KR101826149B1

KR101826149B1 - Transparent surface heating device

Info

Publication number: KR101826149B1
Application number: KR1020150056762A
Authority: KR
Inventors: 이대환; 김동규; 송상민; 김상균; 한송이; 김예슬
Original assignee: 코오롱인더스트리 주식회사; 이대환
Priority date: 2015-04-22
Filing date: 2015-04-22
Publication date: 2018-02-06
Also published as: KR20160125796A

Abstract

A heating layer formed on the substrate and including a conductive material; an electrode connected on the heating layer; and a protective layer formed on the heating layer, wherein the protective layer comprises pores. And a heating element.

Description

Transparent surface heating element {TRANSPARENT SURFACE HEATING DEVICE}

The present invention relates to a transparent surface heating element in which a protective layer containing pores is formed.

Due to the depletion of energy resources, countries around the world are investing heavily in energy conservation research. In accordance with this trend, the surface heating element, which has recently been emphasized, can reduce the electric power by 20% to 40% compared to the electric heating element which is generally used, and it is expected that electric energy saving and economic ripple effect will be great.

In general, the surface heating element uses radiant heat generated by electric power supply, so that it is easy to control the temperature, does not pollute the air, has advantages in hygiene and noise, and is widely used in bedding such as heating mat or pad. In addition, the surface heating element can be used for various types of industrial heating devices such as floor heating of a house, office and workplace, heating of various industrial fields such as painting and drying, a plastic house, a farmhouse, an automobile rearview mirror, a freezing prevention device for parking, Household appliances and the like.

Surface heating elements have been used especially recently, replacing many parts of home heating in Europe. They are new materials that can be applied to industrial dryers, agricultural dryer, health care aids, and building materials besides housing, It is expected that it will be used.

In addition, the configuration and material of the surface heat emission element are variously changed, and research on application of new applications, for example, clothing, frame stove, etc., is continued. Particularly, the use of materials that simultaneously exhibit transparency and conductivity has been applied to fields such as windows and mirrors where transparency is required.

Due to such characteristics, a transparent conductive thin film widely used for a conventional touch screen panel (TSP) can be used as a surface heating element. Any conductive material such as a metal oxide, a metal nanoparticle, a metal nanowire, a metal paste, and a carbon nanostructure may be used as a heating layer.

Particularly, a metal nanowire having a one-dimensional structure or a carbon nanotube or the like forms an electrical network, and a film having high electrical conductivity can be produced when the conductive film is constituted. In addition, since the material of one-dimensional structure has a diameter of several nm to several tens nm, it is excellent in dispersibility and can obtain a transmittance of 85% or more in the visible light region when the film is made into a film.

However, even though the conductive material having a constant aspect ratio, such as metal nanowires or carbon nanotubes, is dispersed in a discontinuous phase, even if the ink is uniformly dispersed, coagulation of conductive materials may occur during the process of being coated on the substrate and dried. In the state where the uniformity is not good, the applied current does not flow uniformly, locally high heat is generated, and uneven heat generation occurs or breakage occurs.

Korean Patent No. 10-1222639 discloses a transparent heating element including graphene. However, the transparent heating element also has poor uniformity in the process of forming graphene on the substrate, and locally high heat is generated on the graphene .

The present invention provides a transparent surface heating element in which a protective layer including pores is formed.

However, the problems to be solved by the present invention are not limited to the above-mentioned problems, and other problems not mentioned can be clearly understood by those skilled in the art from the following description.

According to a first aspect of the present invention, A heating layer formed on the substrate and including a conductive material; An electrode connected to the heating layer; And a protective layer formed on the heating layer, wherein the protective layer comprises pores.

According to one embodiment of the present invention, the protective layer may have a thickness of about 50 nm to about 200 탆, but is not limited thereto.

According to an embodiment of the present invention, the pores of the protective layer may have a size of about 5 nm to about 10 탆, but the present invention is not limited thereto.

According to one embodiment of the invention, the substrate may be transparent, but is not limited thereto.

According to one embodiment of the present invention, the substrate may be a silicon substrate, a glass substrate, or a polymer substrate, but is not limited thereto.

