JP5017638B2 - Method for producing antibacterial Sn-Cu alloy thin film formed article and antibacterial Sn-Cu alloy thin film formed article produced thereby - Google Patents

Description

  TECHNICAL FIELD The present invention relates to a Sn—Cu alloy thin film, a Sn—Cu alloy thin film formed product, and a method for producing a Sn—Cu alloy thin film formed product. More specifically, the present invention relates to an antibacterial Sn—Cu alloy thin film, an antibacterial Sn—Cu alloy thin film formed product, and a method for producing an antibacterial Sn—Cu alloy thin film formed product.

  Thin films such as tin plating are widely used to coat metal utensils for cooking for food processing, but tin plating itself does not have a clear antibacterial property against bacteria. Therefore, it is not possible to prevent transmission of Klebsiella pneumoniae to the elderly who are likely to occur in hospitals.

  In the case of processing food, contamination by various bacteria such as Staphylococcus aureus and pathogenic Escherichia coli O-157 and food poisoning caused thereby are important problems. Therefore, it is required to impart antibacterial properties to thin films such as tin plating.

In order to impart antibacterial properties to tin plating, conventionally, for example, means for applying an antibacterial agent on tin plating is generally used.
In addition, for example, Patent Document 1 discloses an invention in which an antibacterial metal fine powder is added to a tin plating film.

However, even if antibacterial properties are imparted by these means, there is a problem that the effect is not remarkably improved.
In addition, when an antibacterial metal fine powder is added to the tin plating film, there is a problem that the process of producing the product becomes complicated due to the addition process.

On the other hand, as described in Patent Document 2, for example, one of techniques for coating the surface of a metal product is “alloy plating”.
The alloy plating technique usually involves forming an alloy plating thin film by performing simultaneous electrodeposition (alloy electrodeposition) from an aqueous solution. That is, in this alloy plating, an alloy plating thin film is formed by a single operation by simultaneously depositing different types of constituent elements from an aqueous solution on the substrate surface.

  And, some metal elements such as copper, silver, zinc, nickel, lead, cadmium, chromium, palladium, bismuth, etc. may generate a complex complex or a compound ion under certain conditions. Depending on the situation, there are those that change the growth environment of Staphylococcus aureus, Escherichia coli, Neisseria pneumoniae, etc. to an unfavorable state.

Therefore, when performing alloy plating on the base material, it seems that the use of one or more of these metal elements can provide the alloy plating itself with antibacterial properties. Moreover, if such an alloy plating can be realized, not only a special antibacterial treatment is unnecessary after electrodeposition of the plating, but also the production process can be simplified, which is very useful industrially. It seems to be.
JP-A-6-16509 (Claim 3, paragraphs 0012 to 0015, Table 1) JP-A-2005-139474 (Claims 1 to 3, paragraphs 0015 to 0029, FIGS. 1 and 2)

However, since such alloy plating has the following problems, it is extremely complicated and difficult to put into practical use. (1) Electrodeposition of two different metals must be performed at the same potential, (2) Metals that can be used for alloy plating are limited, (3) Chemical species used in the plating bath are cyan-type poisons, The use of deleterious substances, strong acidic solutions, and strong alkaline solutions is often used, and the environmental load is high.
Moreover, (4) S. aureus, Escherichia coli, K. pneumoniae, etc. are permeable to many metals, and there are not many metals that can sterilize these metals. (5) Alloy plating produced by alloy electrodeposition (6) The alloy plating formed by electrodeposition from an aqueous solution may be thermally non-equilibrium and may be altered when used by heating. is there.

  The present invention has been made in view of the above problems, and it is possible to implement an Sn-Cu alloy thin film having excellent antibacterial properties while being inexpensive, and an Sn-Cu alloy thin film having antibacterial properties applied thereto. It is an object of the present invention to provide a method for manufacturing a formed product of Sn—Cu alloy thin film having antibacterial properties reliably and easily under conditions where the environmental load is not high.

