozzle printing method, it is possible to print an unlimited number of conductive heating elements having an aspect ratio of 5 or less in cross section, without limitations in length.

In addition, since the conductive heating element of fine line width is manufactured through the printing method, the process step is simple, the process cost is low, and the heating element can be manufactured at a high speed.

Also, it can be applied to the roll-to-roll process, so that a large-area heating element can be mass-produced with very high productivity.

In addition, since the shape or the interval of the conductive heating element pattern of the fine line width can be controlled as desired through the electric-field robotic nozzle printing method, not only the heating efficiency can be increased but also the fabrication of the heating element capable of freely adjusting the transparency It is possible.

The technical effects of the present invention are not limited to those mentioned above, and other technical effects not mentioned can be clearly understood by those skilled in the art from the following description.

1 to 3 are sectional views of a heating element according to an embodiment of the present invention.
4 is a cross-sectional view of a heating element according to an embodiment of the present invention.
FIG. 5 is a flowchart illustrating a method of manufacturing a heating element using an electric field assisted robotic nozzle printing method according to an embodiment of the present invention. Referring to FIG.
6 is an electron microscope (SEM) image of a conductive heating element having a fine line width.
7 is a scanning electron microscope (SEM) image of a conductive heating element having a fine line width.
8 is a photograph of a transparent heating element using a fine line width conductive heating element manufactured through an electric field assisted robotic nozzle printing according to an embodiment of the present invention.
FIG. 9 is a graph and images of the heat generating characteristics of a heat generating element manufactured according to a manufacturing example.
10 is an image showing a conductive heating element of a heating element according to an embodiment of the present invention.
11 is a view showing a pattern of a conductive heating element of a heating element according to an embodiment of the present invention.

Hereinafter, embodiments of the present invention will be described in detail with reference to the accompanying drawings.

While the invention is susceptible to various modifications and alternative forms, specific embodiments thereof are shown by way of example in the drawings and will herein be described in detail. Rather, the intention is not to limit the invention to the particular forms disclosed, but rather, the invention includes all modifications, equivalents and substitutions that are consistent with the spirit of the invention as defined by the claims.

It will be appreciated that when an element such as a layer, region or substrate is referred to as being present on another element "on," it may be directly on the other element or there may be an intermediate element in between .

Although the terms first, second, etc. may be used to describe various elements, components, regions, layers and / or regions, such elements, components, regions, layers and / And should not be limited by these terms.

Throughout the specification of the present invention, when a part is referred to as "including " an element, it is understood that it may include other elements as well, without excluding other elements unless specifically stated otherwise.

  The word " step (or step) "or" step "used in the specification of the present invention does not mean" step for.

  The term " fine line width " used throughout the specification of the present invention means a line width of about 1.8 mu m or less. When the line width is 1.8 占 퐉 or less, it can not be recognized by the human eye, and a completely transparent heating element can be manufactured.

The term " aspect ratio " used in the entire specification of the present invention means the ratio of the width / height of the cross section to the cross section.

The terms "about "," substantially ", etc. used to the extent that they are used in the specification of the present invention are used in their numerical values or in close proximity to their numerical values when the manufacturing and material tolerances inherent in the meanings mentioned are presented, Accurate or absolute numbers are used to help prevent unauthorized exploitation by unauthorized intruders of the referenced disclosure.

1 to 3 are sectional views of a heating element according to an embodiment of the present invention.

1 to 3, a heating element according to an embodiment of the present invention includes a substrate 100, a conductive heating element 110, and an electrode 120.

The substrate 100 may include at least one selected from the group consisting of a transparent substrate, a translucent substrate, an opaque substrate, a metal substrate, a conductive substrate, an insulating substrate, a carbon substrate, and a composite substrate of a conductor and an insulating film.

In the case of implementing a transparent heat generating element, the substrate 100 may use a transparent substrate. For example, it can be used as a transparent glass substrate to provide a transparent heat generating element.

The conductive heating element 110 is composed of a one-dimensional conductive wire having a curved cross-section and a non-visible in-plane fine line width of 1.8 μm or less, located on at least one side of the substrate 100. The conductive heating element 110 is not particularly limited as long as it is formed on one or more surfaces of the substrate.