According to one embodiment of the present invention, the conductive material may be selected from the group consisting of metal oxides, metal nanowires, carbon nanostructures, metal pastes, metal nanoparticles, and combinations thereof. It is not. The metal oxide may be at least one selected from the group consisting of indium tin oxide (ITO), zinc tin oxide (ZTO), indium gallium zinc oxide (IGZO), zinc aluminum oxide (ZAO), indium zinc oxide (IZO), zinc oxide And the metal nanowires may be selected from the group consisting of silver, gold, platinum, copper, nickel, aluminum, titanium, palladium, cobalt, cadmium, rhodium and combinations thereof And the carbon nanostructure may be selected from the group consisting of graphene, carbon nanotube, fullerene, carbon black, and combinations thereof, and the metal paste may be selected from the group consisting of silver Gold, platinum, copper, nickel, aluminum, titanium, palladium, cobalt, cadmium, rhodium, and combinations thereof. The metal nanoparticles may be silver, For example, a metal selected from the group consisting of copper, nickel, aluminum, titanium, palladium, cobalt, cadmium, rhodium, and combinations thereof.

According to one embodiment of the present invention, the heating layer may have a thickness of about 10 nm to about 500 nm, but is not limited thereto.

According to an embodiment of the present invention, heat may be generated in the heating layer when power is applied through the electrode, but the present invention is not limited thereto.

According to an embodiment of the present invention, the electrode may include a transparent electrode, but is not limited thereto.

According to an embodiment of the present invention, the electrode may be formed of a metal such as silver, gold, platinum, aluminum, copper, chromium, vanadium, magnesium, titanium, tin, lead, palladium, tungsten, nickel, ), Metal nanowires, carbon nanostructures, and combinations thereof, but is not limited thereto.

According to one embodiment of the present invention, the electrodes may be of more than one pair, but the present invention is not limited thereto.

The second aspect of the present invention provides a transparent surface heating element system formed by connecting a plurality of transparent surface heating elements according to the first aspect of the present invention in series or in parallel.

According to one embodiment of the present invention, since the pattern layer is formed on the substrate of the transparent surface heating element, the aggregation phenomenon occurring between the conductive materials in the heating layer including the conductive material is physically prevented, and the uniformity of the conductive material in the heating layer It is possible to improve the heat efficiency and life of the transparent surface heat emission element. Further, since the transparent surface heating element according to one embodiment of the present invention exhibits characteristics of low resistance and high transmittance, it can be applied to various applications. In addition, the transparent surface heating element according to an embodiment of the present invention includes pores in the protective layer to minimize the loss of heat generated in the heating layer, thereby improving the heat insulating effect.

1 is a structural view of a transparent side heating element according to one embodiment of the present invention.

Hereinafter, embodiments and examples of the present invention will be described in detail with reference to the accompanying drawings, which will be readily apparent to those skilled in the art to which the present invention pertains.

It should be understood, however, that the present invention may be embodied in many different forms and is not limited to the embodiments and examples described herein. In order to clearly illustrate the present invention, parts not related to the description are omitted, and similar parts are denoted by like reference characters throughout the specification.

Throughout this specification, when a part is referred to as being "connected" to another part, it is not limited to a case where it is "directly connected" but also includes the case where it is "electrically connected" do.

Throughout this specification, when a member is "on " another member, it includes not only when the member is in contact with the other member, but also when there is another member between the two members.

Throughout this specification, when an element is referred to as "including " an element, it is understood that the element may include other elements as well, without departing from the other elements unless specifically stated otherwise.

As used herein, the terms "about," " substantially, "and the like are used herein to refer to or approximate the numerical value of manufacturing and material tolerances inherent in the stated sense, Accurate or absolute numbers are used to prevent unauthorized exploitation by unauthorized intruders of the mentioned disclosure. Also, throughout the present specification, the phrase " step "or" step "does not mean" step for.

Throughout this specification, the term "combination (s) thereof " included in the expression of the machine form means a mixture or combination of one or more elements selected from the group consisting of the constituents described in the expression of the form of a marker, Quot; means at least one selected from the group consisting of the above-mentioned elements.

Throughout this specification, the description of "A and / or B" means "A, B, or A and B".