The method for producing an antibacterial Sn—Cu alloy thin film-formed product of the present invention that has solved the above problems includes a Cu layer forming step of forming a Cu layer having a layer thickness of 1 to 50 μm on a base material, and a Cu layer. above, the Sn layer forming step of forming a Sn layer having a thickness of 1 to 50 [mu] m, Cu layer and the Sn layer 250 to 400 ° C. the formed substrate was heated under the conditions of 1 to 5 hours, the content of Cu Is an alloy thin film forming step of forming an alloy thin film of Sn and Cu , in which at least one of Cu ₆ Sn ₅ and Cu ₃ Sn is formed , and is heated to form an alloy thin film And cooling the formed base material at a rate of 400 ° C./hour to 50 ° C./minute to form a Sn—Cu alloy thin film-formed product.

Thus, the Cu layer forming step and the Sn layer formation step, to form a Cu layer and a Sn layer of suitable thickness on the matrix of the base material, softened and the Cu layer and the Sn layer by alloy thin film forming step it can be melted to form a alloy thin film. Further, to produce a _Cu 6 Sn ₅ and _Cu 3 Sn by heating in alloy thin film forming step. And a Sn-Cu alloy thin film formation article can be manufactured only by cooling the substrate at an appropriate cooling rate. As a result, the Sn—Cu alloy thin film-formed product manufactured in this way has antibacterial properties because it contains Cu ₆ Sn ₅ and Cu ₃ Sn.
Here, the “alloy thin film” in the present specification refers to a thin film that is alloyed by heat treatment or the like by previously laminating a plurality of different elements and compounds. Here, for example, a thin film obtained by laminating a plurality of layers by plating and then heat-treating it is called an “alloyed plating thin film”, which is obtained by simultaneous electrodeposition as described above. Is different. The same applies to Sn-Cu heat-treated alloyed sputtered thin films and Sn-Cu heat-treated alloyed evaporated thin films.
With such an alloy thin film, Cu ₆ Sn ₅ and Cu ₃ Sn are contained in the alloy thin film, so that the growth environment of Staphylococcus aureus, Escherichia coli, Klebsiella pneumoniae and the like can be changed to an inconvenient state. .

In the method for producing an antibacterial Sn—Cu alloy thin film formed product of the present invention, the Cu layer forming step and the Sn layer forming step are each laminated as a single layer by plating, sputtering, or vapor deposition. Is good.
Thus, Cu layer and Sn layer of appropriate thickness can be easily formed by making Cu layer formation process and Sn layer formation process into plating processing, sputtering processing, or vapor deposition processing. In particular, in the case of plating, since each is formed as a single layer under general conditions, the Cu layer and the Sn layer can be formed without using chemicals with high environmental impact. Similarly, in the case of sputtering or vapor deposition, the Cu layer and the Sn layer can be formed without using chemicals with a high environmental load .

According to the present invention, since a Sn—Cu alloy thin film is formed using tin (Sn) and copper (Cu), there is provided a method for producing a Sn—Cu alloy thin film formed article having excellent antibacterial properties while being inexpensive. Can be provided.
ADVANTAGE OF THE INVENTION According to this invention, the method of manufacturing the Sn-Cu alloy thin film formation goods which have antibacterial property reliably and easily on the conditions where environmental load is not high can be provided .

First, the antibacterial Sn—Cu alloy thin film according to the present invention will be described.
[Sn—Cu alloy thin film]
In the Sn—Cu alloy thin film of the present invention, the content ratio of Sn (tin element) and Cu (copper element) contained in the outermost alloy thin film formed on the substrate is 100−x [atomic%]. X [atomic%], and the alloy thin film has 1 to 10 [mass%] SnO ₂ .
However, in the above content ratio, “x” is the Cu content, and 10 ≦ x ≦ 90, preferably 20 ≦ x ≦ 80, more preferably 30 ≦ x ≦ 70, and even more preferably 40 ≦ x ≦. 60.

Here, as described above, the content ratio of Sn and Cu is 100−x [atomic%]: x [atomic%], that is, the content ratio of Sn and Cu is 90 [atomic%]: 10 [atomic%] ˜ The reason for setting 10 [atomic%]: 90 [atomic%] is to produce the necessary amount of Cu ₆ Sn ₅ and Cu ₃ Sn and SnO ₂ to have antibacterial properties in the alloy thin film. .

