KR100892455B1 - Corrosion-resistant, ultra-hydrophilic and antibacterial thin film coated metal product - Google Patents

Abstract

The present invention provides a metal matrix sheet to easily produce a refrigeration and air-conditioning metal material having excellent hydrophilicity and aging characteristics as well as excellent corrosion resistance and antibacterial and anti-bacterial properties on an industrial scale. After selectively forming a corrosion-resistant thin film on both sides of the coating, and then coating a thin film of superhydrophilic and bactericidal / antimicrobial Ti- (Ag, Cu and / or Co) -OC compound on both sides where the corrosion-resistant thin film is formed or not Provided is a superhydrophilic and bactericidal / antibacterial metal product produced by performing machining to a desired shape and a method for producing the same.

Description

Corrosion resistant, super hydrophilic and antibacterial metal products {CORROSION-RESISTANT, ULTRA-HYDROPHILIC AND ANTIBACTERIAL THIN FILM COATED METAL PRODUCT}

The present invention relates to corrosion resistant, superhydrophilic and bactericidal / antibacterial metal products.

Metal materials having a hydrophilic surface layer formed on the surface have been used very effectively throughout the industrial field. The present invention will be described by taking a heat exchanger as an example.

Heat exchangers that exchange heat by direct or indirect contact of two fluids with different temperatures are widely used in many industrial fields, and are particularly important in heating, air conditioning, power generation, waste heat recovery, and chemical processes.

Among these heat exchangers, the heat exchanger for refrigeration and air conditioning forms fins as expansion surfaces on the air side to improve heat transfer. When the air with humidity passes through the fin during heat exchange, heat transfer occurs due to the low temperature refrigerant supplied into the tube.When the temperature of the fin surface is below the dew point temperature of the air temperature with this humidity, water droplets are generated on the surface of the heat exchanger. This impedes the flow of pressure and thereby increases the pressure drop, the pressure difference between the heat exchanger inlet and outlet. Therefore, in order to supply the same flow rate, the power of the fan must be increased, which brings about power consumption.

In order to solve such a problem, conventionally, as shown in Japanese Patent Laid-Open No. 61-8598, after rust treatment with Cr ⁺⁶ for corrosion resistance on an aluminum sheet of a heat exchanger fin, the silicate thereon (silicate) coating treatment has been performed to impart hydrophilicity to improve the flow of condensate formed on the fin surface. This is commonly referred to as PCM (pre-coated material).

However, in order to solve the corrosion resistance problem, the PCM is required for Cr ⁺⁶ , and since 2006, Cr ⁺⁶ cannot be used in 2006 due to environmental regulations. Therefore, development of a substitute material for Cr ⁺⁶ is required. It became. To date, Cr ^{+ 3} and resin types have been proposed. In addition, TCE (tetrachloroethane) which is inevitably used to clean aluminum during the manufacturing process of the PCM has also been accompanied by environmental pollution. In addition, the PCM initially shows excellent hydrophilic performance, but has a aging characteristic that gradually loses its hydrophilic property over time. In addition, in recent years, a lot of chemicals are used as a wallpaper material, and the silicate material for imparting hydrophilicity is chemically combined with the wallpaper to discolor the wallpaper, and the volatilized material also causes discomfort to humans. .

In addition, efforts have been made to satisfy various needs by forming functional (eg, hydrophilic or hydrophobic) surface layers in existing materials. Such a method for forming a functional surface layer can be classified into 1) depositing a functional surface layer on an existing material, and 2) modifying the surface film of an existing material to have new physical and chemical properties.

However, with the latter method, the problem of restoring the original surface properties after a certain time has been constantly raised because the surface properties change with time. For example, when the metal such as aluminum is treated by the ion beam assisted reaction method, it can be seen that the hydrophilicity of the metal surface is increased because the natural oxide film is removed through the etching phenomenon on the aluminum surface and the functional film is formed on the surface. In this case, the effect of increasing the hydrophilicity through the etching of the natural oxide film is that the growth of the oxide film in the natural state of the aluminum surface over time, the effect of enhancing the hydrophilicity is reduced and the functional film formed on the aluminum surface is extremely thin on the surface Consisting of a thick layer (<few nm), the mechanical resistance to changes in the environment (water, temperature, etc.) over time is so weak that the increased hydrophilic properties are reduced and restored to the original surface properties.

Because of these problems, efforts have been made to form functional surface layers, such as hydrophilicity or hydrophobicity, on metal materials that can maintain physically and chemically stable states.

