TWI246994B - Antifogging element and method for forming the same - Google Patents

Abstract

A coating agent including photocatalyst particles (11) dispersed in a titanium peroxide solution obtainable by causing titanium hydroxide (orthotitanic acid) gel to act with hydrogen peroxide being used as a material for the photocatalyst film (18) is used to a photocatalyst film having photocatalyst particles supported therein. By forming a porous hydrophilic substance film (12) on the photocatalyst film (18), the damages on the film caused by the wiping can be prevented. Also, a film formed by using the coating agent including photocatalyst particles dispersed in a titanium peroxide solution at a temperature of from normal room temperature to 200 DEG C is of high porosity in comparison with a film formed at a higher temperature and with a film not having a photocatalyst particles dispersed therein. Consequently, the photocatalyst film (18) and the hydrophilic substance film (12) have good adhesion property when use with each other.

Description

5. Description of the Invention (1) [Technical Field] The present invention relates to an anti-fog element and a method for forming a hydrophilic substance film which forms a pore of a photocatalyst film on a surface of a substrate, and relates to a method for improving An anti-fog element having a good adhesion resistance to a film and a method for forming the same. [Prior Art] In International Publication W096/29375, it is disclosed that the right, titanium ore (_tase) type Ti〇2 particles are supported by dioxane; and the second is equal to normal temperature ~150. A method of obtaining an anti-fog element at a low temperature of ruthenium. More /, body and 0, will contain anatase type T i 〇 2 (titanium dioxide 1 red stone Untile) type Ti〇Γ 二董", \ emulsified titanium) particles or gold (S i 0 ) 43⁄4 ^ / λ « ^ 2 emulsified titanium) particles and cerium oxide oxygen = cerium; coated on the surface of the substrate to form a photocatalyst film composed of a dioxide-emulsion emulsified titanium. The dioxo-crystal form of dioxane...== degree is heated to make it again; , in the above-mentioned warm crystal form of cerium oxide 2, 2, so that the titanium oxide is condensed in the non-y-y-one to form a photocatalyst film. The anatase type in the membrane of the cerium oxide film is called 微粒 Λ from the surface of the membrane only by wiping, so the Ti 〇 2 particles are easily caused by the problem of damage, resulting in so-called causes. T1 〇2 particles detached and 1246994 V. Description of the invention (2) [Disclosed in the present invention] The use of light-touching media particles in the titanium hydroxide gel (ortho-titanic acid) is obtained = emulsion The composition of the coating agent 'to form a light touch: oxygen: the surface of the film of the titanium soluble film will be damaged by the rubbing. Then: "": The formation of a porous hydrophilic film on the medium, the anti-catalyst can be used to disperse the photo-contacting media particles in the titanium peroxide solution. ^ In addition, the agent is at a temperature from normal temperature to less than 20 (TC temperature The film formed by the film is formed by a film formed under the cloth or a film in which the photo-contacting medium particles are not dispersed, and is more porous and more porous. Therefore, the photocatalyst film and the hydrophilic film are both Very good. ◎ Adhesion between 膑 [Simplified description of the drawings] Fig. 1 is a partial cross-sectional view showing an embodiment of the present invention showing the results of the damage test of the film. The description of the decomposition action of the organic substance or the like of the photocatalyst film by the anti-fogging of the porous hydrophilic material film. The operation and the fourth and fifth drawings show the other parts of the present invention. [Embodiment of various uses of the cut section] Fig. 6 to Fig. 14 are sectional views showing an example of application of the present invention.

