WO2008147066A2

WO2008147066A2 - Method for manufacturing wire for correcting a set of teeth

Info

Publication number: WO2008147066A2
Application number: PCT/KR2008/002787
Authority: WO
Inventors: In Jae Kim
Original assignee: Individual
Current assignee: Individual
Priority date: 2007-05-28
Filing date: 2008-05-19
Publication date: 2008-12-04
Anticipated expiration: 2009-11-28
Also published as: WO2008147066A9; KR20070107633A; WO2008147066A3; KR100919900B1

Abstract

Disclosed is a method of manufacturing a wire for correcting irregularities of teeth. In particular, disclosed is a method of manufacturing a wire for correcting irregularities of teeth, which is harmless to a human body, and is capable of maintaining a tooth color. The inventive method includes the steps of: manufacturing a metal wire from a metal alloy material; chemically etching the surface of the metal wire, and then conducting a thermal treatment; coating a metal material film on the surface of the metal wire so that the surface of the metal wire exhibits a white color, and then conducting a thermal treatment; coating a transparent metal oxide film on the metal material coated on the metal wire; and forming a transparent parylene film on the transparent metal oxide film, and then conducting a thermal treatment.

Description

METHOD FOR MANUFACTURING WIRE FOR CORRECTING A SET OF TEETH

Technical Field

[1] The present invention relates to a method for manufacturing a wire for correcting irregularities of teeth, and in particular to a method of manufacturing a wire for correcting irregularities of teeth, which is not harmful to a human body and is capable of continuously maintaining the color of the teeth. Background Art

[2] For example, as periodontal tissue is destroyed, and alveolar bone is sequentially broken down from an edge of gums and gradually decays due to the progress of periodontitis, a symptom of so-called paradentosis is caused, which renders a tooth adjacent to the periodontitis loose. A remedy for such a tooth suffering from paradentosis is to extract the tooth if the tooth becomes so seriously loose that there is no hope of preserving the tooth, or to fix the tooth together with at least one less-loose tooth adjacent to the tooth if there is a hope of preserving the tooth even though the tooth is loose.

[3] When fixing a plurality of adjacent teeth, a metal wire is typically used. With the elasticity of such a metal wire, the metal wire is wound around the teeth to be fixed in such a manner that load induced when the metal wire is bent or tensioned is applied to and fixes the teeth.

[4] In the above^nentioned method, there are problems in that steps for sequentially winding and attaching the metal wire to the teeth to be fixed should be carried out, the patient always feels a pain due to the load applied to the teeth and suffers troubles due to discomfort, and the metal wire is frontally exposed when the patient opens his or her mouth, which is not pleasant to see.

[5] Recently, there have been proposed methods of fixing teeth using a shape memory alloy. According to a proposed method, a correction member in the form of a shape memory alloy wire undergoes a heat treatment so that its parent phase shape takes a desired shape, i.e. a shape of an anatomically regular tooth row, the correction member is engaged to a patient's tooth row under a low temperature environment, and the correction member is heated to return to its original shape, so that the irreguralities of teeth can be corrected by the elastic force of the correction member.

[6] FIG. 1 is a schematic view and a cross-sectional view showing a conventional wire for correcting irregularities of teeth, respectively.

[7] As shown in FIG. l(a), the wire 10 for correcting irregularities of teeth is similar to an ordinary wire in its external appearance. However, the internal structure of the wire 10 is different from that of the ordinary wire. The structure of the wire 10 and the method of manufacturing the same will be described with reference to FIG. l(b).

[8] FIG. l(b) is a cross-sectional view of the "A" part of the wire shown in FIG. Ia.

[9] As shown in FIG. l(b), the conventional wire 10 for correcting irregularities of teeth consists of a metal wire 11, and a Teflon coating 13 formed on the surface of the metal wire 11. The metal wire 11 may be an ordinary metal wire or a metal wire formed from a shape memory alloy. In addition, the Teflon coating 13 may be formed by coating Teflon on the surface of the metal wire 11 through various coating methods. The Teflon coating 13 is coated so that the wire 10 for correcting irregularities of teeth has a color similar to a tooth color.