Hereinafter, the transparent surface heating element of the present invention will be described in detail with reference to the embodiments, examples and drawings. However, the present invention is not limited to these embodiments and examples and drawings.

1 is a structural view of a transparent surface heating element according to an embodiment of the present invention.

One aspect of the present invention provides a lithographic apparatus comprising: a substrate; A heating layer (200) formed on the substrate and including a conductive material; An electrode 300 connected on the heating layer; And a protective layer (400) formed on the heating layer, wherein the protective layer comprises a pore (500).

The transparent surface heating element includes a substrate 100.

According to one embodiment of the invention, the substrate may be transparent. The substrate may be a conventional substrate, for example, a silicon substrate, a glass substrate, or a polymer substrate, but is not limited thereto.

The silicon substrate may be, for example, a single silicon substrate or a p-Si substrate, and the glass substrate may be one containing, for example, an alkali silicate glass, a non-alkali glass, And the polymer substrate may include, for example, polyimide, polyethersulfone, polyetheretherketone, polyethylene terephthalate, polybutylene terephthalate, polycarbonate, polyacrylate, or polyurethane , But is not limited thereto.

A heating layer (200) is formed on the substrate (100).

The conductive material contained in the heating layer 200 formed on the substrate 100 is uniformly dispersed to physically prevent the conductive material from aggregating and thus the conductive material contained in the heating layer 200 The uniformity is improved. The conductive material is uniformly dispersed in the heating layer 200 so that the current applied to the heating layer 200 can uniformly flow throughout the heating layer 200. As a result, The life can be improved.

The heating layer 200 includes a conductive material.

The conductive material may be, but is not limited to, an inkable material capable of low-cost processing. The heating layer 200 may be formed by applying a solution containing the conductive material on the substrate 100 to form a film or a thin film.

The application of the solution containing the conductive material can be carried out by various methods known in the art. For example, spray coating, bar coating, dip coating, spin coating, slit die coating, curtain coating, gravure coating, reverse gravure coating, roll coating, or impregnation may be used.

The solution containing the conductive material is a solution in which the conductive material is dispersed in a solvent such as water or alcohol in an amount of about 0.1 wt% to about 1.5 wt% as solid content. A solution of less than 0.1% by weight may not produce a sheet resistance due to insufficient network formation between the conductive materials after coating, and a solution of more than 1.5% by weight may cause aggregation of the conductive material in the solution to a large extent, The aggregation may affect the optical properties and may not be effective for pattern formation due to an increase in viscosity.

The conductive material may be selected from the group consisting of metal oxides, metal nanowires, carbon nanostructures, metal pastes, metal nanoparticles, and combinations thereof, but is not limited thereto.

Examples of the metal oxide include indium tin oxide (ITO), zinc tin oxide (ZTO), indium gallium zinc oxide (IGZO), zinc aluminum oxide (ZAO), indium zinc oxide (IZO) , And combinations thereof. However, the present invention is not limited thereto.

The metal nanowires may comprise metal nanowires selected from the group consisting of, for example, silver, gold, platinum, copper, nickel, aluminum, titanium, palladium, cobalt, cadmium, rhodium, But is not limited thereto. Silver nanowires have excellent transparency and conductivity, and when a voltage is applied to a film containing silver nanowires, the heat generation efficiency is excellent. The heat generating layer 200 in the form of a film or a thin film can be formed by applying a solution containing the metal nanowires on the substrate 100.

The carbon nanostructure may include, but is not limited to, those selected from the group consisting of graphene, carbon nanotube, fullerene, carbon black, and combinations thereof. The heating layer 200 in the form of a film or a thin film can be formed by applying a solution containing the carbon nanostructure on the substrate 100.

The metal paste or the metal nanoparticles may be a paste or a metal nanoparticle of a metal selected from the group consisting of silver, gold, platinum, copper, nickel, aluminum, titanium, palladium, cobalt, cadmium, rhodium, But is not limited thereto. By applying the metal paste on the substrate 100, the heating layer 200 in the form of a film or a thin film can be formed. Alternatively, the heating layer 200 in the form of a film or a thin film can be formed by applying a solution containing the metal nanoparticles on the substrate 100.