As a part thereof, Japanese Laid-Open Patent Publication No. 2001-280879 is a heat exchanger having a fin made of a conductive metal material in a metal pipe serving as a passage for a refrigerant, and the fin of the heat exchanger in the atmosphere is filled with compound vapor containing titanium as a source gas. A plasma CVD technique is disclosed in which a heat exchanger coated only with a titanium oxide thin film on the surface of the fin is supplied by flowing in parallel with the surface. The publication discloses that excellent hydrophilicity, antimicrobial activity and deodorization can be obtained through the heat exchanger.

However, the technique disclosed in the above publication is to deposit a titanium oxide thin film on the fin of the heat exchanger in a state in which the fin is mounted on the tube to form a heat exchanger, so that a thin film of uniform thickness cannot be expected on the entire surface of the fin. Hydrophilicity and aging characteristics are poor, and also there is a problem that does not guarantee the productivity enough to be directly applied to industrial production.

Accordingly, an object of the present invention is to provide a superhydrophilic and bactericidal / antimicrobial metal product having excellent hydrophilicity and aging characteristics, and excellent corrosion resistance and antibacterial and antimicrobial properties, and a method for producing the same.

In addition, the present invention forms a thin film having corrosion resistance, superhydrophilicity, and / or antibacterial properties on a sheet-shaped metal base material, and then mechanically processes the metal base material into a desired shape to easily form a superhydrophilic thin film on an industrial production scale. It aims to produce.

In addition, an object of the present invention is to uniformly form a thin film having effective superhydrophilicity and / or bactericidal and antibacterial properties on both surfaces of a sheet metal base material.

In addition, an object of the present invention is to form a thin film having excellent antibacterial and antibacterial properties on a metal material for refrigeration and air conditioning without additional post treatment or pretreatment.

The present invention for achieving the above object, the super-hydrophilic and bactericidal / antimicrobial metal product, characterized in that the super-hydrophilic and antibacterial Ti- (Ag, Cu and / or Co) compound thin film is coated on both sides of the base material In providing. The compound thin film may be a compound thin film of any one of Ti-Ag-O-based, Ti-Cu-O-based, Ti-Co-O, and Ti-Ag-Cu-Co-O-based compounds. The compound thin film contains, in atomic%, 15 to 22% of Ti, 3 to 10% of Ag, 3 to 10% of Cu, 3 to 10% of Co, and 45 to 65% of O. Preferably, the compound thin film is additionally a thin film containing the C and / or H component. In addition, the compound thin film is, in atomic%, 15 to 22% of Ti, 3 to 10% of Ag and / or 3 to 10% of Cu, 3 to 10% of Co, and 45 to 65% of O And, additionally, 20 to 25% C and / or 20 to 25% H. In addition, a corrosion-resistant thin film is further coated between the base material and the Ti- (Ag, Cu and / or Co) compound thin film, the corrosion-resistant thin film is characterized in that the Si-O-based compound thin film.

Further, the corrosion resistant thin film preferably contains 20 to 25% Si and 45 to 65% O in atomic%. In addition, the thin film is characterized in that the coating using a plasma, the total thickness of the thin film is characterized in that 1 to 200nm, the metal base material is characterized in that the aluminum base material. In addition, the metal sheet coated with the thin film may be machined into a desired shape.

In addition, the present invention, by continuously coating a thin film of Ti- (Ag, Cu and / or Co) compound having superhydrophilicity and antimicrobial by using a plasma on both sides of the sheet-shaped metal base material continuously supplied in the vacuum chamber, The present invention provides a method for producing a superhydrophilic and antibacterial / antimicrobial metal product characterized by machining a sheet coated with a thin film to a desired shape. In addition, the compound thin film is preferably a compound thin film of one of the Ti-Ag-O-based, Ti-Cu-O-based, Ti-Co-O-based, Ti-Ag-Cu-Co-O-based compound. The compound thin film is preferably a thin film containing C and / or H.

In addition, the coating of the compound thin film is preferably performed by introducing a reactive gas, a vapor phase titanium precursor, a vapor phase silver precursor, a vapor phase cobalt precursor and / or a vapor phase copper precursor, and a carrier gas into the vacuum chamber. The vapor phase silver precursor and / or vapor phase copper precursor and the introduction amount of the carrier gas satisfy the ranges of 100 to 200 sccm and 100 to 200 sccm, respectively, and the introduction ratio of the gases is carrier gas: vapor phase silver precursor and / or Or a gaseous copper precursor = 1: 1 to 1: 2.