2190-4347-PF; Peterliou.ptd Page 5 V. Invention description (3) 10~ substrate, 1 8~ photocatalyst film, 32~ mirror body, 3 6~reflective film, 4 4~ power supply, 54, 56~ clip Electrode 1 2~ hydrophilic material film, 30 0 to automotive rear view mirror, 3 4 to mirror accessory, 4 2 to panel heater, 50 to transparent electrode film, [best embodiment of the invention] In the light, a colloidal (ortho-titanium agent) is used as a coating crystal form of a coating method such as a substantially sub-coating method or an impregnation method obtained by peroxidation. The present invention is to form a photocatalyst film on the surface of a substrate. The photocatalyst comprising the anti-fog element forming a porous hydrophilic substance film on the re-catalyst film and dispersing the photo-contacting medium particles in a titanium peroxide solution obtained by causing hydrogen peroxide to act on the titanium hydroxide coagulating acid) Membrane material. Here, in general, the so-called titanium peroxide solution is usually hydrogenated as a sol solution of amorphous titanium oxide in a gel-like titanium hydroxide gel (ortho-titania). Since the titanium peroxide solution is composed of titanium, oxygen, and hydrogen, the purity is high. The method of forming a film by dispersing photocatalyst granules in a titanium oxide solution, and t, for example, 'you spray coating method, (4) coating method, and flow = by a titanium oxide solution The photocatalyst dispersed in the film is dried and dehydrated and condensed, and the photocatalyst film carrying the photo-contacting media particles in the titanium film is formed in the non-1246994 -----_- five, invention description (4) The temperature of the utn heat treatment is preferably at room temperature ~ less than 200 V, often less than 150 ° c, better, 赍,, 4 1 η η > 丄丄 #, on h ~ 士士ΛΛ 2 ang dish ~ 100 C or so good. By room temperature ~100. The porphyrin membrane is more porous than the high-temperature treatment. The combination of the membrane and the hydrophilic membrane can be applied in the coating step of the coating agent. The cloth step and the coating are carried out later. In addition, in the invention, the photo-touch media particles refer to the photocatalyst action when the light is encountered. ΓΓ ΓΓ 由 由 由 由 由 由 由 由 由 最佳 最佳 最佳 最佳 最佳 最佳 最佳 最佳 最佳 过 过 过 过 过 过 过 过 过 过 过: Users can do it. For example, Ti〇2, Zn0, w〇3, 〇 〇, 'Fe2〇3# 〇, 持, Λ 及 及 及 及 及 及 及 及 及 及 及 及 及 及 及 及 及 及 及 及 及 及 及 及 及 及 及 及. The crystal structure of Τι〇2 has a rutile type and an anatase type is good because of the large photocatalytic effect of the anatase type.

If the irradiation corresponds to the anatase type of T i 〇, the bond between the 'X', the qcmnm of the kiln, the hard, and the interstitial space (the bond gap i is about 39 - the outer line of the rabbit, it will be inside the excited Electron generation: The generated electrons and holes react with oxygen and water present on the surface of the hydrophilic substance to form a peroxide anion (萁, (0H). The above generated 〇2_ or · 0H system The emulsification power of the organic substance having a strong 4 to 7 can be attached to the surface of the hydrophilic substance film can be reduced by the knife. Even if other light-contacting medium particles are used, the port utilizes a wave corresponding to the bonding gap of the photocatalyst; The same effect as anatase type Ti〇2 is obtained. Hibiscus 2190-4347-PF; Peter1iou.ptd Page 7 12469994 5 invention description (5) In the invention, the towel is used by using a titanium oxide solution "two (10) The above film is formed at room temperature to less than 2. 膑 吏 吏 : : : : : : 非晶 非晶 非晶 非晶 非晶 非晶 非晶 非晶 非晶 非晶 非晶 非晶 非晶 非晶 非晶 非晶 非晶 非晶 非晶 非晶 非晶 非晶 非晶 非晶 非晶 非晶 非晶 非晶 非晶 非晶 非晶 非晶 非晶 非晶 非晶 非晶 非晶 非晶 非晶= film. Light is preferably in the range of 40 to 20 〇 nm. From the viewpoint, it is in the present invention. +, the hydrophilic material film is formed by at least the watch car 4: the hydrophilic material film is made of a material having high hydrophilicity, and the hydrophilic substance m' can be used with a hydrophilic substance: Rotary coating Cloth method, impregnation coating method, spray coating method: coating method such as f 2 dynamic coating method... becomes porous film. In addition, 'Ion implantation method or sputtering method, I empty space can also be used. : = PVD method, * A film of a hydrophilic substance such as Si〇2 is formed into a film. In addition, as a material of a hydrophilic substance, for example,:

A metal oxide such as Si 〇 2, A 丨 2 〇 3 or the like. The above metal oxide generally exhibits hydrophilicity because it has a hydrophilic OH group. - According to experiments by the inventors, etc., it is obtained that Si A has the best hydrophilicity. On the right, in the present invention, by making the hydrophilic material film 丨〇〇 nm or less, the electrons or holes generated in the photocatalyst film can sufficiently react with the hydrophilic material film, oxygen, and water. The film thickness of the hydrophilic material film is preferably 1 〇 nm or more from the viewpoint of surface damage, and 1 〇 丨〇 from the viewpoint of maintaining the antifogging effect when the line is not irradiated. The second of 〇nm is better. Scope Next, the following is a brief description of the preferred embodiment of the anti-fog element of the present invention. 1246994 V. Description of the Invention (6). Fig. 1 shows an anti-fog element using a titanium peroxide plasma film 12 in which a solution of a photocatalyst film 18 is formed on a substrate 10'. When a hydrophilic substance is formed by using oxygen peroxide, the film is formed under normal temperature to less than 200 t: 彳 θ 2 to form a film, and here, ruthenium is used in the titanium peroxide solution. Film formation in J liquid, and at room temperature ~ less than 2 〇〇; = film formation of the particles in the amorphous called photocatalyst two ^ f theory can be at room temperature ~ 15 (rc low temperature 4 = : 2 Touching the media particles. For example, it is made up of a solution of particles such as polyoxane which has been so-called amorphous cerium oxide in the form of so-called amorphous cerium oxide. Film-formed anti-fog element: two ': titanium ore type T 1 02 The anti-fog element formed by the invention; damage == piece: using κ ^ ^ ^ bright field r into the 仃 comparison. JL community 娄 25 〇n , the evaluation method is to wipe the film repeatedly for 500 times, 150^ pieces without scratches. The result of the former anti-fog element: observed flaws, and the use of this method to film the person did not observe the scar, although the above The detailed reason for the result is unknown, but it is presumed that because the anatase-type Ti〇2 particles in the element are only supported by the ruthenium dioxide film, the Ti〇2 particles are easily rubbed to cause Ti〇. 2 The particles fall off and cause damage. Another, ί : 5 :: The anti-fog element of the present invention is presumed to be non-fogging due to the surface of the anti-fog element The anatase type Ti〇2 in the shape of Ti曰2 does not fall off, so page 9 2190-4347-PF; Peterli〇u.ptd V. Invention description (7) Highly resistant to damage. The anti-fog element of Si and the former is appreciable on the film; in the case of a wide range of =, according to the anti-fog element of the structure of Fig. 1, 'τ is as 笫 = one due to the surface of the hydrophilic material film 12 system In the case of the image, the wettability of the surface of the thin tube phenomenon is improved and the trait is improved. Therefore, the water droplets are diffused into a film shape to play the antifogging pro 2', so that the adhesion is applied to automotive rearview mirrors and bathrooms. Mirror, steam if the above, etc. 'water droplets are not easy to bead-like adhesion, identify two households: glass: outside, when running into the porous opening 20, θ is well served. This or the organic matter in the atmosphere or Ν〇χ The organic matter, etc., is such that the light in the photocatalyst film 18 == sub: hole pair. The generated electrons and holes are formed by the hydrophilic substance, and the oxygen present on the surface of the hydrophilic substance film 12 is Aqueous peroxide anion (02-) or radical (.0H). In addition, porous hydrophilic substance The porous opening of the plasma membrane can be opened to the surface of the photocatalyst film to allow the organic substance or N〇x running into the porous opening to directly contact the photocatalyst film to obtain a high photocatalytic reaction. However, when the hydrophilic substance is When the film is Si〇2 or the like, as shown in Fig. 3, even if the porous opening does not reach the surface of the photocatalyst film (i.e., stops at a strong oxidizing power to the 02- or .OH system, when it is opened 2 附着 附着 附着 附着 附着 附着 附着 附着 附着 附着 附着 附着 附着 附着 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 ) On the way to the surface of the photocatalyst film), the ray 〇 2 is mainly ultraviolet ray), and the light-emitting material film produced by the reaction, or the photocatalytic film produced by the photocatalyst film is sufficient. In the case of a thin η hole, the organic matter or yt of the opening of the porous parent can be decomposed and removed by running on the surface of the substrate 10 and the light adhering to the porous fourth image. A film 1-5 is formed between the film 15 and the catalyst film 18. In the case of an intermediate film, the material is a tantalum film. In the above, η # lifts, for example, when the substrate is an organic catalyst: the L t film is light that can be passed through the photocatalyst film A 浐; 5; C 谕 以 4 4 4 4 4 4 4 4 4 4 4 4 4 4 4 4 4 4 4 4 4 4 4 4 4 4 4 4 4 4 4 4 4 4 4 4 4 4 4 4 Further, when the substrate slo 2 is in the high temperature treatment step, for example, S 1 〇 2 is used as the diffusion preventing film. An anti-fog mirror is formed by forming an intermediate film 15 made of a metal reflective film such as cr or A1 between the surface of the substrate 10' and the photocatalyst film 18. Although the first to fifth figures are all a single-sided film, the present invention is limited. Further, according to the present invention, an anti-fog element can be produced at a normal temperature to a temperature of less than 2 〇 (lower rc). Therefore, even when a soda lime glass is used for the substrate, the dish does not require an alkali diffusion preventing film. Moreover, since it is a low-temperature process, the reflective film is not easily oxidized, and the reflectance is not impaired. Further, since the processing temperature is lowered, energy can be saved, work can be shortened, and cost can be reduced. If the invention is based on the present invention, Both the photocatalyst film and the hydrophilic film can be formed at a low temperature and by a wet method, so that manufacturing can reduce the cost.