When the Cu content is less than 10 [atomic%], Cu is too small, so that a sufficient amount of Cu ₆ Sn ₅ and Cu ₃ Sn cannot be generated. Therefore, the amount of Cu ²⁺ generated is reduced, and the desired antibacterial property may not be obtained.
On the other hand, when the Cu content exceeds 90 [atomic%], since there is too much Cu, the Sn—Cu alloy thin film cannot be produced at low cost.

  The content ratio of Sn and Cu can be adjusted by appropriately changing various conditions such as the concentration, temperature, current, and voltage of the solution used when forming the Sn—Cu alloy thin film.

Then, Cu to Sn-Cu alloy thin film of the present invention is contained in, which forms at least one of Cu ₆ Sn ₅ and Cu ₃ Sn, the total value of its formation rate, the Sn-Cu alloy thin film 10 to 100% of the amount of Cu contained.
That is, when the Cu content x [atomic%] satisfies 10 ≦ x ≦ 90 in the content ratio, Cu contained in the Sn—Cu alloy thin film is at least with respect to the entire Sn—Cu alloy thin film. 1 [atomic%] Cu forms Cu ₆ Sn ₅ and Cu ₃ Sn.
Thus, by defining the total value of the formation ratios of Cu ₆ Sn ₅ and Cu ₃ Sn formed by Cu contained in the alloy thin film to be within a specific range, the synergistic effect of these compounds enables yellow grape The growth environment can be changed to an unfavorable state with respect to bacteria such as cocci, Escherichia coli, and Klebsiella pneumoniae.

Note that Cu ₆ Sn ₅ and Cu ₃ Sn can produce Cu ²⁺ and have antibacterial properties as long as at least one of them is contained. Therefore, the content ratio of Cu ₆ Sn ₅ and Cu ₃ Sn is not particularly limited, and may be 0: 100 to 100: 0.

Further, when a large amount of SnO ₂ is contained, the surface becomes white. Therefore, the smaller the appearance, the better. If the content is 1 to 10% by mass, an excellent appearance can be obtained. On the other hand, if the content of SnO ₂ exceeds 10 [atomic%], the properties of the original Sn—Cu alloy thin film, particularly the appearance such as color tone, may be inferior.

As described above, when the Sn and Cu content ratios in the Sn—Cu alloy thin film and the total value of the formation ratios of Cu ₆ Sn ₅ and Cu ₃ Sn satisfy a specific range, the Sn ² Cu alloy thin film is formed from the Cu ^{2 +} Can be generated to obtain the effect of oligodynamics (Oligodynamie). In general, it is not easy to generate Cu ²⁺ from Cu ₆ Sn ₅ or Cu ₃ Sn, but it is suggested that Cu ²⁺ is likely to be locally generated when bacteria or the like come into contact with such a compound. ing. Further, it is considered that Cu ²⁺ is more easily generated by a potential difference generated between the Sn—Cu alloy thin film and Cu ₆ Sn ₅ or Cu ₃ Sn. By these actions and synergistic effects, it is possible to sterilize by reducing the activity of bacterial proteins or generating active oxygen that is a cytotoxin, and the Sn-Cu alloy thin film can have antibacterial properties. .

  In particular, as an Sn—Cu alloy thin film having such an action, an Sn—Cu heat-treated alloyed plating thin film formed by laminating a Cu layer and an Sn layer and performing a heat treatment at 200 to 400 ° C., Sn— A Cu heat-treated alloyed sputtered thin film or a Sn—Cu heat-treated alloyed vapor-deposited thin film is preferable. A means for obtaining such a Sn—Cu alloy thin film will be described later.

[Sn-Cu alloy thin film-formed product]
Next, the antibacterial Sn—Cu alloy thin film-formed product of the present invention will be described.
The antibacterial Sn—Cu alloy thin film-formed product of the present invention can be obtained by applying the above-described Sn—Cu alloy thin film to a substrate.
As a base material which coat | covers a Sn-Cu alloy thin film, what has electroconductivity and heat resistance is preferable, However, What does not have electroconductivity and heat resistance may be used. As such a base material, for example, steel lumber, aluminum lumber, aluminum alloy lumber, copper lumber, copper alloy lumber and other metal lumber can be suitably used, but is not limited thereto, for example, engineering plastics Plastic lumber, glass lumber, or a mixed lumber thereof can also be suitably used.