In addition, before continuously coating the Ti- (Ag, Cu, and / or Co) compound thin film, continuously coating the corrosion resistant thin film by using a plasma in a vacuum chamber on both sides of the sheet-shaped metal base material continuously supplied. Preferably, the corrosion-resistant thin film is characterized in that the Si-O-based compound. In addition, the coating of the corrosion resistant thin film is characterized in that it is carried out by introducing a reactive gas, a gaseous silicon precursor and a carrier gas into the vacuum chamber. In addition, the introduction ratio of the reactive gas and the carrier gas is preferably in the range of 1: 10 to 1: 20. In addition, the introduction ratio of the carrier gas and the vapor phase silicon precursor may satisfy the range of 1: 1 to 1: 2.

In addition, the reactive gas is preferably air or O ₂ , the carrier gas is preferably at least one selected from the group consisting of He, N ₂ , Ar, the total thickness of the corrosion-resistant thin film and titanium compound thin film is 1 to 200nm. It is characterized by.

In addition, the metal base material is characterized in that the aluminum base material, the metal product is characterized in that the fin for the heat exchanger.

DETAILED DESCRIPTION Hereinafter, embodiments of the present invention in which the above object can be specifically realized are described with reference to the accompanying drawings.

1 and 2 is a preferred embodiment of a plasma polymerization apparatus for coating a thin film of Ti- (Ag, Cu and / or Co) -OC compound having superhydrophilicity and antibacterial property on a sheet-shaped metal base material according to the present invention. An example is shown. The structure of the apparatus is first connected to the coating chamber 2 is connected to a vacuum pump (not shown) for forming a vacuum in the chamber 2, and the metal sheet continuously between the electrodes 6 installed in both up, down, left and right sides (8) is supplied. Here, as illustrated in FIG. 1, an example in which the electrode 6 is provided above and below the metal sheet 8 and the metal sheet 8 is horizontally supplied will be described. After the thin film of Ti- (Ag, Cu and / or Co) -OC compound having superhydrophilicity and antibacterial property was continuously coated on both surfaces of the metal sheet 8 by the plasma generated between the electrodes, the metal sheet 8 is discharged from the coating chamber 2. The power source 10 is applied to the electrode 6.

In addition, a reactive gas is introduced into the coating chamber through the valve 22 from the reactive gas cylinder 20, which preferably contains a reactive gas which may be air or oxygen.

Here, the component which corresponds to silver and copper or cobalt precursor which are coat | coated so that it may have antimicrobial activity was shown by attaching "b" to the reference number.

Further, a liquid phase of titanium tetraisopropoxide [Ti (OC ₃ H ₇ ) ₄ ] in a liquid state contained in the receiving containers 30 and 30b pressurized by the pressurizing portions 32 and 32b. Titanium precursor or liquid silver, copper or cobalt precursor are introduced into the same vaporizer 40 by the pressure difference through the liquid mass flow controller (MFC) 38, 38b, and vaporized titanium vaporized through the vaporizer 40 Precursors and vapor phase silver, copper or cobalt precursors are also introduced into the coating chamber 2.

At this time, a piping gas between the liquid MFC 38 and the vaporizer 40, preferably carrier gas, which may be helium, argon and nitrogen, is introduced to help introduce the vapor phase titanium precursor into the coating chamber 2 later. All. This carrier gas is accommodated in the carrier gas cylinder 50 and is introduced into the pipe via a separate valve 52. The vaporizer 40 has a structure in which the heater coil 42 is wrapped around the liquid titanium precursor and the liquid silver, copper or cobalt precursor to be vaporized by heating (80 ° C. to 120 ° C.).

Here, the ratio of introduction of the reactive gas and the carrier gas into the coating chamber 2 is preferably about 3: 1, and the ratio of introduction of the carrier gas and the gaseous precursor is about 1: 3.

In addition, the introduction ratio of the carrier gas and the gaseous phase silver, copper or cobalt precursor introduced into the coating chamber 2 is preferably about 1: 1.