[10] Although a wire for correcting irregularities of teeth was manufactured by forming a

Teflon coating on a metal wire surface in the past, so that the wire for correcting irregularities of teeth exhibits a tooth color as described above, there was a problem due to denunciation in terms of harmfulness of Teflon to a hunan body. Therefore, what is urgently needed is to provide a wire for correcting irregularities of teeth which is harmless to a hunan body. Disclosure of Invention Technical Problem

[11] The present invention is made to solve the above^nentioned problems of the prior art, and the present invention is intended to provide a method of manufacturing a wire for correcting irregularities of teeth which is harmless to a human body. Technical Solution

[12] In order to solve the above-mentioned problems, there is provided a method of manufacturing a wire for correcting irregularities of teeth including the steps of: manufacturing a metal wire from a metal alloy material; chemically etching the surface of the metal wire and then conducting a thermal treatment; coating a metal material on the surface of the metal wire so that the surface of the metal wire exhibits a white color, and then conducting a thermal treatment; coating a transparent metal oxide film on the metal material coated on the metal wire; and forming a transparent parylene film on the transparent metal oxide film, and then conducting a thermal treatment to the metal wire. [13] Prior to coating the transparent metal oxide film, the inventive method further includes the step of chemically etching the surface of the metal material, and then conducting a thermal treatment.

[14] The metal wire may be formed from a material selected from a stainless steel, NiTi, a nickel (Ni)-based alloy, a copper (Cu)-based alloy, and an aluninun (Al)-based alloy.

[15] In addition, prior to chemically etching the surface of the metal wire, the surface of the metal wire is supersonically cleaned using an alkali, an organic solvent or super- pure water.

[16] The surface-etching of the metal wire is conducted using an etching solution prepared by mixing any of CuCl , FeCl , HCl, H SO , HNO , H PO , HF and H O

2 3 2 4 3 3 4 2 2 with H 2 O or an organic solvent.

[17] In addition, the metal wire is electrolytically or electrolessly etched in the etching solution. Due to this surface treatment, indentations with a width and a depth in the range of 0.1 μm to 50 μm is formed. Preferably, the surface-treated metal wire is wet- cleaned using any of an alkali, an organic solvent and super-pure water.

[18] The thermal treatment conducted after the chemical etching of the surface of the metal wire is performed under atmospheric pressure or within a vacuun chamber for 1 minute to 48 hours at a temperature of 50 ⁰C to 300 ⁰C.

[19] In addition, the metal material on the surface of the metal wire is coated using wet or dry electrolytic plating.

[20] The metal material coated on the metal wire surface is any of Ag, Zn, Sn, In, Pt, W,

Ni, Cr, Al, and Pd or a mixture thereof. Preferably, the metal material is coated on the entire surface of the metal wire at a thickness of 0.1 μm to 20 μm.

[21] The thermal treatment conducted after the coating of the metal material is performed under atmospheric pressure or within a vacuun chamber for 1 minute to 48 hours at a temperature of 50 ⁰C to 300 ⁰C.

[22] In addition, the surface-etching of the metal material is conducted using an etching solution prepared by mixing any of HCl, H SO , HNO , H O and a mixture thereof

2 4 3 2 2 with H O. Preferably, the surface-etching of the metal material is performed for 1 second to 5 minutes at a temperature of 10 ⁰C to 100 ⁰C. [23] In addition, the thermal treatment conducted after the chemical etching of the surface of the metal material is performed under atmospheric pressure or within a vacuun chamber for 1 minute to 48 hours at a temperature of 50 ⁰C to 300 ⁰C. [24] In addtion, the transparent metal oxid film may be formed by coating a raw material in a sol state formed by nano-size particles through a vaccum spraying process. [25] In addition, the transparent metal oxide film is formed from any of ITO, ZnO, TiO ,

2

Al O , Ta O , ZrO , SiO , GeO , Y O , La O , HfO , CaO, In O , SnO , MgO, WO ,

2 3 2 5 2 2 2 2 3 2 3 2 2 3 2 2 and WO , or a mixture thereof.