1246994

The embodiments (the sixth embodiment of the present invention are described in the sixth to the first embodiment). The embodiment is applied to the rearview mirror for an automobile (the G picture is the province, the window for the vehicle is not returned), and the embodiment 6 to 8 (1st to 1st 3) is applied to the apricot ^ i ^ example (the same as in the case of a window glass for buildings). Figure 14 is an example of a mirror for a bathroom. • The film formation conditions in the examples are as follows. Substrate · Lime-lime glass • Photocatalyst film τ.η • 夕 才 股份有限公司 ΤΑΚ ΤΑΚ (containing anatase type Τ1 〇 2 granules of titanium oxide solution) Film formation temperature: 1 Q 〇 film thickness: 75 毫Micron (nm) • Hydrophilic material film, material: N-103X (Si02 coating agent) manufactured by Kokusai Co., Ltd. Film formation temperature: 2 5 °C Film thickness: 20 nm (1) Example 1 (Fig. 6) The rearview mirror 30 for a vehicle is constructed as a door mirror (d〇〇r mirr〇: r) or a fender mirror. A mirror attachment 34 is housed in the mirror body 32 in the rear view mirror 3 . The mirror attachment 34 is formed of a Ti 2 film 18 and a porous shape in front of the transparent glass substrate. The film 12 is formed on the film 12, and a reflection film 36 of Cr, A1 or the like is formed on the back surface of the transparent glass substrate 10. Vehicle rear image system

2190-4347-PF; Peterliou.ptd Page 12 1246994 V. INSTRUCTION DESCRIPTION (10) 'Reflected by the reflective film 36 through the Si〇2 film 12, the Ti〇2 film 18, and the transparent glass substrate 10' and follows the opposite The path into the driver's field of vision. The organic substance or the like which has entered the porous opening of the film of the Si 2 film 2 can be decomposed by the redox reaction initiated by the photocatalytic reaction of the τ i film 18. (2) Example 2 (Fig. 7) The mirror attachment 40 of the rearview mirror 38 of the vehicle is formed by forming a Ti〇2 film 18 and a porous 3丨02 film 12 on the front surface of the transparent glass substrate 1 A reflection film 36 of Cr, A1 or the like is formed on the back surface of the transparent glass substrate 10. The panel heater 4 2 as a heating element is attached to the entire area of the reflective film 36 by an adhesive, an adhesive, or the like, and is energized by the power source 44. If the panel heater 4 2 is, for example, a PTC (Positive Characteristic Thermistor) panel heater, it can be directly driven by the battery power of the automobile without requiring a temperature control circuit or the like. The PTC panel heater is composed of a polymer planar heat generating body to which PTC characteristics have been imparted (an electrode such as silver or copper is disposed on a conductive resin, and a pE film is laminated). The water droplets which are diffused into a film shape on the S i 02 film 12 can be effectively removed (evaporated) by the heating of the panel heater 42. (3) Example 3 (Fig. 8) The mirror attachment 48 of the automotive rearview mirror 46 is formed by sequentially forming a transparent electrode film 50 such as I TO or a TiO 2 film 18 as a heating element in front of the transparent glass substrate 1 . The porous S i 02 film 12 is formed on the back surface of the transparent glass substrate 10 to form a reflection film 36 such as Cr or A1. A clip electrode 54, 56 is attached to the upper and lower sides of the laminate of the transparent glass substrate 10 and the transparent electrode film 50, and is transparent by being supplied from the power source 44 to the transparent electrode film 50.