At this time, the fine line width of the conductive heating element 110 may be 1.8 占 퐉 or less. More specifically, the line width may be 100 nm to 1 占 퐉 or less.

Therefore, since the fine line width of the conductive heating element 110 is 1.8 占 퐉 or less, it will be almost invisible to the eye. That is, there is an advantage that a transparent heat generating element 110 having a fine line width of 1.8 μm or less and capable of realizing a transparency of 90% or more can be provided.

The fine line width of the conductive heating element 110 of 1.8 μm or less can be manufactured by an electric field assisted robotic nozzle printing method. It is very difficult to realize a conductive heating element having a fine line width of 1.8 μm or less by ink-jet printing or electrohydrohynamic jet printing, which is a typical drop-on-demand type printing method. In addition, the conductive heating element 110 can be manufactured without restrictions on the length by an electric field assisted robotic nozzle printing method.

Accordingly, the conductive heating element 110 composed of the one-dimensional conductive wire having a fine line width can be manufactured in various patterns by using the electric field assisted robotic nozzle printing method. The one-dimensional conductive wire is characterized by being arranged in one direction and constituted of one wire from one electrode to the other electrode.

The conductive wires constituting the conductive heating element have a shape aligned from one electrode to the other electrode, and the aligned wires may have a straight line shape, a curved wave form, an aligned zigzag or a twisted shape. have.

The conductive heating element may be formed of a combination of one or more conductive wires, and the individual conductive wires may be continuously connected from one electrode to the other electrode.

In addition, the conductive heating element 110 manufactured by the electric field assisted robotic nozzle printing method includes a heating element having a curved cross section. More specifically, the heating element has a circular, oval, semicircular, arcuate, squashed circular, A distorted elliptical or distorted arcuate wire form, or a hollow, circular hollow, hollow hollow elliptical, hollow semicircular or hollow hollow arcuate tube shape.

The cross section of the conductive heating element, that is, the cross section of the conductive wire constituting the conductive heating element may include an aspect ratio of 10 or less, and more preferably, the cross-sectional aspect ratio is 5 or less. For example, when the cross section of the conductive heating element has a width of 1 占 퐉 and a height of 0.2 占 퐉, the cross-sectional aspect ratio may be 5. Therefore, when the cross-sectional aspect ratio is 5 or less, the width of the cross section of the conductive heating element is 1 占 퐉, and the height is 0.2 占 퐉 or more. Therefore, when the cross-sectional aspect ratio is 5 or less, the width of the cross-section of the conductive heating element is small and the height is large, thereby realizing the invisible fine line width and maintaining the heat generation property by increasing the heat- have.

In addition, the conductive heating element 110 may include a linear shape, a spiral shape, a zigzag shape, or a twisted shape. Therefore, by arranging the conductive heating elements 110 on the substrate 100 in various pattern shapes or by adjusting the intervals of these patterns, not only the heat efficiency can be increased, but also the transparency can be freely adjusted.

In addition, the conductive heating element 110 on the substrate 100 may be a pattern in which the vertical direction between the electrodes and the horizontal patterns between the electrodes and the electrodes are aligned with each other. For example, the conductive heating element 110 having a fine linewidth fabricated by a printing method can be formed in a lattice-like structure, and in this case, the temperature uniformity of the heating element can be further improved.

The conductive heating element 110 may include a metal, a metal oxide, or a conductive polymer. The metal may include at least one selected from the group consisting of gold, silver, copper, titanium, platinum, aluminum, cobalt, chromium, magnesium, silicon, tungsten, stainless steel and nickel. The metal oxide may include at least one selected from the group consisting of indium tin oxide, indium zinc oxide, indium gallium zinc oxide, tin oxide, zinc oxide, gallium zinc oxide, nickel oxide, copper oxide and aluminum oxide have. The conductive polymer may include at least one selected from the group consisting of PEDOT, PANI, P3HT, PPY, PT, PPS, PAC, PPV and derivatives thereof.

The electrode 120 may be electrically connected to the conductive heating element 110. For example, the electrode 120 may be formed at an end, an upper portion, a lower portion, or a side surface of a conductive heating element having a fine line width .