At this time, the reactive gas, gaseous titanium precursor or gaseous silver, copper or cobalt precursor and the carrier gas are laminated outside the coating chamber 2 as shown in the figure, and the coating chamber 2 through one pipe 60. It may be introduced into the interior, or may be introduced into the coating chamber 2 through a separate pipe, and then laminated into one pipe inside the coating chamber 2. Although the laminated pipe 60 is shown in a shape introduced through one hole of the coating chamber 2 in FIG. 1, directly and directly below the metal sheet 8 coated with the mixed gas introduced through the pipe 60. It is preferable to discharge the

However, since the vapor phase titanium precursor or vapor phase silver, copper or cobalt precursor is condensed at low temperature, the vapor phase titanium precursor or vapor phase silver, copper or cobalt precursor condenses on the inner wall of the pipe 60 when the pipe 60 is maintained at room temperature. There is a problem. Therefore, in order to prevent condensation of the copper or cobalt precursor, the vapor phase titanium precursor or the vapor phase silver is wound around the outer wall of the pipe through which the vapor phase titanium precursor gas flows and maintained at a predetermined temperature (80 ° C to 120 ° C) or more. It is good to let. This also applies to piping in a region in which liquid titanium or liquid silver flows through copper or cobalt precursor. The heating wire is also wound around the outer wall of the pipe to maintain a temperature above a predetermined temperature to prevent condensation of titanium, silver, copper or cobalt precursor on the inner wall of the pipe.

The present invention relates to Ti- (Ag, Cu and / or Co) -OC having superhydrophilicity and bactericidal and antimicrobial properties by using a plasma on a metal sheet 8 continuously supplied into the vacuum chamber 2 having the above-described configuration. The system compound thin film is continuously coated, and the metal sheet coated with the thin film is machined into a desired shape, and as an example, a fin of a refrigeration and air conditioning heat exchanger is manufactured.

In addition, the liquid is added to give the thin film and antibacterial, it can be divided into the structure of Figures 1 and 2 depending on how the copper or cobalt precursor is introduced into the vaporizer in relation to the liquid titanium precursor. First, in the structure of FIG. 1, the MFC 38 for the liquid titanium precursor and the MFC 38b for the liquid silver, copper, or cobalt precursor are separately formed, and the liquid precursors passing through the gas flow through a separate pipe and then pass through the vaporizer. Vaporized and then introduced into the vacuum chamber. Alternatively, since both are in liquid form, it may be configured to pass through one MFC 38 and then be introduced into the vaporizer, as shown in FIG. 2.

However, although the configuration of FIGS. 1 and 2 assumes that only one precursor such as silver, copper or cobalt is introduced, it is also possible to introduce one or more of these precursors. In this case, since only the container and pipe configuration for introducing them, those skilled in the art will be able to easily introduce a plurality of precursor gases while using the above construction principles.

The present invention relates to Ti- (Ag, Cu and / or Co) -OC having superhydrophilicity and bactericidal and antimicrobial properties by using a plasma on a metal sheet 8 continuously supplied into the vacuum chamber 2 having the above-described configuration. A compound thin film is continuously coated, and the metal sheet coated with the thin film is machined into a desired shape to produce fins of a heat exchanger for refrigeration and air conditioning.

On the other hand, Figure 3 shows another embodiment of a plasma polymerization apparatus for producing a superhydrophilic and bactericidal / antibacterial metal sheet in accordance with the present invention. In the case of using the plasma polymerizer configuration of FIG. 3, first, the corrosion-resistant Si-O-based compound thin film is successively coated on both sides of the sheet-shaped metal base material, and then the superhydrophilic Ti- is coated on both sides of the sheet-shaped metal base material coated with the corrosion-resistant thin film. The (Ag, Cu and / or Co) -OC compound thin film can be continuously coated. The polymerization apparatus is characterized in that after coating a corrosion-resistant thin film layer on a sheet-shaped metal base material, and subsequently coating a super hydrophilic and antibacterial thin film layer, by dividing the coating chamber (2) in two and coating the corrosion resistant thin film first, The above-described configuration of the polymerization apparatus is employed as it is, except that the superhydrophilic and antibacterial thin film is coated. Therefore, the same reference numerals are given to the same apparatus. In addition, since the structure for forming the corrosion-resistant thin film also corresponds similarly to the structure for forming the superhydrophilic and bactericidal / antimicrobial thin film, the same reference numerals are added to the same reference numerals.

First, the coating chamber 2 is connected with a vacuum pump not shown in the drawing for forming a vacuum in the chamber. As shown in FIG. 3, a metal sheet 8 is continuously provided between the electrodes 6 disposed up and down. Supplied. After the corrosion resistant thin film is continuously coated on both sides of the metal sheet 8 by the plasma generated between the electrodes, and then the superhydrophilic and antibacterial thin film is continuously coated, the metal sheet 8 is coated with a coating chamber ( From 2). Power sources 10 and 10a are applied to the electrodes 6 and 6a.