3

[26] The transparent metal oxide film may be coated at a thickness in the range of 1 nm to

1 μm. Preferably, the transparent metal oxide film is coated in a vacuum chamber at a temperature of 15 ⁰C to 300 ⁰C. [27] The transparent parylene film is formed by using at least one of C

(di-chloro-para-xylylene)-type, N (di-para-sylylene)-type, D

(tetra-chloro-para-xylylene)-type, F(Octafluoro-[2,2]para-xylylene)-type, HT-type, A- type, and AM-type dimers. [28] In addition, the thickness of the transparent parylene film is in the range of 1 μm to 50 μm. [29] In addition, the thermal treatment conducted after the formation of the transparent parylene film is conducted under atmosphere or within a vacuum chamber for 1 minute to 48 hours at a temperature of 50 ⁰C to 250 ⁰C. [30]

Advantageous Effects

[31] According to the inventive method of manufacturing a wire for correcting irregularities of teeth, it is possible to prevent a transparent metal material exhibiting a tooth color from being changed by coating a transparent parylene film after the transparent metal material is coated. In addition, since the wire manufactured according to the present invention makes a user feel the wire as if the wire is one with the user's teeth, it is possible to reduce discomfort.

[32] In addition, as being coated with a parylene film on the outermost surface, the wire for correcting irregularities of teeth is harmless to a hunan body, and capable of providing improved comfort when it is put on a set of teeth. Brief Description of the Drawings

[33] FIG. 1 is a schematic view and a cross-sectional view of a conventional wire for correcting irregularities of teeth, respectively;

[34] FIG. 2 is a schematic view and a cross-sectional view of a wire for correcting irregularities of teeth manufactured according to an embodiment of the present invention, respectively;

[35] FIG. 3 is constitutional formulas of dimers according to embodiments of the present invention; [36] FIGs. 4 to 7 are microscopic photographs of surface-treated metal wires according to embodiments of the present invention; and

[37] FIGs. 8 and 9 are microscopic photographs of metal wires with a white surface- treated metal material according to embodiments of the present invention. Best Mode for Carrying Out the Invention

[38] Now, the actions and embodiments of the inventive wire for correcting irregularities of teeth will be described with reference to accompanying drawings.

[39] FIG. 2 is a schematic view and a cross-sectional view of a wire for correcting irregularities of teeth manufactured according to an embodiment of the present invention, respectively.

[40] As shown in FIG. 2(a), the wire 20 for correcting irregularities of teeth is similar to an ordinary wire in its external appearance. However, the internal structure of the wire 20 is different from that of an ordinary wire. The shape and method of manufacturing the wire 20 will be described with reference to FIG. 2(b).

[41] FIG. 2(b) is a cross-sectional view of the "A" part of the wire shown in FIG. 2(a), which is presented so as to describe an embodiment of the present invention.

[42] As shown in FIG. 2(b), the wire 20 for correcting irregularities of teeth according to an embodiment of the present invention includes an elongated metal wire 21, a white metal material 23 coated on the surface of the metal wire 21, a transparent metal oxide film 24 coated on the surface of the metal material 23, and a parylene film 25 formed on the transparent metal oxide film 24.

[43] The metal wire 21 is formed from a metal alloy including an ordinary metal alloy material and a shape memory alloy material. Preferably, the metal alloy material for forming the metal wire 21 may be any of stainless steel, NiTi, a Ni-based allow, a Ti- based alloy, a Cu-based alloy, and an Al-based alloy

[44] When an ordinary metal is deformed over the elastic limit thereof, it will not return to its original shape, even if it is heated or cooled. However, seme kinds of alloys formed in a proper shape at a high temperature will return to their original shapes if they are deformed at room temperature and then heated.