For example, as shown in FIGS. 1 to 3, the electrode 120 may be formed on the side (the case of FIG. 1), the upper end (the case of FIG. 2) ). ≪ / RTI >

The electrodes 120 may be used without limitation to electrodes that exhibit conductivity commonly used in the art. For example, gold, silver, copper, titanium, platinum, aluminum, cobalt, chromium, A transparent electrode including at least one selected from the group consisting of ITO, graphene, carbon nanotube, and silver nanowire; a metal electrode including at least one metal or alloy selected from the group consisting of tungsten, stainless steel, and nickel; , PEDOT, PANI, P3HT, PPY, PT, PPS, PAC, PPV and derivatives thereof, but the present invention is not limited thereto.

According to the present invention, by using the conductive heating element 110 having a fine line width, it is possible to provide an invisible transparent heating element. In addition, by controlling the pattern shape or the interval of the conductive heating element 110 having a fine line width, it is possible to provide a heating element which can increase the heating efficiency and freely adjust the transparency.

4 is a cross-sectional view of a heating element according to an embodiment of the present invention.

Referring to FIG. 4, a heating element according to an embodiment of the present invention includes a substrate 100, a conductive heating element 110, an electrode 120, and a protective layer 130.

The heating element of FIG. 4 is the same as that of the heating element of FIG. 1 except that it further includes the protective layer 130, and only the protective layer 130 will be described in detail.

The protective layer 130 is disposed on the conductive heating element 110. Accordingly, the protective layer 130 protects the conductive heating element from oxidation problems caused by contact with the outside.

The protective layer 130 may include at least one selected from the group consisting of a transparent material, a translucent material, an opaque material, a metal material, a conductive material, an insulating material, a carbon material, and a composite material of a conductor and an insulating layer.

A method of manufacturing a heating element according to an embodiment of the present invention will be described.

A method of manufacturing a heating element according to an embodiment of the present invention includes the steps of preparing a substrate, forming a conductive heating element composed of a one-dimensional conductive wire having a curved cross-section on the substrate and having a fine linewidth of less than 1.8 [ And forming an electrode electrically connected to the conductive heating element pattern.

First, the substrate is prepared. The substrate may include at least one selected from the group consisting of a transparent substrate, a translucent substrate, an opaque substrate, a metal substrate, a conductive substrate, an insulating substrate, a carbon substrate, and a composite substrate of a conductor and an insulating film.

Then, a conductive heating element having a fine line width is formed on the substrate.

The step of forming the conductive heating element may be performed by an electric field assisted robotic nozzle printer.

For example, such an electric field assisted robotic nozzle printer

i) a solution storage device for containing a printing solution;

ii) a nozzle device for discharging the solution supplied from the solution storage device;

iii) a voltage applying device for applying a voltage to the nozzle;

iv) a collector for fixing the substrate;

v) a voltage application device for applying a voltage to the substrate;

vi) a robot stage for moving the collector in a horizontal direction;

vii) a micro distance adjuster for moving the collector in a vertical direction; And

viii) a lithotripter supporting the collector.

The step of forming the conductive heating element may include preparing a printing solution by mixing the material for manufacturing a conductive heating element into distilled water or an organic solvent, injecting the printing solution into a nozzle of the electric field assisted robotic nozzle printer, A step of ejecting the printing solution from the nozzle to the substrate in accordance with an electric field, and a step of forming the conductive heating element of the fine line width on the substrate by the printing solution discharged to the substrate.

When the conductive heating element is formed, the length of the fine line width can be adjusted to 1.8 μm or less by adjusting the concentration of the printing solution, the magnitude of the voltage applied from the outside, and the moving speed of the robot stage. For example, the length of the fine line width of the conductive heating element to be formed can be reduced by decreasing the concentration of the printing solution, decreasing the voltage of the electric field applied from the outside, or increasing the moving speed of the robot stage.