In addition, the reactive gas is introduced into the coating chamber 2 through the valves 22 and 22a from the reactive gas cylinders 20 and 20a, which preferably contain the reactive gas which may be air or oxygen.

In addition, a liquid phase of titanium tetraisopropoxide [Ti (OC ₃ H ₇ ) ₄ ] in a liquid state contained in the receiving containers 30 and 30a pressurized by the pressurizing portions 32 and 32a. The titanium precursor and the liquid silver, the copper or cobalt precursor and the liquid silicon precursor, HMDSO in the liquid state, are introduced into the vaporizers 40 and 40a by the pressure difference through the liquid mass flow controllers 38, 38a and 38b. Vapor phase titanium precursor and vaporized silver, copper or cobalt precursor and vapor phase silicon precursor vaporized via vaporizers 40 and 40a are also introduced into the coating chamber 2. At this time, a carrier gas, which may be helium, argon and nitrogen, is introduced into the piping between the liquid MFCs 38 and 38a and the vaporizers 40 and 40a. , Copper or cobalt precursors are introduced into the coating chamber (2). These carrier gases are accommodated in the carrier gas cylinders 50 and 50a and are introduced into the pipe via separate valves 52 and 52a. The vaporizers 40 and 40a are provided with heater coils 42 and 42a wrapped around them so as to vaporize the liquid titanium precursor, the liquid silver, copper or cobalt precursor, and the liquid silicon precursor by heating (80 ° C. to 120 ° C.). Has a structure.

Here, the introduction ratio of the gases introduced into the coating chamber 2 for coating the corrosion resistant thin film ranges from 1: 10 to 1: 20 of the reactive gas and the carrier gas, and 1 of the carrier gas and the silicon precursor. It is preferable to achieve the range of 1: 1: 1.

At this time, the reactive gas, gaseous titanium, gaseous silver, copper or cobalt precursor or silicon precursor and carrier gas are laminated outside the coating chamber 2 as shown in the drawing through the one pipe (60, 60a) (2) It may be introduced inside, or may be introduced into the coating chamber 2 through a separate pipe, and then laminated into one pipe in the coating chamber 2. 3 shows that the laminated pipes 60 and 60a are introduced through one hole of the coating chamber 2, but the metal sheet 8 coated with the mixed gas introduced through the pipes 60 and 60a is shown. It is preferable to discharge directly above and directly below.

However, since the vapor phase titanium precursor or the vapor phase silver, the copper or cobalt precursor and the silicon precursor are condensed at a low temperature, when the pipes 60 and 60a are kept at room temperature, the vapor phase titanium or silicon precursors are formed on the inner wall of the pipes 60 and 60a. There is a problem of condensation. Therefore, in order to prevent condensation of the vapor phase titanium or silicon precursor, it is preferable to wind the heating wires 64 and 64a on the outer wall of the pipe through which the vapor phase titanium precursor gas flows and maintain the temperature above a predetermined temperature (80 ° C to 120 ° C). . The same applies to the pipes 66 and 66a in the region where the liquid titanium or silicon precursor flows. Heat wires 68 and 68a are also wound around the outer walls of the pipes 66 and 66a to maintain a temperature higher than a predetermined temperature to prevent condensation of titanium precursors or silver, copper or cobalt precursors and silicon precursors on the inner walls of the pipes 66 and 66a. .

For the convenience of explanation, the above-described configuration is an example of coating a super hydrophilic and antibacterial thin film immediately after coating a corrosion resistant thin film, but in some cases after performing a process of coating the corrosion resistant thin film on a metal sheet (that is, It is also possible to uncoil the sheet, coat the corrosion-resistant thin film and roll the sheet back into a roll), and to coat the superhydrophilic and antibacterial thin film by a separate process (in this case it is possible to use one chamber). Will be). In addition, it may be possible to configure after installing the intermediate medium (for cooling process, etc.) between the separate chambers without continuously installing as described above.

The present invention first coats the corrosion-resistant Si-O-based compound thin film by using a plasma on the metal sheet 8 continuously supplied into the vacuum chamber 2 having the above-described configuration, and then the metal having the corrosion-resistant thin film coated thereon. A superhydrophilic and bactericidal / antibacterial thin film is successively coated using plasma on the sheet, and the metal sheet coated with the thin film is machined into a desired shape to produce fins of a heat exchanger for refrigeration and air conditioning as an example.

