KR101775894B1 - Transparent exothermic film and method of manufacturing the same - Google Patents

Abstract

A transparent heat generating film and a manufacturing method thereof are disclosed. According to an embodiment of the present invention, there is provided a transparent heat generating film comprising a substrate and 0.1 to 10.0% by weight of zinc (Zn), 0.1 to 10.0% by weight of titanium (Ti) And a CZT (Cu-Zn-Ti) layer containing a component-based alloy. Therefore, in the production of a transparent heat-generating film, a heat-generating electrode is formed using a CZT (Cu-Zn-Ti) alloy, whereby the electric conductivity and heat generation efficiency of the transparent heat-generating film can be improved.

Description

FIELD OF THE INVENTION [0001] The present invention relates to a transparent heat generating film,

The present invention relates to a transparent heat generating film and a method of manufacturing the same, and more particularly, to a transparent heat generating film having excellent electric conductivity and improved heat generating efficiency and a method of manufacturing the same.

The area heating element that exerts heat by electric resistance has a relatively low power consumption rate in the range of 20 to 40% as compared with a general heating device, and has a relatively excellent heat generation efficiency. In addition, smoothness and durability also have very excellent structural properties.

Such surface heating elements can be used not only for residential heating devices such as bedding mats, cushions, and domestic dry sauna devices, but also for various industrial heating devices such as an anti-icing device for automobile glass, a condensation preventing device for a refrigerator, Anti-icing devices, and the like.

The planar heating element generally coats a transparent heating substrate with a conductive heating material. Electrodes are placed at both ends of the conductive heating material. If a direct current voltage or an alternating voltage is applied to both electrodes, a current flows through the conductive heating material and heat is generated.

The conductive heating materials used in the surface heating elements are various. Typically used are metal heating elements such as iron, nickel, chromium, platinum and the like, and non-metallic heating elements such as conductive metal oxides and carbon are also used. In recent years, attempts have been made to use carbon-based materials as conductive heating materials. Typically, there are carbon nanotubes (CNTs). However, since carbon nanotubes have high dispersibility and electrical conductivity, they have a high resistance and can not withstand heat for a long time at a high temperature. Therefore, there is a problem that a heating element is broken, so that it is difficult to use the carbon nanotube alone in a heating element. Therefore, in order to lower the resistance of carbon nanotubes, carbon nanotubes and silver (Ag) nanowires are mixed and used as a heating element. However, there is a problem that the silver nanowires are agglomerated at a high temperature to deteriorate their properties.

Further, such a heat generating material may be a transparent conductive oxide (TCO) having transparency while being conductive. For example, ITO (Indium Tin Oxide), ZTO (Zinc Tin Oxide), IGZO (Indium Gallium Zinc Oxide), ZAO (Zinc Aluminum Oxide), IZO (Indium Zinc Oxide), ZnO .

The transparent conductive oxide is excellent in safety and abrasion resistance, and has a transparency of 80% or more in a visible region, and has transparency while exhibiting conductivity, so that it is widely used as an electrode or a transparent heating element. However, since the conductivity of the transparent conductive oxide is lower than that of a metal such as silver in a planar heating element having a large area, when the electrode is used as a heating electrode, the heating efficiency is lowered or the time for raising the temperature to a certain level is prolonged There is a problem.

Korean Patent Laid-Open Publication No. 10-2011-0083895

The present invention provides a transparent heat generating film having excellent electric conductivity and improved heat generating efficiency by forming a heating electrode using a CZT (Cu-Zn-Ti) alloy in the production of a transparent heat generating film.

According to the present invention, there is also provided a method of manufacturing the transparent heat generating film.

A transparent heat generating film according to an embodiment of the present invention includes a substrate and a three-component system in which 0.1 to 10.0% by weight of zinc (Zn), 0.1 to 10.0% by weight of titanium (Ti) And a CZT (Cu-Zn-Ti) layer containing an alloy.

Also, according to an embodiment of the present invention, the CZT layer may include a metal pattern.

According to an embodiment of the present invention, the line width of the metal pattern may be 1 to 50 탆.

Also, according to an embodiment of the present invention, the pitch between adjacent metal patterns may be 100 to 2,000 mu m.

Also, according to an embodiment of the present invention, the thickness of the metal pattern may be 50 to 300 nm.