The heating layer 200 may have a thickness of, for example, about 10 nm to about 500 nm, but is not limited thereto. For example, the heating layer 200 may have a thickness of from about 10 nm to about 400 nm, from about 50 nm to about 300 nm, from about 100 nm to about 200 nm, from about 10 nm to about 300 nm, from about 10 nm to about 500 nm, from about 10 nm to about 500 nm, from about 10 nm to about 100 nm, from about 10 nm to about 50 nm, from about 10 nm to about 30 nm, from about 10 nm to about 20 nm, From about 100 nm to about 500 nm, from about 200 nm to about 500 nm, from about 300 nm to about 500 nm, from about 400 nm to about 500 nm, from about 100 nm to about 400 nm, or from about 200 nm to about 300 nm But is not limited thereto. If the thickness exceeds 500 nm, the resistance is lowered but the transmittance is lowered and the optical characteristics such as the haze (Hz) and the yellowness index (YI) are increased. When the thickness is less than 10 nm, . Preferably, the thickness may be from about 30 nm to about 300 nm.

According to an embodiment of the present invention, the transparent plane heating element according to the present invention includes a protective layer 400 formed on the heating layer 200 to protect the heating layer 200, (500). The protective layer 400 may be, for example, a transparent polymer resin, and may be in the form of a film or a thin film, but is not limited thereto.

According to one embodiment of the present invention, the protective layer 400 includes pores 500, and the pores 500 may be formed in the protective layer 400, The heat loss generated in the heat generating layer 200 can be minimized and the heat insulating effect can be improved.

The protective layer 400 may have a thickness of about 50 nm to about 200 탆, but is not limited thereto. For example, the protective layer may have a thickness of from about 70 nm to about 200 μm, from about 100 nm to about 200 μm, from about 200 nm to about 200 μm, from about 300 nm to about 200 μm, from about 400 nm to about 200 μm, From about 500 microns to about 200 microns, from about 750 microns to about 200 microns, from about 1 micron to about 200 microns, from about 10 microns to about 200 microns, from about 100 microns to about 200 microns, from about 150 microns to about 200 microns, From about 50 nm to about 600 nm, from about 50 nm to about 100 nm, from about 50 nm to about 100 nm, from about 50 nm to about 10 nm, from about 50 nm to about 1 nm, from about 50 nm to about 800 nm, From about 50 nm to about 100 nm, from about 50 nm to about 100 nm, from about 70 nm to about 150 탆, from about 100 nm to about 100 탆, from about 500 nm to about 50 탆, or from about 1 탆 to about 10 Mu m, but is not limited thereto. If the thickness is less than 50 nm, the function of protecting the heat generating layer 200 may be degraded or reliability may be deteriorated. Preferably, the thickness may be from about 100 nm to about 200 nm.

The pores 500 of the protective layer may have a size of about 5 nm to about 10 탆, but are not limited thereto. The pore size of the protective layer may be, for example, from about 5 nm to about 10 m, from about 10 nm to about 10 m, from about 50 nm to about 10 m, from about 100 nm to about 10 m, from about 500 nm to about 10 From about 1 micron to about 10 microns, from about 5 microns to about 10 microns, from about 5 nanometers to about 5 microns, from about 10 nanometers to about 1 micron, from about 50 nanometers to about 900 nanometers, from about 100 nanometers to about 800 nanometers, But is not limited to, from about 200 nm to about 700 nm, from about 300 nm to about 600 nm, or from about 400 nm to about 500 nm. More preferably, if the pore size is similar to the wavelength of light, the coating layer becomes opaque, and thus the pores may have pores of several hundred nanometers or less smaller than the wavelength of light.

According to an embodiment of the present invention, when power is applied through the electrode 300, heat is generated in the heating layer. Air is trapped in the micropores by the pores 500 of the protective layer and convection of the air trapped in the micropores is suppressed to minimize the loss of heat generated in the heating layer 200, have.

The electrode 300 may be formed on the heating layer 200 or the protection layer 400, but is not limited thereto. The electrodes 300 may be more than one pair. The electrode 300 may be formed by various wet and dry coating processes. For example, it is possible to use coatings such as gravure printing, flexographic printing, comma printing, slit coating, spray coating, screen printing, offset printing, lamination, lift-off, sputtering, ion plating, chemical vapor deposition, , Laser molecular beam deposition, pulsed laser deposition, or atomic layer deposition.