[45] This is called as shape memory effect, which is caused because such alloys remember a given shape as an arrangement of atoms. Such an effect appears in an alloy which is transformed without diffusion. A parent phase atom arrangement at a high temperature is also remembered in such an alloy when the alloy is deformed at a low temperature transformation, and atoms are rearranged to their original arrangement when the alloy is heated. [46] Due to this effect, a great amount of force is produced while a shape memory alloy is returning to its original shape. As a result, such a shape memory alloy is used for tightening a mechanical part, beyond being used as a sensing device. Therefore, a metal wire formed from a shape memory alloy material can be employed to correct irregularities of teeth.

[47] The metal material 23 coated on the surface of the metal wire formed from a shape memory alloy material and an ordinary metal alloy material allows the surface of the metal wire 21 to exhibit a white color similar to a tooth color.

[48] The metal material 23 coated on the surface of the metal wire 21 may be coated through wet or dry electrolytic plating.

[49] Preferably, the metal material 23 coated on the surface of the metal wire 21 is any of

Ag, Zn, Sn, In, Pt, W, Ni, Cr, Al, and Pd, or a mixture formed by mixing two or more these components.

[50] The transparent metal oxide 24 coated on the surface of the white metal material 23 may be formed by vacuun-depositing any of ITO, ZnO, TiO , Al O , Ta O , ZrO , SiO

2 2 3 2 5 2

, GeO , Y O , La O , HfO , CaO, In O , SnO , MgO, WO , and WO , or a mixture

2 2 2 3 2 3 2 2 3 2 2 3 thereof.

[51] Preferably, the transparent metal oxide 24 has a thickness in the range of 1 nm to 1 μm, and is formed through plasma sputtering, e-beam evaporation, thermal evaporation, or ion plating. In addition, it is possible to form such a transparent metal oxide 24 by vacuum-spraying a raw material in a sol state formed by nano-size particles.

[52] A film 25 of transparent parylene, which is a high molecular compound, is coated on the transparent metal oxide film 24. Preferably, the transparent parylene film 25 is formed at a thickness in the range of 1 μm to 50 μm.

[53] The parylene is a material verified as being harmless to a himan body. The parylene is capable of being evenly coated on the transparent metal oxide film 24, has fine surface roughness, and feels soft. Consequently, the parylene-coated wire for correcting regularities of teeth provides comfort when it is put on a set of teeth. Mode for the Invention

[54] Now, the inventive method of manufacturing the above-mentioned wire for correcting irregularities of teeth will be described.

[55] The inventive method of manufacturing a wire for correcting irregularities of teeth includes the steps of: manufacturing a metal wire from a metal alloy material; chemically etching the surface of the metal wire, and then conducting a thermal treatment; coating a metal material film on the surface of the metal wire so that the surface of the metal wire exhibits a white color, and then conducting a heat treatment; coating a transparent metal oxide film on the metal material coated on the metal wire; and forming a transparent parylene film on the transparent metal oxide film, and then conducting a thermal treatment to the metal wire.

[56] Meanwhile, the inventive method may further include the step of chemically etching the surface of the metal material, and then conducting a thermal treatment, prior to coating the transparent metal oxide film.

[57] Each of the steps of the inventive method of manufacturing a wire for correcting irregularities of teeth will be described in detail.

[58] Firstly, a metal wire 21 is prepared from a metal alloy material. In particular, the metal wire 21 may be formed from any of a Ni-based alloy, a stainless steel (SUS), NiTi, a Ti-based alloy, a Cu-based alloy, and an Al-based alloy. Such a metal wire 21 has elasticity and tension.

[59] After preparing the metal wire 21, the surface of the metal wire 21 is chemically etched. Then, a thermal treatment is conducted. Prior to chemically etching the surface of the metal wire 21, the surface of the metal wire is preferably supersonically cleaned using an alkali, an organic solvent, or super-pure water. That is, the surface of the metal wire 21 is preferably cleaned prior to conducting chemical etching.

[60] Any etching solution capable of forming indentations on the surface of the metal wire 21 can be employed for etching the surface of the metal wire 21. In the present invention, an etching solution prepared by mixing any of CuCl , FeCl , HCl, H SO ,

2 3 2 4

HNO , H PO , HF and H O , or a mixture thereof with H O or an organic solvent

3 3 4 2 2 2

(methanol, ethanol, isopropyl alcohol, etc.) is used.