According to an embodiment of the present invention, the metal pattern may be at least one selected from the group consisting of stripe, grid, zigzag, rhombic, and circular.

According to an embodiment of the present invention, the CZT layer may include at least one selected from the group consisting of silver (Ag), gold (Au), copper (Cu), aluminum (Al), and carbon nanotubes .

According to an embodiment of the present invention, the CZT layer may further include a blackening layer disposed on one side or both sides of the CZT layer.

According to an embodiment of the present invention, the blackening layer may include a first blackening layer disposed between the substrate and the CZT layer, and a second blackening layer disposed on the CZT layer.

According to an embodiment of the present invention, the blackening layer may include any one of CZTO (Cu-Zn-Ti-O) and CZTN (Cu-Zn-Ti-N).

Also, according to an embodiment of the present invention, the thickness of the blackening layer may be 10 to 50 nm.

According to an embodiment of the present invention, the transparent heat generating film may have a visible light transmittance of 80% or more, a haze value of 0.5 to 6%, and a surface resistance value of 5 to 500? / Cm 2.

In addition, according to an embodiment of the present invention, an optical layer disposed between the substrate and the CZT layer may be further included.

According to an embodiment of the present invention, the CZT layer may further include a blackening layer disposed on one side or both sides of the CZT layer.

According to an embodiment of the present invention, the optical layer may include at least one selected from the group consisting of silicon (Si), niobium (Nb), and zirconium (Zr).

Also, according to an embodiment of the present invention, the thickness of the optical layer may be 1 to 20 占 퐉.

A method of manufacturing a transparent heat generating film according to an embodiment of the present invention is a method of manufacturing a transparent heat generating film according to an embodiment of the present invention, wherein a three-component system in which zinc (Zn) is 0.1 to 10.0% by weight, titanium (Ti) is 0.1 to 10.0% To form a CZT (Cu-Zn-Ti) layer.

According to an embodiment of the present invention, the CZT layer may be formed by forming a metal layer by sputtering a CZT (Cu-Zn-Ti) target on the substrate, applying a photoresist on the metal layer to form a photoresist layer Forming a photoresist layer on the photoresist layer, exposing the photoresist layer using a mask to cure a portion of the photoresist layer, developing the exposed photoresist layer to form a phototray, etching the metal layer to form a metal pattern, And then removing it.

Also, according to an embodiment of the present invention, the CZT layer may include the metal pattern.

According to an embodiment of the present invention, the metal layer may be formed by sputtering the CZT target, which is a three-component alloy including zinc (Zn), titanium (Ti), and copper (Cu).

According to an embodiment of the present invention, the metal layer may include a first target including zinc (Zn), a second target including titanium (Ti), and a third target including copper (Cu). CZT target can be simultaneously formed by sputtering.

According to the present invention, in the production of a transparent heat-generating film, a heat-generating electrode is formed using a CZT (Cu-Zn-Ti) alloy so that the electric conductivity and heat generation efficiency of the transparent heat-generating film can be improved.

Further, a blackening layer is deposited on the electrode formed using the CZT (Cu-Zn-Ti) alloy by using the CZT (Cu-Zn-Ti) alloy to reduce the reflectance of the transparent heat generating film to secure visibility .

1 is a plan view of a transparent heat generating film according to an embodiment of the present invention.
2 is a cross-sectional view of a transparent heat generating film according to an embodiment cut along a line II 'in FIG.
FIGS. 3 and 4 are cross-sectional views of a transparent heat generating film according to an embodiment cut along a line II 'in FIG.
5 and 6 are cross-sectional views of a transparent heat generating film according to an embodiment cut along the line II 'in FIG.
Figs. 7 to 11 are cross-sectional views for explaining a method of manufacturing the transparent heat generating film of Figs. 1 and 2. Fig.
12 is a graph showing a change in temperature with time after application of a voltage of 20 V to a transparent heat generating film 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. The following embodiments are provided to fully convey the spirit of the present invention to a person having ordinary skill in the art to which the present invention belongs. The present invention is not limited to the embodiments shown herein but may be embodied in other forms. For the sake of clarity, the drawings are not drawn to scale, and the size of the elements may be slightly exaggerated to facilitate understanding.