Using a plasma polymerization apparatus having the above configuration, a metal sheet having superhydrophilicity and bactericidal and antibacterial properties was produced. These were machined into heat exchanger fin shapes as described above and their physical and surface properties were measured. This is illustrated in the description of the preferred embodiments below. However, the scope of the present invention should not be limited by the description of the embodiments described below, and the scope of the present invention will be limited only by the description of the claims which will be described later.

Example

plasma Of coating film  Produce

After forming a vacuum at 0.001 to 0.5 Torr (10 ^-3 Torr in this embodiment) by using a vacuum pump in the vacuum chamber 2, the metal sheet 8 is connected to the anode and the electrode 6 And a constant distance (30 to 150 mm), the heater coil 42 of the vaporizer was energized by heating (80 ℃ ~ 120 ℃) to vaporize the liquid precursor. The heating wire wound on the outer walls of the pipes 60 and 66 was also energized and heated (80 ° C. to 120 ° C.) to prevent the vapor phase precursor from condensing on the pipe inner wall. The gaseous precursor gas, the carrier gas and the reactive gas were introduced into the vacuum chamber 2 through the piping and discharged directly above and directly below the metal sheet 8. When the desired working vacuum degree is obtained by the injected gas, the power is turned "ON" to the mixed gases between the electrodes 6 continuously formed in the flow direction of the metal sheet 8 with respect to the pipe 60. Plasma was formed. Accordingly, superhydrophilic Ti-OC compound thin films, Ti-Si-OC compound thin films, Ti-Co-OC compound thin films, and Ti-Si-Co-OC compound thin films were coated on both surfaces of the metal sheet 6.

In the plasma treatment, the current ranged from 0.1 to 0.5 A, the flow rate of the carrier gas of helium or argon and nitrogen gas was 30 to 100 sccm, the flow rate of the reactive gas of oxygen or air was 30 to 100 sccm, and the vacuum degree in the chamber during plasma treatment. Was maintained at 0.2 to 0.5 Torr.

Composition and Thickness Analysis of Coated Thin Films

The composition of the treated thin film sample was analyzed by X-ray photoelectric spectroscopy (XPS), which infers the surface composition by measuring molecular specific absorption and emission wavelengths using X-rays, and the thickness was sputtered at a fixed speed. The composition was analyzed by AES (Atomic Emission Spectrometry). The results are shown in FIGS. 4 to 5.

4 is XPS data when the HMDSO corrosion resistant thin film is first formed and then the titanium compound thin film is formed. In atomic%, 19.4% C, 58.3% O, 2.5% Si, 19.8% Ti were analyzed. It was confirmed that the obtained compound thin film was a Ti-Si-O-C compound thin film.

5 is XPS data when a thin film containing a Co component is formed. In atomic%, 18.3% C, 59.1% O, 18.9% Ti, and 3.7% Co were analyzed. It was confirmed that the obtained compound thin film was a Ti-Co-O-C compound thin film.

Although not shown in the drawings, when only the superhydrophilic compound thin film was coated, a Ti-OC-based thin film was obtained, and after forming a corrosion resistant thin film, and then forming a thin film containing a Co component to impart antibacterial and antibacterial properties, A Ti-Si-Co-OC based thin film was obtained.

That is, as a result of the analysis, there was a slight difference depending on the conditions, the titanium compound thin film according to the present invention is commonly 15 to 22 atomic% Ti, 45 to 65 atomic% O, 20 to 25 atomic% C and / Or H, 20 to 25 atomic% Si and 3 to 10% Co. As described above, the Si component was analyzed when the corrosion resistant thin film was first coated, and these components were analyzed when silver, copper or cobalt were coated together to impart antibacterial and antibacterial properties.

In addition, according to the present embodiment, the total thicknesses of the corrosion resistant thin film, the superhydrophilic thin film, and the bactericidal / antibacterial thin film coated on the surface of the metal sheet were 1 to 200 nm by AES measurement data analyzing the composition according to the depth while sputtering at a fixed speed. appear.

6A and 6B show scanning electron microscope (SEM) images of the Ti-O-C-based compound thin film and the Ti-Co-O-C-based compound thin film according to the present invention, respectively. It can be confirmed that both of them obtained very dense thin films.

Evaluation of Corrosion Resistance of Thin Films

Corrosion resistance was in accordance with the Salt Spray Test according to KS D9502, which is a method for evaluating the corrosion resistance of metal materials or metal materials applied with plating, inorganic coating and organic coating. The salt concentration was 5 ± 1% and the temperature was 35 ± 2 ° C. Corrosion resistance was evaluated by visual observation.