2190-4347-PF; Peterliou.ptd Page 13 1246994 V. Description of Invention (11) The electrode film 50 is heated to effectively remove water droplets which are diffused into a film form on the surface of the Si 02 film 12. (4) Example 4 (Fig. 9) The mirror attachment member 5 of the rearview mirror of the automobile is formed by forming a T i 〇 2 film 18 and a porous si 〇 2 film 1 2 in front of the transparent glass substrate 1 . A reflection film 36 of Cr, A1 or the like is formed on the back surface of the transparent glass substrate 10. The clamping electrodes 54, 56 are attached to the upper and lower sides of the mirror assembly 58. By energizing the power source 44 to the reflective film 36 (which also serves as a heating element), the reflective film 36 can be heated to be effectively removed at the S i The surface of the film 12 is diffused into a film-like water droplet. (5) Example 5 (Fig. 1) The rear view mirror 60 of the automobile is constructed as a surface mirror (mirror having a reflecting film formed on the front side of the base member). The mirror attachment 62 is formed in sequence on the front surface of the glass substrate 10' (not necessarily transparent) (: 1«, 41, etc., the reflective film 36, the Ti〇2 film 18, the porous Si 〇2 film 12, and The glass substrate 1A is attached to the back surface or the panel heater 42. The panel heater 42 is heated by the power source 44. The reflection film 36 itself can be used as the heating element in the same manner as in Fig. 9. In place of the panel heater 42. (6) Example 6 (Embodiment 11) The brake window 64 is a side surface (the surface on the outer side or the inner side of the vehicle) of the transparent glass substrate 10 constituting the window glass body. i 〇a is formed by forming a T i A film 18 and a porous S i 〇 2 film 12 and being transparent (colorless transparent, colored transparent). T 1 〇 2 film 18 , porous s 丨〇 2 When the membrane cartridge 2 is on the outside of the vehicle, the effect of removing raindrops or the like can be obtained, and if it is inside the vehicle, the effect of removing water droplets such as fogging can be obtained.

1246994

(7) Embodiment 7 (Fig. 1 2) The window 66 for an automobile is formed on the surface of the side of the transparent glass plate constituting the window glass body (the surface on the outer side of the vehicle or the inner side of the vehicle) i〇a. & is formed into a transparent electrode film 50 such as ITO, a Ti 2 film 18, and a porous si 2 film 2, and is formed in a transparent shape as a whole. The sandwich electrodes 54 and 56 are attached to the upper and lower sides of the laminate of the transparent glass substrate 10 and the transparent electrode film, and the transparent electrode film 5 is heated by being energized from the power source 44 to the transparent electrode film 50. The water droplets which are diffused into a film form on the surface of the Si 〇 2 film 12 are effectively removed. (8) Example 8 (Fig. 13) The window 6.8 for automobiles is formed on both sides of a transparent glass substrate 1 to form a τ丨〇2 film 18 and a porous si ? film 1 2 so that both sides are protected. Mild. It is also possible to arrange a transparent electrode film of 1] [〇 etc.] between the surface of the transparent glass substrate 1 and the ruthenium film 18. (9) In the bathroom mirror 70, the film 18 and the porous Si〇2 film 12 are formed on the front surface of the transparent glass substrate 1 and Cr is formed on the back surface of the transparent glass substrate 1 A1 special reflective film 36. A heat generating body (a panel heater such as P T C or the like) may be disposed on the back surface of the reflective film 36, and a transparent electrode film such as ITO may be disposed between the transparent glass substrate 1 and the ITO film 18. Further, in the above embodiments, the substrate member is formed of a glass substrate. However, a substrate other than glass (plastic, metal, or the like) may be used.