1 is a plan view of a transparent heat generating film according to an embodiment of the present invention. FIG. 2 is a cross-sectional view of a transparent heat generating film according to an embodiment cut along a line I-I 'in FIG.

Referring to FIGS. 1 and 2, a transparent heating film 1000 according to an embodiment of the present invention includes a substrate 100 and a CZT (Cu-Zn-Ti) layer 200.

The substrate 100 is a transparent insulating substrate, and may be a glass substrate or a transparent plastic substrate. For example, the substrate 100 may comprise silicon, polyacrylate, polyethylene, polyurethane, epoxy, polycarbonate, polyethylene naphthalate (PEN), polyethylene terephthalate (PET), polyimide, have.

The CZT layer 200 is disposed on the substrate 100 and includes a ternary alloy containing 0.1 to 10.0% by weight of zinc (Zn), 0.1 to 10.0% by weight of titanium (Ti), and the balance of copper .

The total amount of the zinc (Zn) and titanium (Ti) in the CZT layer 200 may be 20 wt% or less, more preferably 10.0 wt% or less, Heat efficiency and corrosion resistance can be improved. On the other hand, when the sum of the Zn and Ti contents exceeds 20% by weight, the function as the metal conductive layer may be deteriorated.

The alloy contained in the CZT layer 200 may have a particle diameter of 0.1 to 50 nm. Therefore, by using the nano-level particles, heat generation characteristics and radiation efficiency can be improved and the transparency of the CZT layer 200 can be improved.

When the conductive layer is formed of the CZT layer 200, it has high corrosion resistance, excellent selectivity for arousal, low resistance, excellent signal transmission even when formed into a fine line width and space, uniformity of etching Can be obtained. In addition, pinholes hardly occur, and pinholes of 3 mu m or less are generated even if pinholes are rarely generated. Therefore, there is no fear of disconnection even if patterning is performed with a fine line width.

The CZT layer 200 may be formed of a metal such as Ag, Au, Cu, Al, and CNT in an amount of 0.1 to 10 wt% You can include attachments. Thus, the electrical conductivity of the CZT layer 200 can be improved.

The CZT layer 200 includes a metal pattern. For example, the line width w of the metal pattern may be 1 to 50 탆. Further, the pitch p between adjacent metal patterns may be 100 to 2,000 mu m. Further, the thickness (t1) of the metal pattern may be 50 to 300 nm, so that sufficient mechanical strength can be maintained.

The metal pattern may be patterned by various methods, for example, but not limited to, a photolithography process, a reverse offset process, a gravure offset process, or the like. The metal pattern according to an embodiment of the present invention can be formed through a photo process using a photoresist.

The metal pattern may have various patterns, for example, a stripe pattern, a grid pattern, a zigzag pattern, a rhombus pattern, and a circular pattern. Referring to FIG. 1, the metal pattern according to an exemplary embodiment of the present invention may have a zigzag pattern, but the present invention is not limited thereto.

That is, the metal patterns adjacent to each other have a specific pattern in which the metal patterns are spaced apart from each other, so that some of the patterns become disconnection, so that the heat generating characteristic can be maintained by the current applied from the other side even if the current is not applied at one side. In addition, the metal pattern may be formed over the entire surface of the substrate 100 to uniformly generate heat from the front surface of the transparent heat generating film 1000 to improve heat uniformity.

For example, the transparent heat generating film 1000 may have a visible light transmittance of 80% or more, a haze value of 0.5 to 6%, and a surface resistance value of 5 to 500? / Cm 2.

FIGS. 3 and 4 are cross-sectional views of a transparent heat generating film according to an embodiment cut along a line I-I 'in FIG.

The transparent heat generating films 2000 and 2100 according to the embodiment of FIGS. 3 and 4 include the black heat layers 210 and 220 in the transparent heat generating film 1000 according to the embodiment of FIGS. 1 and 2 And has the same configuration except for the above. Hereinafter, redundant description will be simplified or omitted.

Referring to FIGS. 1 to 4, the transparent heat generating films 2000 and 2100 include blackening layers 210 and 220 disposed on one side of the CZT layer 200.

Referring to FIG. 3, the transparent heat generating film 2000 includes a first blackening layer 210 disposed on the CZT layer 200.