Table 1. Evaluation of corrosion resistance by salt spray test

As can be seen from Table 1, in the case of the uncoated Bare Al sheet exhibited a front corrosion in each salt spray condition, it was confirmed that the corrosion resistance is very poor, the conventional PCM (Pre Coated Metal) employing a wet coating ) Also found that the number of corrosion defects as shown in the table, respectively, it was confirmed that they have a good corrosion resistance compared. However, in the case of the aluminum sheet coated with the Ti compound thin film according to the present invention, it was confirmed that the corrosion resistance is very excellent, and furthermore, after forming the HMDSO coating layer before coating the Ti compound thin film, and coating the titanium compound thin film thereon It was confirmed that it has extremely excellent corrosion resistance.

7A and 7B show surface photographs after 15 days of a salt spray test for sheets having Bare Al sheets and HMDSO + Ti compound thin films, respectively. As can be seen from the figure, the front surface corrosion occurred in the Bare Al sheet, the sheet formed with a thin film according to the present invention showed an extremely excellent corrosion resistance characteristics of less than 10 pitting (pitting) number.

Hydrophilicity of thin films and Aging  characteristic

Hydrophilicity evaluation was done by dropping a quantitative (0.1 cc) drop of water at a height of 10 mm to measure the drop size on the sample surface. The better the hydrophilicity, the better the droplet's spread, and the larger the droplet's size. The hydrophobic, the smaller the droplet's spread, the smaller the droplet size. Figure 8a shows the shape of the water droplets on the surface having a hydrophilic water droplet size corresponds to 9 ~ 11 mm, Figure 8b shows the shape of the water droplets on the hydrophobic surface corresponding to the water droplet size is 2 to 3 mm.

In addition, the hydrophilic performance after 300 cycles is compared with the initial hydrophilicity by repeatedly treating the treated specimen with distilled water for 10 minutes immersion / 10 minutes to evaluate the aging characteristics of hydrophilicity.

9 shows the experimental results described above. Although the thin film according to the present invention treated by plasma after 300 cycles of acceleration has no change in hydrophilic performance, the conventional PCM has excellent initial hydrophilic performance but it can be seen that the hydrophilic performance is degraded and aged as the hydrophilic surfactant is dissolved in water. there was. Bare Al is initially hydrophobic, but upon acceleration, an Al ₂ O ₃ oxide layer is formed on the surface of aluminum, resulting in slightly improved hydrophilic performance.

10 shows yet another result of aging experiments for the titanium compound thin film and the conventional PCM thin film according to the present invention up to 1000 cycles. In the case of the thin film according to the present invention, the hydrophilic performance was insignificant and the hydrophilic performance (water droplet size of 9 mm or more) was maintained as it is, but in the case of the conventional PCM, it was confirmed that the hydrophilic performance deteriorated rapidly as the number of cycles increased.

Antimicrobial Properties of Thin Films

Antibacterial and bactericidal performance was evaluated by the film sticking method according to the standard FC-TM-20-2003 to the antimicrobial and sterilization rate of Staphylococcus aureus and Escherichia coli.

The evaluation results for Staphylococcus are shown in FIG. 11, and the evaluation results for Escherichia coli are shown in FIG. Both the Staphylococcus aureus and Escherichia coli in the film had an initial cell count of 1.8 X 10 ^5, but after 24 hours, the film was adhered to the Ti-Co-OC compound thin film coated metal sheet according to the present invention. The antimicrobial and sterilization rates were less than 10 for all, and the antimicrobial and sterilization rates were 99.9% or more, which showed extremely good sterilization and antibacterial properties. Similar results were obtained when copper and silver were contained in addition to cobalt.

Table 2. Antimicrobial Test

In addition, Table 2 is a table showing the analysis of the antimicrobial properties of the thin film, the antimicrobial performance was evaluated by the film sticking method (film sticking method, standard: FC-TM-20-2001), in this experiment copper / antibacterial compound (Cu) compound was used.

As shown in Table 2, even when the titanium compound (Ti-OC) thin film according to the present invention was irradiated with UV, excellent antibacterial properties were obtained, but in the case of containing cobalt, copper or silver according to the present invention, UV irradiation Without this extremely good bactericidal and antibacterial properties were obtained.