Such a conductive heating element may include a metal, a metal oxide, or a conductive polymer. The metal may include at least one selected from the group consisting of gold, silver, copper, titanium, platinum, aluminum, cobalt, chromium, magnesium, silicon, tungsten, stainless steel and nickel. The metal oxide may include at least one selected from the group consisting of indium tin oxide, indium zinc oxide, indium gallium zinc oxide, tin oxide, zinc oxide, gallium zinc oxide, nickel oxide, copper oxide and aluminum oxide have. The conductive polymer may include at least one selected from the group consisting of PEDOT, PANI, P3HT, PPY, PT, PPS, PAC, PPV and derivatives thereof.

In addition, such a conductive heating element may have a shape in which the cross section of the heating element is a circle, an ellipse, a semicircle, an arcuate shape, a distorted circle, a distorted semicircular shape, a distorted elliptical shape or a distorted arcuate wire shape, or a hollow, circular, oval, And may be in the form of an empty arcuate tube.

The formation of such a conductive heating element in the form of a wire or a tube can be determined by the diffusion rate of the conductive heating element materials. For example, if the conductive heating element is copper, it may be in the form of a hollow circular tube. In another example, when the conductive heating element is silver, it may be in the form of a circular wire.

In addition, the aspect ratio of the cross section of such a conductive heating element is 5 or less, and the length of the heating element can be adjusted to 1 mm or more.

That is, the conductive heating element 110 can be manufactured without restrictions on the length by an electric field assisted robotic nozzle printing method. Accordingly, the conductive heating element 110 can be manufactured in a variety of pattern shapes using a one-dimensional conductive wire having a fine line width by using an electric field assisted robotic nozzle printing method. The one-dimensional conductive wire is characterized by being arranged in one direction and constituted of one wire from one electrode to the other electrode. Aligned wires can be perfectly straight and wavy.

The organic solvent may include at least one selected from the group consisting of DMF, DMSO, IPA, THF, CF, CB, TCE, ethanol, methanol, acetone, toluene, acetic acid and nitric acid.

In the preparing of the printing solution, the printing solution may further include at least one organic material selected from the group consisting of PVA, PVAc, PVP, PMMA, PEO, PVK, PS and PVDF.

The externally applied electric field is an electric field formed by applying a voltage of -30 kV to 30 kV to the nozzle or the substrate at a voltage of -30 kV to 30 kV at the same time.

On the other hand, in order to print the conductive heating element of fine line width horizontally aligned with high alignment, the interval between the nozzle and the substrate may be vertically adjusted to 10 to 300 mm. Preferably 1 mm to 10 mm.

And then an electrode electrically connected to the conductive heating element is formed. The method of forming such an electrode may include at least one selected from the group consisting of drop casting, spin coating, electron beam evaporation, thermal evaporation, vacuum evaporation, and printing.

Meanwhile, in order to improve the conductivity and exothermic characteristic between the step of forming the conductive heating element and the step of forming the electrode or the step of forming the electrode, a heat treatment step, a vacuum drying step or a light irradiation step .

The heat treatment is performed in a gas atmosphere containing at least one selected from the group consisting of air, oxygen, nitrogen, hydrogen, and argon. The heat treatment step may be heat treated for 1 minute to 5 hours at a temperature range of 40 占 폚 to 900 占 폚. In addition, the heat treatment step may be characterized by heat treatment one to five times, but is not limited thereto.

The light irradiation step is characterized by irradiating light using an excimer laser, an infrared laser, or a UV laser. The light irradiation step at this time may be light irradiation for 0.001 second to 5 hours in a wavelength range of 150 nm to 500 占 퐉. The light irradiation step may be irradiated once to 50 times, but is not limited thereto.

In addition, the process of manufacturing the conductive heating element by the electric field assisted robotic nozzle printing method is also applicable to the roll-to-roll process, so that it is possible to mass-produce a large-sized heating element with very fast and high productivity. But is not limited to.

Hereinafter, a method of manufacturing a heating element including a conductive heating element pattern using an electric field assisted robotic nozzle printing method will be described with reference to FIG.

FIG. 5 is a flowchart illustrating a method of manufacturing a heating element using an electric field assisted robotic nozzle printing method according to an embodiment of the present invention. Referring to FIG.

Referring to FIG. 5, first, a printing solution for fabricating a conductive heating element pattern is prepared (S100).