4, the transparent heat generating film 2100 includes a first blackening layer 210 disposed on the CZT layer 200 and a second blackening layer 210 disposed between the substrate 100 and the CZT layer 200. [ And a blackening layer 220.

The transparent heat generating films 2000 and 2100 according to an embodiment of the present invention may include a blackening layer in contact with the CZT layer 200. Here, the blackening may be a conductive heat generating pattern layer made of a metal CZT layer is blackened. By performing such a blackening treatment, the visibility problem that the metal material is visually recognized by the consumers due to the high reflectivity of the metal material can be solved. In addition, the blackening layer may also serve to prevent natural oxidation of the conductive heating pattern layer, so that the sheet resistance can be increased or minimized due to oxidation.

For example, in the region R 1 where the CZT layer 200 is disposed and the region R 2 where the substrate 100 is exposed after the patterning of the substrate 100, The reflectance difference between the two regions is large, so that the metal pattern can be visually recognized. However, if the difference in reflectance (| R1-R2 |) between the region R1 where the CZT layer 200 is disposed and the region R2 where the substrate 100 is exposed is defined as Equation (1) can be satisfied, and there is little difference in reflectance between the two regions, so that the metal pattern is not visually recognized and index-matching is achieved.

| R1-R2 | <5% (1)

The first blackening layer 210 may function not only as a blackening function but also as an oxidation preventing layer. The blackening layer is formed by treating CZT, which is a three-component system alloy, with N ₂ or O ₂ , and it can prevent natural oxidation by complementing the property of a metal material having a good oxidation property. Therefore, You can.

For example, the thickness t2 of the first blackening layer 210 may be 10 to 50 nm. If the thickness of the first blackening layer 210 is less than 10 nm, the reflectance and the oxidation preventing effect may be deteriorated. If the thickness of the first blackening layer 210 exceeds 50 nm, the tack- time may become longer, which may reduce the economic efficiency.

The second blackening layer 220 can improve the adhesion between the substrate 100 and the CZT layer 200 together with the blackening function of lowering the reflectivity of the CZT layer 200. Therefore, the adhesive layer, which has been conventionally included for the purpose of improving the adhesion between the substrate and the conductive pattern layer, can be omitted, thereby simplifying the process, reducing the process cost, and reducing the thickness of the film.

For example, the thickness of the second blackening layer 220 may be 10 to 50 nm. When the thickness of the second blackening layer 220 is less than 10 nm, the reflectance and the adhesion improving effect may be deteriorated. When the thickness of the second blackening layer 220 exceeds 50 nm, the tack- time may become longer, which may reduce the economic efficiency.

The blackening layer may include any one of CZTO (Cu-Zn-Ti-O) and CZTN (Cu-Zn-Ti-N) The blackening layer 220 may be formed of the same or different materials.

For example, the blackening layer containing CZTO (Cu-Zn-Ti-O) may be a three-component system having 0.1 to 10.0% by weight of zinc (Zn), 0.1 to 10.0% by weight of titanium (Ti) And may be a metal film formed by the reaction of the alloy and oxygen (O ₂ ).

For example, the blackening layer containing CZTN ((Cu-Zn-Ti-N)) may include zinc oxide (Zn) in an amount of 0.1 to 10.0 wt%, titanium (Ti) in an amount of 0.1 to 10.0 wt% Or may be a metal film formed by reaction of a component-based alloy with nitrogen (N ₂ ).

Since the blackening layer is etched and removed in the same process as the CZT layer 200, the blackening layer may have the same line width and pitch as the CZT layer 200.

FIGS. 5 and 6 are cross-sectional views of a transparent heat generating film according to one embodiment taken along the line I-I 'in FIG.

The transparent heat generating films 3000 and 3100 according to the embodiment of FIGS. 5 and 6 may further include an optical layer 230 in the transparent heat generating films 2000 and 2100 according to the embodiment of FIGS. 3 and 4 And has the same configuration except for the above. Hereinafter, redundant description will be simplified or omitted.

1 to 6, the transparent heat generating films 3000 and 3100 include an optical layer 230 disposed between the substrate 100 and the CZT layer 200.