[61] The metal wire 21 is surface-treated by being electrolytically or electrolessly etched in a state it is submerged in the etching solution. With this heat treatment, the surface of the metal wire 21 is formed with indentations. The indentations have a width and a depth in the range of 0.1 μm to 20 μm. The surface-treated metal wire is wet-cleaned by using any of an alkali, an organic solvent, and water.

[62] FIGs. 4 to FIG. 7 show microscopic photographs of the surfaces of metal wires 21 treated through chemical etching, respectively. Here, FIG. 4 shows a microscopic photograph taken after a metal wire 21 of SUS was etched for 20 minutes with HCl (at 45 ⁰C), and FIG. 5 shows a microscopic photograph taken after an metal wire 21 of SUS was etched for 5 minutes by a solution formed by mixing sulfuric acid and water in the ratio of 1 to 2 (at 75 ⁰C). FIG. 6 shows a microscopic photograph taken after a metal wire 21 of NiTi was etched for 1 minute by aqueous solution of FeCl (at 40 ⁰C), and FIG. 7 shows a microscopic photograph after a metal wire 21 of NiTi was etched for 1 minute by aqueous solution of FeCl (at 50 ⁰C).

[63] Such a chemically etched metal wire 21 is thermally treated under a predetermined condition. The heat treatment conducted after chemical etching is performed under atmospheric pressure or in a vacuun chamber with a pressure of not more than 0.1 μTorr at a temperature in the range of 50 ⁰C to 300 ⁰C for 1 minute to 48 hours.

[64] After coating the white metal material 23 on the entire surface of the metal wire 21, the transparent metal oxide film 24 may be coated on the surface of the metal material 23 directly, or after the surface of the metal material 23 is chemically etched.

[65] When the chemical etching is previously conducted for the surface of the metal material 23, a predetermined etching solution is used. That is, the surface-etching of the metal material 23 is conducted using an etching solution prepared by mixing any of HCl, H SO4, HNO , and H O or a mixture thereof with H O.

2 3 2 2 2

[66] FIG. 8 shows a microscopic photograph (enlarged 500 X) of a metal wire of NiTi after the white metal material 23 was coated, and then the surface of the metal material 23 was etched for 18 sec using a solution formed by mixing HNO and H O, and FIG.

3 2

9 shows a microscopic photograph (enlarged 500 X) of an SUS metal wire after the white metal material 23 was coated and then the surface of the metal material 23 was etched for 50 sec using a solution formed by mixing HNO and H O.

[67] The surface-etching of the metal material 23 using an etching solution is performed for 1 second to 5 minutes at a temperature of 10 ⁰C to 100 ⁰C. After the chemical etching is conducted for the surface of the metal material, a thermal treatment is conducted. The thermal treatment is performed in a vacuun chamber with a pressure of not more than 0.1 μTorr for 1 minute to 48 hours at a temperature of 50 ⁰C to 300 0C.

[68] After the surface-etching is conducted for the metal material 23 and the thermal treatment is performed, the transparent metal oxide film 24 is coated.

[69] The transparent metal oxide film 24 is formed on the surface of the metal material 23 through sputtering, thermal vacuum evaporation, e-beam evaporation, or ion plating.

[70] Meanwhile, the transparent metal oxide film 24 may be formed on the surface of the metal material 23 by coating a row material in a sol state formed by nano-size particles through a vacuum spraying process.

[71] The transparent metal oxide film 24 may be formed from various metal oxides if they can be transparently colored. Any of ITO, ZnO, TiO , Al O , Ta O , ZrO , SiO , GeO ,

2 2 3 2 5 2 2 2

Y O , La O , HfO , CaO, In O , SnO , MgO, WO , and WO , or a mixture prepared by

2 3 2 3 2 2 3 2 2 3 nixing at least two of these components may be preferably used in the present invention.