The electrode 300 is not particularly limited as long as it is a conductive material, and may be, for example, transparent, but is not limited thereto. The electrode 300 may be formed of a metal such as silver, gold, platinum, aluminum, copper, chromium, vanadium, magnesium, titanium, tin, lead, palladium, tungsten, nickel, ), Metal nanowires, carbon nanostructures, and combinations thereof, but is not limited thereto. The metal nanowires may comprise metal nanowires selected from the group consisting of, for example, silver, gold, platinum, copper, nickel, aluminum, titanium, palladium, cobalt, cadmium, rhodium, But is not limited thereto. The carbon nanostructure may include, but is not limited to, those selected from the group consisting of graphene, carbon nanotube, fullerene, carbon black, and combinations thereof.

According to another aspect of the present invention, there is provided a transparent surface heating element system formed by connecting a plurality of transparent surface heating elements according to one aspect of the present invention in series or in parallel.

Hereinafter, the present invention will be described in more detail with reference to the following examples. However, the following examples are for illustrative purposes only and are not intended to limit the scope of the present invention.

[Example]

[Example 1]

A solution of nanowires dispersed in water was stitched for 30 minutes. The silver nanowire solution dispersed on the PET substrate was bar coated. The substrate coated with the silver nanowires was dried in an oven at 80 ° C for 2 minutes to obtain a silver nanowire film.

Subsequently, an overcoating solution of 1.0 wt% was bar-coated on the silver nanowire film. Thereafter, the film was dried at 100 DEG C and treated with a UV curing machine at 300 mJ to form a polymer film, and a transparent conductive film containing a silver nanowire film and an overcoat layer was obtained on the substrate.

Subsequently, electrodes were formed on both ends of the film through screen printing to produce a transparent heating element.

Next, a solution prepared by mixing ethanol and acetone in a ratio of 6: 4 as a solvent is prepared in order to prepare a porous film. TEOS (tetraethoxysilane) was used as a silica precursor, hydrochloric acid was used as a catalyst, CTAB (cetyltrimethylammonium bromide) was used as a surfactant, and distilled water (DI-water) was further used. The molar ratio of TEOS, ethanol, distilled water, hydrochloric acid, and CTAB is as follows.

TEOS: ethanol: distilled water: hydrochloric acid: CTAB = 1: 20: 5: 0.005: 0.03

After mixing ethanol and acetone, distilled water and hydrochloric acid were added, followed by addition of the pre-dissolved CTAB at 70 ° C. and stirring for 2 hours. TEOS was added to the stirred solution, stirred at room temperature for 30 minutes, and then spin-coated on a glass substrate. At this time, the spin speed was 3,000 rpm and the spinning was carried out for 30 seconds. The coated thin film was evaporated at room temperature for one day and then heat-treated at 150 ° C to decompose the surfactant to obtain a porous film having a plurality of pores and a porosity of 30%.

Subsequently, the prepared porous protective film was laminated on the top of the heating element on which the electrodes were formed.

[Example 2]

A transparent heating element was prepared in the same manner as in Example 1, and a porous film was prepared in the following molar ratio.

TEOS: ethanol: distilled water: hydrochloric acid: CTAB = 1: 20: 5: 0.005: 0.05

A porous film having a porosity of about 40% was obtained.

[Example 3]

TEOS: ethanol: distilled water: hydrochloric acid: CTAB = 1: 20: 5: 0.005: 0.07

A porous film having a porosity of about 50% was obtained.

[Comparative Example 1]

A transparent heating element was prepared in the same manner as in Example 1, but the porous protective film was not laminated.

[Experimental Example 1]

The surface heat resistance of the transparent heating element obtained in Examples 1 to 3 and Comparative Example 1 was measured with a low resistance meter [loresta-GP MCP-T610 (Mitsubishi Chemical Corporation)] before the porous film was laminated, The average value (Rs,? /?) Was measured. The uniformity of sheet resistance (Rs uniformity,%) was calculated using the standard deviation values.