5, the transparent heat generating film 3000 includes a first blackening layer 210 disposed on the CZT layer 200 and a second blackening layer 210 disposed between the substrate 100 and the CZT layer 200, (230). 6, the transparent heat generating film 3100 includes a first blackening layer 210 disposed on the CZT layer 200, an optical layer 230 disposed on the substrate 100, And a second blackening layer 220 disposed between the layer 230 and the CZT layer 200.

For example, the optical layer 230 may include silicon (Si), niobium (Nb), and zirconium (Zr). For example, the thickness t3 of the optical layer 230 may be 1 to 20 占 퐉. The transparent heat generating films 3000 and 3100 may include the optical layer 230 to improve the visibility of the CZT layer 200.

That is, since the optical layer 230 is disposed between the substrate 100 and the CZT layer 200, the region R1 where the CZT layer 200 is disposed and the region where the optical layer 230 is exposed (| R1-R2 |) between the two regions can satisfy the following expression (2), and the difference in reflectance between the two regions can be reduced to improve the visibility.

| R1-R2 | < 1.5% (2)

Figs. 7 to 11 are cross-sectional views for explaining a method of manufacturing the transparent heat generating film of Figs. 1 and 2. Fig.

1 to 11, there is provided a method for manufacturing a transparent heat generating film according to an embodiment of the present invention, wherein 0.1 to 10.0% by weight of zinc (Zn), titanium (Ti) (Cu-Zn-Ti) layer 200 comprising a ternary alloy of 0.1 to 10.0% by weight and a balance of copper (Cu).

Referring to FIG. 7, a metal layer M is formed by sputtering a CZT (Cu-Zn-Ti) target on the substrate 100.

For example, the CZT target may be a three-component alloy including zinc (Zn), titanium (Ti), and copper (Cu). Accordingly, the metal layer M may be formed by sputtering the CZT target, which is a three-component alloy including zinc (Zn), titanium (Ti), and copper (Cu).

Alternatively, the CZT target may comprise a first target comprising zinc (Zn), a second target comprising titanium (Ti) and a third target comprising copper (Cu). Thus, the metal layer M may be formed by simultaneously sputtering the CZT target comprising a first target comprising zinc (Zn), a second target comprising titanium (Ti) and a third target comprising copper (Cu) .

8 to 11, a transparent heat generating film according to an embodiment of the present invention forms the CZT layer 200 by a photolithography process using photoresist. However, the CZT layer 200 may be patterned by a reverse offset process, a gravure offset process, or the like as well as a photolithography process. Hereinafter, a method of manufacturing the transparent heat generating film by forming the CZT layer 200 through a photo process will be described.

Referring to FIG. 8, photoresist is applied on the metal layer M to form a photoresist layer PR. For example, the photoresist can be applied through processes such as spin coating, slit coating, and the like. Preferably, the photoresist can be applied through spin coating. For example, the photoresist may be a positive type photoresist. The positive type photoresist is then cured in the unexposed area, and the exposed area can be removed through development to form a pattern. For example, the photoresist layer PR may be formed to a thickness of 0.5 to 20 탆.

The solvent in the photoresist layer PR may be removed to soft bake the photoresist layer PR to cure the photoresist layer PR for exposure. Also, the photoresist layer PR can be brought into close contact with the metal layer 120 through the soft bake, and the force applied when the photoresist layer PR is applied through the spin coating can be relaxed. In addition, a smooth surface can be formed while removing minute bubbles of the photoresist layer PR through the soft bake. For example, the soft bake may be conducted at 105 to 115 캜 for 1 to 10 minutes before exposure.

Thereafter, the photoresist layer PR is exposed using a mask MASK. The mask MASK includes a slit region through which light is transmitted so that a part of light provided at the front surface is reflected or absorbed and a part of the remaining light is transmitted to the photoresist layer PR. For example, the exposed light includes ultraviolet light, for example, the amount of light provided may be 30 mJ / cm &lt; ² &gt;. The exposure method includes proximity exposure, contact exposure, and the like.

Referring to FIG. 9, the exposed photoresist layer PR is developed to form a photoresist PR '. A part of the photoresist layer PR is removed using a developing solution, thereby forming a photoresist PR '. The developer may be an alkaline developer. For example, the developer may be 2.38% tetramethyl ammonium hydroxide (TMAH) although it is not limited thereto.