[72] The transparent metal oxide film 24 formed as described above should be formed in a thickness which allows the wire for correcting irregularities of teeth to provide comfort when the wire is put on a set of teeth. The transparent metal oxide film 24 is preferably coated at a thickness of about 1 nm to 1 μm.

[73] If the transparent metal oxide 24 is vacuum-deposited, the deposition is conducted preferably at a temperature of 15 ⁰C to 300 ⁰C. The transparent metal oxide 24 is formed by introducing oxygen gas into the vacuun chamber at a flow rate of 1 to 200 seem. In addition, the transparent metal oxide 24 is plasma-treated, wherein it is desirable to introduce argon gas into the vacuun chamber at a flow rate of 50 seem to 500 seem, and to maintain the pressure of the chamber at 1 mTorr to 20 mTorr while the transparent metal oxide film is being plasma-treated.

[74] After the metal oxide film 24 is formed on the metal material 23, the transparent parylene film 25 is formed on the metal oxide film 24, and a thermal treatment is conducted. The coated parylene film 24 prevents the color of the white metal material 23 from being changed, and makes it possible to manufacture a wire for correcting irregularities of teeth, which is harmless to a human body. In consideration of the feeling provided to a user when the wire for correcting irregularities of teeth is put on, it is desired that the thickness of the transparent parylene film is in the range of 1 μm to 50 μm.

[75] The transparent parylene film is formed on the transparent metal oxide film using a dimer material, preferably using at least one of C (di-chloro-para-xylylene)-type (FIG. 3(a)), N (di-para-sylylene)-type (FIG. 3(b)), D (tetra-chloro-para-xylylene)-type (FIG. 3(c)), F(Octafluoro-[2,2]para-xylylene)-type (FIG. 3(d)), HT-type (FIG. 3(e)), A-type (FIG. 3(f)), and AM-type (FIG. 3(g)) dimers.

[76] The transparent parylene film 25 is formed by vaporizing a dimer at a temperature of

50 ⁰C to 250 ⁰C in a vaporizer, decomposing the dimer into monomers by making the dimer pass through a pyrolysis at a temperature of 550 ⁰C to 850 ⁰C, and then maintaining the partial pressures of the monomers within a vacuun chamber at 10 mTorr to 100 mTorr, so that the monomers are deposited on the surface of the transparent metal oxide film.

[77] After the transparent parylene film 25 is formed as described above, a thermal treatment is conducted within a vacuum chamber with a pressure of not more than 0.1 μTorr for 1 minute to 48 hours at a temperature of 50 ⁰C to 250 ⁰C. [78] The present invention can be implemented in various forms without being limited to the above-mentioned embodiments, which are presented so as to completely disclose the present invention, and to allow an ordinary skilled person in the art to fully grasp the scope of the present invention. Industrial Applicability

[79] The inventive method of manufacturing a wire for correcting irregularities of teeth can be used for persons who wish to correct irregularities of teeth, mainly in dental clinics. A wire manufactured according to the present invention is characterized by the fact that it is harmless to a himan body, and is capable of maintaining a tooth color.

Claims

[1] A method of manufacturing a wire for correcting irregularities of teeth, comprising the steps of: manufacturing a metal wire from a metal alloy material; chemically etching the surface of the metal wire, and then conducting a thermal treatment; coating a metal material film on the surface of the metal wire so that the surface of the metal wire exhibits a white color, and then conducting a thermal treatment; coating a transparent metal oxide film on the metal material coated on the metal wire; and forming a transparent parylene film on the transparent metal oxide film, and then conducting a thermal treatment.

[2] The method as claimed in claim 1, further comprising the step of chemically etching the surface of the metal material, and then conducting a thermal treatment, prior to coating the transparent metal oxide film.

[3] The method as claimed in claim 1 or 2, wherein the metal wire is formed from a material selected from a stainless steel, NiTi, a nickel (Ni)-based alloy, a copper

(Cu)-based alloy, and an aluminum (Al)-based alloy.