Subsequently, the conductive heating element pattern of fine line width can be manufactured (S200) by the electric field assisted robot nozzle printing.

Subsequently, a subsequent process such as heat treatment may be performed on the conductive heating element pattern having a fine line width (S300).

Accordingly, a conductive heating element pattern having a fine line width can be formed on the substrate (S400).

And then the electrode is brought into contact with the conductive heating element pattern of the fine line width formed next (S500).

According to the present invention, since a conductive heating element having a fine line width is manufactured through a printing method, a process step is simple, a process cost is low, and a heating element can be manufactured at a high speed.

In addition, it is possible to form the conductive heating element pattern of the fine line width without limitation of the length through the electric field robotic nozzle printing method, and the shape or the interval of the pattern can be controlled as desired so that the heating efficiency can be increased, It is possible to manufacture a heating element capable of freely adjusting the temperature of the heating element.

Manufacturing example

The conductive heating element of fine line width was fabricated by the electric field assisted robotic nozzle printing method.

To the precursor _{(C 2 AgF 3 O 2,} 21 wt%) and the copper precursor _{(C 4 CuF 6 O 4,} 6.25 wt%), PVP (Polyvinyl pyrrolidone) (10 wt%) in dimethylformamide and tetrahydrofuran To prepare a metal precursor / PVP composite printing solution.

The concentration of the metal precursor / PVP composite printing solution was 31 wt%. The prepared metal precursor / PVP hybrid printing solution was placed in a syringe of the electric field assisted robotic nozzle printer, and the metal precursor / PVP hybrid printing solution was discharged from the nozzle while applying a voltage of about 0.5 kV to the nozzle.

A metal line precursor / PVP composite nano pattern having a fine line width aligned on the substrate of the collector moved by the robot stage was formed. At this time, the diameter of the used nozzle was 100 mu m, and the distance between the nozzle and the collector was 7 mm.

The moving distance in the Y axis direction of the robot stage was 100 mu m and the moving distance in the X axis direction was 15 cm. The size of the collector was 20 cm x 20 cm, and the size of the substrate on the collector was 2.5 cm x 2.5 cm. The type of the substrate was a transparent glass substrate.

Thereafter, the metal precursor / PVP composite nanopattern having the fine line widths aligned in the furnace is subjected to heat treatment in air at a temperature of 300 ° C to 500 ° C for 5 minutes to 2 hours to pyrolyze the PVP organic polymer, The copper precursor is reduced to silver nano-grains and copper nano-grains, and a conductive silver-copper composite nano-pattern heating element composed of the silver nanogram and the copper nanogram is formed.

Thus, a fine line width conductive silver - copper composite nano pattern heating element for a heating element having an area of 2.5 cm × 2.5 cm was fabricated by using a method of manufacturing a fine line width conductive heating element manufactured by an electric field assisted robotic nozzle printing method.

6 is an electron microscope (SEM) image of a conductive heating element having a fine line width.

Referring to FIG. 6, it can be seen that a conductive heating element having fine line width aligned in one direction can be manufactured by using an electric field assisted robotic nozzle printing method.

7 is a scanning electron microscope (SEM) image of a conductive heating element having a fine line width.

Referring to FIG. 7, it can be seen that a fine line-width conductive heating element arranged in a lattice form can be manufactured by using an electric field assisted robotic nozzle printing method.

8 is a photograph of a transparent heating element using a fine line width conductive heating element manufactured through an electric field assisted robotic nozzle printing according to an embodiment of the present invention.

Referring to FIG. 8, as a heating element manufactured according to a manufacturing example, more specifically, a fine line width conductive silver-copper composite nano-pattern heating element manufactured on a glass substrate having an area of 2.5 cm x 2.5 cm, And a transparent heating element in which electrodes are formed using silver paste at both ends. Accordingly, it can be seen that a transparent heating element including a transparent heating element having a fine line width can be provided by using an electric field assisted robotic nozzle printing method.

FIG. 9 is a graph and images of the heat generating characteristics of a heat generating element manufactured according to a manufacturing example. 9 (a) is a graph showing changes in surface temperature with time according to voltage application of a heating element according to an embodiment of the present invention, and Figs. 9 (b) and 9 (c) The temperature distribution of the heating element according to the example is a thermal image measured using a thermal imaging camera.