According to the present invention, it is possible to easily produce a refrigeration and air conditioning metal material having a thin film having excellent hydrophilic performance and aging characteristics and excellent corrosion resistance and antibacterial and antibacterial properties on an industrial production scale.

In addition, according to the present invention, a thin film having effective superhydrophilicity and / or bactericidal and antimicrobial properties can be uniformly formed on both surfaces of a sheet metal base material. In addition, according to the present invention it is possible to form a thin film excellent in antibacterial and antibacterial to the metal material for refrigeration and air conditioning without a separate post treatment or pretreatment such as UV treatment.

The features and advantages of the present invention may be better understood with reference to the following accompanying drawings in conjunction with the following detailed description of embodiments of the invention, of which:

1 is a conceptual diagram showing an example of an apparatus for continuously coating a super-hydrophilic and antibacterial titanium-cobalt thin film on a sheet-shaped metal base material using a plasma in accordance with an embodiment of the present invention.

FIG. 2 is a conceptual view illustrating another example of an apparatus for continuously coating a superhydrophilic and antibacterial titanium-cobalt thin film on a sheet-shaped metal base material using plasma according to another embodiment of the present invention.

3 is a coating of a corrosion-resistant thin film on a sheet-shaped metal base material continuously using a plasma according to another embodiment of the present invention, and then a superhydrophilic and antimicrobial compound thin film on the sheet-shaped metal base material using a plasma A conceptual diagram showing a device for continuous coating.

4 is XPS data for analyzing the surface composition of a metal sheet coated with a corrosion resistant and superhydrophilic thin film according to the present invention.

5 is XPS data for analyzing the surface composition of a metal sheet coated with a superhydrophilic and antibacterial thin film according to the present invention.

6A and 6B are scanning electron microscope (SEM) photographs showing microstructures of a titanium compound thin film and a titanium-cobalt compound thin film coated according to an embodiment of the present invention, respectively.

7a and 7b are photographs showing the surface state after 15 days after the salt spray test for the Bare Al sheet and the sheet coated with corrosion resistance and superhydrophilic thin film according to the present invention.

8A and 8B are photographs showing the degree of spreading of water droplets when the surface has hydrophilicity (FIG. 11A) and when the surface has hydrophobicity (FIG. 11B) in a test for evaluating hydrophilicity / hydrophobicity of the surface. .

9 is a graph showing the aging characteristics of a Bare Al sheet, a conventional PCM sheet, and a sheet coated with a titanium compound thin film according to the present invention.

10 is another graph showing aging characteristics of a sheet coated with a titanium compound thin film according to the present invention and a conventional PCM sheet.

11 is a film adhesion test results showing the bactericidal and antimicrobial properties of staphylococcus aureus against the titanium-cobalt compound thin film according to the present invention.

12 is a film adhesion test results showing the bactericidal and antimicrobial properties of E. coli against the titanium-cobalt compound thin film according to the present invention.

Claims (9)

Si-O- (coated on the substrate, containing 20-25% Si, 45-65% O, and the remainder consisting of at least one of C and H and inevitable impurities C)-(H) type corrosion resistant thin film, 3 to 10% Ag, 3 to 10% Cu, 3 to 10%, containing 15 to 22% Ti and 45 to 65% O, in atomic%, coated on the corrosion resistant thin film Ti- (Ag, Cu, Co) -O- (C)-containing any one element selected from the group consisting of Co and containing the remainder composed of at least one of C and H and inevitable impurities Corrosion-resistant, superhydrophilic and antibacterial metal products comprising (H) superhydrophilic and antimicrobial compound thin films. The method of claim 1, The compound thin film is a Ti-Ag-O- (C)-(H) -based, Ti-Cu-O- (C)-(H) -based, Ti-Co-O- (C)-(H) -based compounds A corrosion resistant, superhydrophilic and bactericidal / antibacterial metal product, characterized in that it is one compound thin film. The method according to claim 1 or 2, The corrosion resistant thin film and the compound thin film are corrosion-resistant, super hydrophilic and bactericidal / antibacterial metal product, characterized in that the coating on the metal base material by using a plasma. The method of claim 3, Corrosion resistance, super hydrophilic and bactericidal / antibacterial metal product, characterized in that the total thickness of the thin film is 1 to 200 nm. The method of claim 3, Corrosion resistance, super hydrophilic and bactericidal / antibacterial metal product, characterized in that the metal base material is an aluminum base material. The method of claim 5, The aluminum base material coated with the thin film in sequence has a sheet shape, and can be machined to a desired shape. delete delete delete

Images