In order to firmly cure the photopattern PR ', a hard bake may be performed. For example, the hard bake may be performed at 125 to 135 ° C for 1 to 10 minutes after exposing the phot pattern PR '.

Referring to FIG. 10, the metal layer M is etched using the photoresist PR 'as a mask to form a metal pattern.

The CZT layer 200 includes the metal pattern. The metal pattern may have various patterns, for example, a stripe pattern, a grid pattern, a zigzag pattern, a rhombus pattern, and a circular pattern. Referring to FIG. 1, the metal pattern according to an exemplary embodiment of the present invention may have a zigzag pattern, but the present invention is not limited thereto.

The metal layer M is etched using an etchant, which may include, for example, phosphoric acid, nitric acid, and acetic acid.

The metal pattern M may be formed by removing part of the metal layer M by immersing the metal layer M for 30 to 60 seconds using the etchant.

Referring to FIG. 11, the photoresist pattern PR 'can be removed using a peeling liquid, and thus the CZT layer 200 can be exposed.

For example, there is no limitation on the type of the peeling liquid, but THB-S2 manufactured by JSR Corporation may be used. The photopattern PR 'may be immersed in the peeling liquid at a temperature of 50 to 60 ° C for 5 to 20 minutes.

12 is a graph showing a change in temperature with time after application of a voltage of 20 V to a transparent heat generating film according to an embodiment of the present invention.

The transparent heat generating film produced according to the method of manufacturing the transparent heat generating film according to Figs. 7 to 11 can be produced according to the following embodiments.

Example  One

A metal layer including a CZT alloy was deposited to a thickness of 200 nm on the substrate by sputtering in an Ar atmosphere using a CZT target having the content of Example 1 shown in Table 1 below. The substrate was coated with I-line (365 nm) positive photoresist (AZ GXR-601) at a spin coating rate of 3,900 rpm to a thickness of 1 μm and then soft baked at 110 ° C. for 90 seconds. The substrate coated with the photoresist was irradiated with light of 30 mJ / cm ² using an exposure machine, and immersed in water at room temperature using a TMAH developer. The photoresist-developed substrate was spin-spray-etched for 1 minute using a thermosetting resin (RAM yarn RCE-021) to form a photopattern, and the exposed area of the photoresist layer was removed with a peeling liquid RAM (RSP-903) for 1 minute, washed with water and removed to prepare a transparent heat-generating film having a patterned CZT layer.

Example  2

A metal layer was deposited on the substrate using a CZT target having the content of Example 2 shown in Table 1 below.

Example  3

A metal layer was deposited on the substrate using a CZT target having the content of Example 3 shown in Table 1 below.

Example  4

A metal layer was deposited on the substrate using a CZT target having the content of Example 4 shown in Table 1 below.

Example  5

A metal layer was deposited on the substrate using a CZT target having the content of Example 5 shown in Table 1 below, and the remaining conditions were the same as those in Example 1.

Example  6

A metal layer was deposited on the substrate using a CZT target having the content of Example 6 shown in Table 1 below.

Example  7

A metal layer was deposited on the substrate using a CZT target having the content of Example 7 shown in Table 1 below.

Example  8

A metal layer was deposited on the substrate using a CZT target having the content of Example 8 shown in Table 1 below. The rest of the conditions were the same as in Example 1.

Example  9

A metal layer was deposited on the substrate using a CZT target having the content of Example 9 shown in Table 1 below.

Cu (% by weight) Zn (% by weight) Ti (% by weight) Example 1 90 0.5 9.0 Example 2 90 1.0 9.0 Example 3 90 1.5 8.5 Example 4 90 2.0 8.0 Example 5 90 2.5 7.5 Example 6 90 3.5 6.5 Example 7 90 4.5 5.5 Example 8 90 5.5 4.5 Example 9 90 6.5 3.5

In Table 1, the sum of the contents of Zn and Ti is 10% by weight, and the result is shown in FIG.

The transparent heat-generating films prepared in Examples 1 to 9 were cut into 200 mm x 200 mm and laminated on 500 mm x 500 mm glass using an adhesive film. A voltage of 20 V was applied to each transparent heat-generating film, and the degree of temperature rise with time was measured with an IR vision camera, and the result is shown in FIG.