Referring to FIG. 9, it can be seen that when a voltage between 3 V and 12 V is applied, the exothermic temperature rises as the applied voltage is increased. At this time, it can be seen that the exothermic temperature reaches the maximum temperature within one minute.

10 is an image showing a conductive heating element of a heating element according to an embodiment of the present invention. Referring to FIG. 10, it can be seen that a copper conductive heating element manufactured using an electric field assisted robotic printing method can be manufactured in a circular shape in which the cross section of the heating element is hollow.

11 is a view showing a pattern of a conductive heating element of a heating element according to an embodiment of the present invention. 11 (a) and 11 (b)), a zigzag pattern (Fig. 11 (c)), or a straight line pattern (Fig. 11 (d)).

It should be noted that the embodiments of the present invention disclosed in the present specification and drawings are only illustrative of specific examples for the purpose of understanding and are not intended to limit the scope of the present invention. It will be apparent to those skilled in the art that other modifications based on the technical idea of the present invention are possible in addition to the embodiments disclosed herein.

100: substrate 110: conductive heating element
120: electrode 130: protective layer

Claims (31)

Board;
A conductive heating element disposed on at least one surface of the substrate and having a curved cross section and formed of a one-dimensional conductive wire having a fine line width of not more than 1.8 탆 which is invisible; And
And an electrode electrically connected to the conductive heating element. The method according to claim 1,
The conductive wires constituting the conductive heating element may have a shape aligned from one electrode to the other electrode, and the aligned conductive wires may have a straight line shape, a curved wave form, an aligned zigzag or a twisted shape And a heating element. The method according to claim 1,
Wherein the conductive heating element is formed of a combination of at least one conductive wire and the individual conductive wires are connected seamlessly from one electrode toward the other electrode. The method according to claim 1,
Wherein the conductive wire constituting the conductive heating element is manufactured by an electric field assisted robotic nozzle printing method. The method according to claim 1,
The conductive wire constituting the conductive heating element may be in the form of a wire having a circular cross section, an elliptical cross section, an arcuate cross section, a distorted circular cross section, a distorted round cross section, a distorted elliptical cross section or a distorted arcuate cross section, or a round hollow, hollow hollow, semi- A heating element comprising an arcuate tube shape hollowed out. The method according to claim 1,
Wherein the aspect ratio of the cross section of the conductive heating element is 5 or less, and the length of the conductive heating element is 1 mm or more. The method according to claim 1,
Wherein the conductive heating element includes a spiral shape. The method according to claim 1,
Wherein the conductive heating element on the substrate is arranged such that the vertical direction between the electrodes and the horizontal patterns between the electrodes and the electrodes are aligned with each other. The method according to claim 1,
Wherein the substrate comprises at least one selected from the group consisting of a transparent substrate, a translucent substrate, an opaque substrate, a metal substrate, a conductive substrate, an insulating substrate, a carbon substrate, and a composite substrate of a conductor and an insulating film. The method according to claim 1,
The electrode may be formed of a metal such as gold, silver, copper, titanium, platinum, aluminum, cobalt, chromium, magnesium, silicon, tungsten, stainless steel, nickel, ITO, graphene, carbon nanotube, silver nanowire, , Alloy nanowires, PEDOT and derivatives thereof, PANI and derivatives thereof, P3HT and derivatives thereof, PPY and derivatives thereof, PT and derivatives thereof, PPS and derivatives thereof, PAC and derivatives thereof, and PPV and derivatives thereof And at least one selected. The method according to claim 1,
Wherein the conductive heating element includes a metal, a metal oxide, or a conductive polymer. 12. The method of claim 11,
Wherein the metal comprises at least one selected from the group consisting of gold, silver, copper, titanium, platinum, aluminum, cobalt, chromium, magnesium, silicon, tungsten, stainless steel and nickel. 12. The method of claim 11,
Wherein the metal oxide includes at least one selected from the group consisting of indium tin oxide, indium zinc oxide, indium gallium zinc oxide, tin oxide, zinc oxide, gallium zinc oxide, nickel oxide, copper oxide and aluminum oxide. 12. The method of claim 11,