2190-4347-PF; Peterli〇u.ptd Page 15 1246994 V. INSTRUCTIONS (13) 270 substrates, etc., can be used for the substrate member or building window: member. t Catalyst reaction. Also, etc. & when 'the role of the window line by sunlight: two light-touch media particles (Ti〇2) because 丄: even light touch,,,;: therefore can also get UV insulation @ ^ $ for absorption of ultraviolet Formed inside the room (in the car) two tongues: to the removal effect of raindrops, etc., in addition to the effect. t can be used to obtain water droplets such as fog and fog to form anti-fog on both sides. μ 去 ' 'The anti-fog element of the present invention can be used in the Mei Tuo surname μ to form a reflective film for the automobile. When the reflective member is formed on the substrate member, it can be used as a mirror for the rearview mirror room of an automobile. In the case of the catalyst reaction 1, when it is used as a bath photocatalyst, it is obtained by hunting ultraviolet light from a battalion light.

Claims (1)

124^94?-1 丨I---H^t#^i8〇122988, sheep q 曰&lt;6...1 ~- The above photo-contacting film forms a photocatalyst film, and then forms a hydrophilic layer The material film, in which the S photocatalyst film is at room temperature ~ less than 200. The catalyst at the temperature of 〇:::: The amorphous titanium oxide film carries the photo-contacting media particles. 2 Oxidation = Photocatalyst film is used to disperse the photo-contacting media particles in the titanium-soluble one: in the gel (ortho-titanate) The effect of the obtained peroxidation less than 200 t, the western production agent / / / = coating agent through the above-mentioned room temperature ~ coating method, wear = double: D: transfer coating method, impregnation coating method, The mist of the mouth is taken off by the cloth or the dynamic coating method, and after the film is formed, it is dried, and the mixture is opened to form a photocatalyst film carrying the photocatalyst particles in the amorphous titanium oxide film. The titanium oxide solution is substantially composed of titanium, oxygen, and hydrogen, and the composition of the porous hydrophilic material film is Si〇24Ai2〇3, and the photocatalyst film has a thickness of 40 to 20 nm, and the hydrophilicity of the porous material is porous. The material film thickness is 10 to 100 nm. The anti-fog element according to claim 1, wherein an intermediate film is formed between the surface of the substrate and the photocatalyst film, and when the substrate is an organic material, the middle of the tanning system is used. membrane. 3. The anti-fog element according to claim 1, wherein the defense element is transparent as a whole to constitute a window for an automobile. 4. The anti-fog element according to claim 1, wherein the substrate is a transparent substrate member, and a 17th tribute 2190-4347-PF2.ptc 1246994 is filed on the inside of the clarified substrate member. </ RTI> </ RTI> <RTIgt; </ RTI> <RTIgt; </ RTI> <RTIgt; </ RTI> <RTIgt; </ RTI> <RTIgt; </ RTI> <RTIgt; </ RTI> <RTIgt; The transparent photocatalyst film reacted by the photocatalyst further forms a porous transparent hydrophilic substance film on the photocatalyst film to form an anti-fog mirror having a hydrophilic surface. The anti-fog element according to the fourth aspect of the invention, wherein the anti-fog element is used to constitute a rearview mirror for an automobile. 7. The anti-fog element according to claim 5, wherein the anti-fog element is used to constitute a rearview mirror for an automobile. 8) a method for forming an anti-fog element, wherein a photocatalyst film is formed on a surface of a substrate, and a porous hydrophilic material film is formed on the photocatalyst film, wherein: the photo-contacting medium particles are dispersed to make hydrogen peroxide A coating agent composed of a titanium peroxide solution obtained by applying a titanium oxide solution obtained by using a titanium hydroxide gel (orthotic acid) is used as a material of the photocatalyst film; and the coating agent is allowed to pass through a normal temperature to a temperature of less than 2 Å. (: at a temperature of φ ^ ί ^ Ϊ, dip coating method, spray coating method, roller coating method or flow ί): ΐ φ φ 成 成 成 成 成 成 成 成 成 成 成 成 成 成 成 成 成 成 成 成 成 成The amorphous qing solution is essentially composed of chin and yttrium, and the composition of the hydrophilic material film of the sulphate is si〇^Ai2〇3, and the photocatalytic film has a thickness of 40 to 200 nm, and the porous Hydrophilic substance Page 18 2190.4347-PF2.ptc 1246994 Case No. 90122988 修正 Amendment 6 Patent application The film thickness is 10~100nm. 2190-4347-PF2.ptc Page 19 1111·