In addition, examples of Sn-Cu alloy thin film-formed products formed by these base materials and Sn-Cu alloy thin films include, for example, cooking utensils such as tableware, pans, sinks, triangular corners, door knobs, handrails, etc. Of course, it can be applied to articles that come into contact with water, water supply pipes and sewer pipes, and air conditioners such as air conditioners.
These Sn—Cu alloy thin film-formed products can be manufactured as follows.

[Method for producing Sn-Cu alloy thin film-formed product]
Next, the manufacturing method of the Sn-Cu alloy thin film formation product of this invention is demonstrated.
Sn-Cu method of manufacturing an alloy film formed article of the present invention comprise a Cu layer forming step, a Sn layer forming step, and alloy thin film forming step and a cooling step.
Hereinafter, the contents of each step will be described.

(Cu layer forming step)
In the Cu layer forming step, a Cu layer of 1 to 50 μm, preferably 1 to 20 μm, more preferably 1 to 10 μm is formed on the substrate substrate. If the Cu layer is formed with such a layer thickness, a Sn—Cu alloy thin film can be stably obtained.
Here, when the layer thickness of the Cu layer to be formed is less than 1 μm, the layer thickness is too thin, the mechanical strength of the formed Sn—Cu alloy thin film is weak, and may be easily peeled off. Absent. In addition, a sufficient amount of Cu ₆ Sn ₅ and Cu ₃ Sn may not be generated.
On the other hand, if the thickness of the Cu layer is larger than this, the dimensional accuracy of the product may be affected. In addition, since the production time becomes long in the film forming process, the industrial merit is lowered.
Therefore, in this invention, the layer thickness of Cu layer formed at a Cu layer formation process shall be 1-50 micrometers.

(Sn layer forming step)
In the Sn layer forming step, an Sn layer having a layer thickness of 1 to 50 μm, preferably 1 to 20 μm, more preferably 1 to 10 μm is further formed on the Cu layer. If the Sn layer is formed with such a layer thickness, a Sn—Cu alloy thin film can be stably obtained.
Here, if the thickness of the Sn layer to be formed is less than 1 μm, since the layer thickness is too thin, the mechanical strength of the formed Sn—Cu alloy thin film is weak and may be easily peeled off. Absent. In addition, a sufficient amount of Cu ₆ Sn ₅ and Cu ₃ Sn may not be generated.
On the other hand, if the Sn layer is too thick because the Sn layer is too thick, the dimensional accuracy of the product may be affected. In addition, since the production time becomes long in the film forming process, the industrial merit is lowered. Furthermore, there is also that you are SnO ₂ that is often generated, there is a possibility that poor appearance such as color tone.
Therefore, in the present invention, the thickness of the Sn layer formed in the Sn layer forming step is set to 1 to 50 μm.

  The means for forming the Cu layer and the Sn layer are not particularly limited as long as each can be formed as a single layer with a layer thickness within a predetermined range. As a means of forming these layers, a conventionally known plating process (reference: Nikkan Kogyo Shimbun, Ltd. Surface Treatment Engineering, Fundamentals and Applications, Surface Technology Association, ISBN4-526-04522-5 Latest Surface Treatment Technology Overview, Industrial Technology Service Center, ). Examples of such plating treatment include a wet plating method such as an electroplating method (electrolytic plating method) and a chemical plating method, or a dry plating method such as a hot dipping method. Such plating treatment is particularly preferable from the viewpoint of mass production without using chemicals or the like with high environmental load and at low cost. In particular, the electroplating method with simple condition control is preferable in that a cyanide compound is not used and a sulfur compound or a chloride compound can be used. In addition, it is also possible to plate with respect to the base material which does not have electroconductivity by the electroless-plating method.

Further, as another means for forming the Cu layer and the Sn layer, for example, it can also be performed by a conventionally known sputtering process or vapor deposition process (Reference: Nikkan Kogyo Shimbun, Ltd., Surface Treatment Engineering Fundamentals and Applications, ISBN4) -526-04522-5 Latest Surface Treatment Technology Overview Industrial Technology Service Center). Sputtering and vapor deposition are inferior to plating in terms of mass production, but are advantageous in that they do not use chemicals with high environmental impact.
Also, in the plating process, chemicals with a high environmental load must be used, so it is difficult to form alloy plating by simultaneous electrodeposition. On the other hand, in the sputtering process and the vapor deposition process, as described above, a chemical with a high environmental load is not used. Therefore, an alloy thin film can be formed by a single operation by simultaneous sputtering process or simultaneous vapor deposition process of Cu and Sn. Is possible.