Wherein the conductive polymer comprises at least one selected from the group consisting of PEDOT, PANI, P3HT, PPY, PT, PPS, PAC, PPV and derivatives thereof. The method according to claim 1,
And a protective layer disposed on the conductive heating element. 16. The method of claim 15,
Wherein the protective layer comprises at least one selected from the group consisting of a transparent material, a translucent material, an opaque material, a metal material, a conductive material, an insulating material, a carbon material, and a composite material of a conductor and an insulating film. Preparing a substrate;
Forming a conductive heating element made of a one-dimensional conductive wire having a curved cross-section on the substrate and having an invisible fine line width of 1.8 mu m or less; And
And forming an electrode electrically connected to the conductive heating element. 18. The method of claim 17,
The forming of the conductive heating element may include:
Wherein the electric field assisted robotic nozzle printer is implemented by an electric field assisted robotic nozzle printer,
i) a solution storage device for containing a printing solution;
ii) a nozzle device for discharging the solution supplied from the solution storage device;
iii) a voltage applying device for applying a voltage to the nozzle;
iv) a collector for fixing the substrate;
v) a voltage application device for applying a voltage to the substrate;
vi) a robot stage for moving the collector in a horizontal direction;
vii) a micro distance adjuster for moving the collector in a vertical direction; And
and viii) a step of supporting the collector. 19. The method of claim 18,
The forming of the conductive heating element may include:
Preparing a printing solution by mixing a conductive heating material production material into distilled water or an organic solvent;
Injecting the printing solution into a nozzle of the electric field assisted robotic nozzle printer and discharging the printing solution from the nozzle to the substrate according to an external electric field; And
And forming a conductive heating element of a fine line width on the substrate by the printing solution discharged onto the substrate. 18. The method of claim 17,
Wherein the conductive heating element comprises a metal, a metal oxide, or a conductive polymer. 20. The method of claim 19,
Wherein the externally applied electric field is an electric field formed by applying a voltage of -30 kV to 30 kV to the nozzle or the substrate at a voltage of -30 kV to 30 kV at the same time. 20. The method of claim 19,
Wherein the gap between the nozzle and the substrate is adjusted to be 10 to 300 mm vertically. 18. The method of claim 17,
The conductive wire constituting the conductive heating element may be in the form of a wire having a circular cross section, an elliptical cross section, an arcuate cross section, a distorted circular cross section, a distorted round cross section, a distorted elliptical cross section or a distorted arcuate cross section, or a round hollow, hollow hollow, semi- Including an arcuate hollow tube shape,
Wherein the aspect ratio of the cross section of the conductive heating element is 5 or less and the length of the conductive heating element is adjusted to 1 mm or more. 18. The method of claim 17,
Between the step of forming the conductive heating element and the step of forming the electrode, or after the step of forming the electrode,
Further comprising a heat treatment step, a vacuum drying step, or a light irradiation step to improve conductivity and heat generation characteristics. 25. The method of claim 24,
Wherein the heat treatment step is performed in a gas atmosphere including at least one selected from the group consisting of air, oxygen, nitrogen, hydrogen, and argon. 25. The method of claim 24,
Wherein the heat treatment step is performed at a temperature ranging from 40 ° C to 900 ° C for 1 minute to 5 hours. 25. The method of claim 24,
Wherein the light irradiation step comprises irradiating light using an excimer laser, an infrared laser, or a UV laser. 25. The method of claim 24,
Wherein the light irradiation step is performed in a wavelength range of 150 nm to 500 占 퐉 for 0.001 second to 5 hours. 18. The method of claim 17,
Wherein the step of forming the conductive heating element is performed by a roll-to-roll process. Transparent glass substrate; And
The transparent electrode layer is formed on the transparent glass substrate by using the heat generating element according to any one of claims 1 to 16, or the transparent element including the heat generating element manufactured by the method for manufacturing a heat generating element according to any one of claims 17 to 29. Heat glass. A heating mirror comprising a heating element according to any one of claims 1 to 16, or a heating element manufactured by the method for manufacturing a heating element according to any one of claims 17 to 29.

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