[4] The method as claimed in claim 1 or 2, wherein prior to chemically etching the surface of the metal wire, the surface of the metal wire is supersonically cleaned using an alkali, an organic solvent or super-pure water.

[5] The method as claimed in claim 1 or 2, wherein the surface-etching of the metal wire is conducted using an etching solution prepared by mixing any of CuCl ,

FeCl , HCl, H SO , HNO , H PO , HF and H O with H O or an organic solvent.

3 2 4 3 3 4 2 2 2

[6] The method as claimed in claim 5, wherein the metal wire is electrolytically or electrolessly etched in the etching solution.

[7] The method as claimed in claim 6, wherein indentations with a width and a depth in the range of 0.1 /M to 50 /M are formed on the metal wire due to the surface treatment.

[8] The method as claimed in claim 7, wherein the surface-treated metal wire is wet- cleaned using any of an alkali, an organic solvent and super-pure water.

[9] The method as claimed in claim 1 or 2, wherein the thermal treatment conducted after the chemical etching of the surface of the metal wire is performed under at- mospheric pressure or in a vacuun chamber for 1 minute to 48 hours at a temperature of 50 ⁰C to 300 ⁰C.

[10] The method as claimed in claim 1 or 2, wherein the metal material on the surface of the metal wire is coated using wet or dry electrolytic plating.

[11] The method as claimed in claim 10, wherein the metal material coated on the metal wire surface is any of Ag, Zn, Sn, In, Pt, W, Ni, Cr, Al, and Pd or a mixture thereof.

[12] The method as claimed in claim 11, wherein the metal material is coated on the entire surface of the metal wire at a thickness 0.1 μm to 20 μm.

[13] The method as claimed in claim 1 or 2, wherein the thermal treatment conducted after the coating of the metal material is conducted under atmospheric pressure or within a vacuum chamber for 1 minute to 48 hours at a temperature of 50 ⁰C to 300 ⁰C.

[14] The method as claimed in claim 2, wherein the surface-etching of the metal material is conducted using an etching solution prepared by mixing any of HCl,

H SO , HNO , H O and a mixture thereof with H O.

2 4 3 2 2 2

[15] The method as claimed in claim 14, wherein the surface-etching of the metal material is performed for 1 second to 5 minutes at a temperature of 10 ⁰C to 100 0C.

[16] The method as claimed in claim 2, wherein the thermal treatment conducted after the chemical etching of the surface of the metal material is conducted under atmospheric pressure or within a vacuun chamber for 1 minute to 48 hours at a temperature of 50 ⁰C to 300 ⁰C.

[17] The method as claimed in claim 1 or 2, wherein the transparent metal oxide film is formed by coating a raw material in a sol state formed by nano-size particles using a vacuun spraying process.

[18] The method as claimed in claim 17, wherein the transparent metal oxide film is formed from any of ITO, ZnO, TiO , Al O , Ta O , ZrO , SiO , GeO , Y O , La

2 2 3 2 5 2 2 2 2 3 2

O , HfO , CaO, In O , SnO , MgO, WO , and WO , or a mixture thereof.

3 2 2 3 2 2 3

[19] The method as claimed in claim 18, wherein the transparent metal oxide film is coated at a thickness of 1 nm to 1 μm.

[20] The method as claimed in claim 19, wherein the transparent metal oxide film is coated in a vacuun chamber at a temperature of 15 ⁰C to 300 ⁰C.

[21] The method as claimed in claim 1 or 2, wherein the transparent parylene film is formed by using at least one of C (di-chloro-para-xylylene)-type, N (di-para-sylylene)-type, D (tetra-chloro-para-xylylene)-type, F(octafluoro-[2,2] para-xylylene)-type, HT-type, A-type, and AM-type dimers.

[22] The method as claimed in claim 21, wherein the thickness of the transparent parylene film is in the range of 1 μm to 50 μm.

[23] The method as claimed in claim 1 or 2, wherein the thermal treatment conducted after the formation of the transparent parylene film is conducted under atmosphere or within a vacuun chamber for 1 minute to 48 hours at a temperature of 50 ⁰C to 250 ⁰C.