[Experimental Example 2]

The visible light transmittance (%) and haze (Hz%) of the transparent heating elements obtained in Examples 1 to 3 and Comparative Example 1 were measured using a UV spectrometer (Nippon Denshoko, NDH2000).

[Experimental Example 3]

To evaluate the exothermic characteristics of the transparent heating elements obtained in Examples 1 to 3 and Comparative Example 1,? T (占 폚) (heating temperature-atmospheric temperature) was measured based on a voltage of 12 V applied.

The results of Experimental Examples 1 to 3 are shown in Table 1 below.

division Permeability (%) Hz (%) Rs (Ω / □) Rs Uniformity (%) ΔT (° C) Example 1 88 1.6 30 7 10 Example 2 87 1.5 31 6 12 Example 3 87 1.5 30 5 13 Comparative Example 1 88 1.4 31 7 7

As can be seen from the above Table 1, it can be confirmed that the heating elements having the protective layer having pores as shown in Examples 1 to 3 exhibited higher heating characteristics at the same voltage.

While the present invention has been particularly shown and described with reference to exemplary embodiments thereof, it is to be understood that the invention is not limited to the disclosed exemplary embodiments and the exemplary embodiments, and various changes and modifications may be made without departing from the scope of the present invention. It is evident that many variations are possible by those skilled in the art.

100: substrate 200: heating layer
300: electrode 400: protective layer
500: Groundwork

Claims

materials;
A heating layer formed on the substrate and including a conductive material;
An electrode connected to the heating layer; And
A protective layer formed on the heat generating layer to protect the heat generating layer and including a transparent polymer resin,
Wherein the transparent surface-heating element is a transparent surface-
The transparent surface heating element includes pores formed in the protective layer. Air trapped in the pores and convection of air trapped in the pores are suppressed, thereby minimizing loss of heat generated in the heating layer Which improves the adiabatic effect.
Transparent surface heating element.

The method according to claim 1,
Wherein the protective layer has a thickness of 50 nm to 200 占 퐉.

The method according to claim 1,
Wherein the pores of the protective layer have a size of 5 nm to 10 mu m.

The method according to claim 1,
Wherein the substrate is transparent.

The method according to claim 1,
Wherein the substrate comprises a silicon substrate, a glass substrate, or a polymer substrate.

The method according to claim 1,
Wherein the conductive material comprises at least one selected from the group consisting of metal oxides, metal nanowires, carbon nanostructures, metal pastes, metal nanoparticles, and combinations thereof.

The method according to claim 6,
Wherein the metal nanowires comprise metal nanowires selected from the group consisting of silver, gold, platinum, copper, nickel, aluminum, titanium, palladium, cobalt, cadmium, rhodium and combinations thereof.

The method according to claim 6,
Wherein the carbon nanostructure comprises a material selected from the group consisting of graphene, carbon nanotube, fullerene, carbon black, and combinations thereof.

The method according to claim 6,
Wherein the metal paste comprises a metal selected from the group consisting of silver, gold, platinum, copper, nickel, aluminum, titanium, palladium, cobalt, cadmium, rhodium and combinations thereof.

The method according to claim 6,
Wherein the metal nanoparticles comprise a metal selected from the group consisting of silver, gold, platinum, copper, nickel, aluminum, titanium, palladium, cobalt, cadmium, rhodium and combinations thereof.

The method according to claim 1,
Wherein the heating layer has a thickness of 10 nm to 500 nm.

The method according to claim 1,
And heat is generated in the heating layer when power is applied through the electrode.

The method according to claim 1,
Wherein the electrode comprises a transparent electrode.

The method according to claim 1,
Wherein the electrode is selected from the group consisting of silver, gold, platinum, aluminum, copper, chromium, vanadium, magnesium, titanium, tin, lead, palladium, tungsten, nickel, alloys thereof, indium-tin- And combinations thereof. &Lt; RTI ID = 0.0 > 11. < / RTI >

The method according to claim 1,
Wherein the electrodes are at least one pair.

A transparent surface heating element system, comprising a plurality of transparent surface heat emission elements according to any one of claims 1 to 15 connected in series or in parallel.