The line resistance of the transparent heat generating film prepared in Example 1 was 20?, And when a voltage of 20 V was applied, the heat generation amount of 11.2 W was exhibited. The heating phenomenon was measured with an IR vision camera and the temperature rose to 35 degrees within 10 minutes.

Referring to FIG. 12, it can be seen that the temperature of the transparent heat generating film manufactured according to Examples 1 to 9 was raised to about 35 ° C. within 2 minutes and 30 seconds.

While the present invention has been described with reference to exemplary embodiments, it is to be understood that the invention is not limited thereto. Those skilled in the art will readily obviate modifications and variations within the spirit and scope of the appended claims. It will be understood that various changes and modifications may be made therein without departing from the spirit and scope of the invention.

1000, 2000, 2100, 3000, 3100: Transparent heating film
100: substrate 200: CZT layer
210: first blackening layer 220: second blackening layer
230: optical layer PR: photoresist layer
PR ': Photo pattern M: metal layer

Claims (21)

Board; And
(Cu-Zn-Ti) layer comprising a ternary alloy of 0.1 to 10.0% by weight of zinc (Zn), 0.1 to 10.0% by weight of titanium (Ti) and the balance copper In addition,
Wherein the CZT layer includes a metal pattern, and a pitch between adjacent metal patterns is 100 to 2,000 mu m. delete The transparent heat generating film according to claim 1, wherein the line width of the metal pattern is 1 to 50 μm. delete The transparent heat generating film according to claim 1, wherein the metal pattern has a thickness of 50 to 300 nm. The transparent heat generating film according to claim 1, wherein the metal pattern is at least one selected from the group consisting of stripe, grid, zigzag, rhombic, and circular. The method of claim 1, wherein the CZT layer further comprises at least one selected from the group consisting of silver (Ag), gold (Au), copper (Cu), aluminum (Al), and carbon nanotubes A transparent heat-generating film. The transparent heat generating film according to claim 1, further comprising a blackening layer disposed on one side or both sides of the CZT layer. The method according to claim 8,
A first blackening layer disposed between the substrate and the CZT layer, and a second blackening layer disposed on the CZT layer. The transparent heat generating film according to claim 8, wherein the blackening layer comprises any one of CZTO (Cu-Zn-Ti-O) and CZTN (Cu-Zn-Ti-N). The transparent heat generating film according to claim 8, wherein the thickness of the blackening layer is 10 to 50 nm. The transparent heat generating film according to claim 1, wherein the transparent heat generating film has a visible light transmittance of 80% or more and a surface resistance value of 5 to 500? / Cm 2. The transparent heat generating film according to claim 1, further comprising an optical layer disposed between the substrate and the CZT layer. The transparent heat-generating film according to claim 13, further comprising a blackening layer disposed on one or both sides of the CZT layer. The transparent heat generating film according to claim 13, wherein the optical layer includes at least one selected from the group consisting of silicon (Si), niobium (Nb), and zirconium (Zr). The transparent heat generating film according to claim 13, wherein the thickness of the optical layer is 1 to 20 占 퐉. A step of forming a CZT (Cu-Zn-Ti) layer containing a ternary alloy of 0.1 to 10.0 wt% of zinc (Zn), 0.1 to 10.0 wt% of titanium (Ti) and the balance of copper &Lt; / RTI &
Wherein forming the CZT layer comprises:
Forming a metal layer by sputtering a CZT (Cu-Zn-Ti) target on the substrate;
Applying a photoresist on the metal layer to form a photoresist layer;
Exposing the photoresist layer using a mask to cure some areas;
Developing the exposed photoresist layer to form a photopattern;
Etching the metal layer to form a metal pattern; And
Removing the photo pattern,
Wherein the CZT layer includes a metal pattern, and a pitch between adjacent metal patterns is 100 to 2,000 mu m. delete delete The method of manufacturing a transparent heat generating film according to claim 17, wherein the metal layer is formed by sputtering the CZT target which is a three-component alloy including zinc (Zn), titanium (Ti), and copper (Cu). 18. The method of claim 17, wherein the metal layer is formed by simultaneously sputtering the CZT target comprising a first target comprising zinc (Zn), a second target comprising titanium (Ti) and a third target comprising copper (Cu) Wherein the transparent heat-generating film is formed on the transparent substrate.

Images