(Alloy thin film formation process)
The alloy thin film forming step, a Cu layer and the Sn layer are sequentially formed substrate 250 to 400 ° C., it is heated under conditions of 1-5 hours. Softened and melted the Cu layer and the Sn layer by heating in such conditions, to form the alloy thin film of Sn and Cu.
That is, Cu ₆ Sn ₅ and Cu ₃ Sn are generated by reacting Cu (copper element) in the Cu layer with Sn (tin element) in the Sn layer. At this time, SnO ₂ is generated when it comes into contact with O ₂ in the atmosphere. For this purpose, for example, degassing and heating, or an inert gas atmosphere such as helium gas or argon gas are used. You may heat in. In this way, to ensure the content of SnO ₂ may be in the range of 1 to 10 [atomic%].

At this time, if or when the heating time the heating temperature is lower than 250 ° C. is less than 1 hour, there is a possibility that Cu layer and the Sn layer can not be formed alloy thin film not sufficiently softened and melted . Moreover, there is a possibility that a sufficient amount of Cu ₆ Sn ₅ and Cu ₃ Sn cannot be generated.
On the other hand, when the heating temperature exceeds 400 ° C. or when the heating time exceeds 5 hours, a sufficient amount of Cu ₆ Sn ₅ and Cu ₃ Sn may not be generated due to evaporation of the molten Sn.

(Cooling process)
In the cooling step is heated, the alloy thin film formed substrate was cooled at a rate of 400 ° C. / Time to 50 ° C. / min, and Sn-Cu alloy thin film formed article.
At this time, if the cooling rate is lower than 400 ° C./hour, the oxidation of Sn proceeds and the content of SnO ₂ may increase.
On the other hand, if the cooling rate is faster than 50 ° C. / min, which is not preferable wrinkles entering the alloy thin film formed on the cooling rate is too fast.

Next, an example that satisfies the requirements of the present invention and a comparative example that does not satisfy the requirements of the present invention will be specifically shown and described.
First, using a carbon steel plate of JIS SS 400, it was immersed in a copper sulfate bath (copper sulfate 150 g / L, sulfuric acid 40 g / L) at 25 ° C. Under the condition of electrolysis time of 3 minutes at a current density of 1 A / dm ^2. By electrolysis, a 10 μm thick Cu layer was plated on the carbon steel plate.

Then, the carbon steel sheet in which the Cu layer was formed by changing the electrolysis time from 2 minutes to 20 minutes at a current density of 1 A / dm ^{2 in} a 20 ° C. tin sulfate (30 g / L) -sulfuric acid (180 g / L) bath. An Sn layer having a layer thickness of 1 μm (electrolysis time 2 minutes), 5 μm (electrolysis time 10 minutes), and 10 μm (electrolysis time 20 minutes) was formed by plating.

  These samples were respectively subjected to temperature conditions of 200 ° C. (FIG. 2 (a)), 250 ° C. (FIG. 2 (b)), 300 ° C. (FIG. 3 (a)), and 350 ° C. (FIG. 3 (b)). A Sn—Cu alloyed plating thin film was formed by heating for 1 hour, 3 hours, and 5 hours, respectively. After the heat treatment, the surface of the Sn—Cu alloyed plating thin film was identified by an X-ray diffraction method.

FIG. 1 shows the X of the plating surface formed after forming a Sn—Cu heat-treated alloyed plated thin film having a layer thickness of 15 μm (Cu layer: 10 μm, Sn layer: 5 μm) on a carbon steel plate and heating at 250 ° C. for 5 hours. a line diffraction diagram, in FIG. 2 (a) and (b) and in FIGS. 3 (a) and (b) heat-treating the various alloy thin film formed samples changed thickness of the Sn layer at various temperatures The surface film composition is shown.

Then, three types of bacteria, Escherichia coli ATCC25032, Klebsiella pneumoniae ST101 and Staphylococcus aureus 209P were pre-cultured with 10 mL bouillon at 35 ° C. for 18 hours. Thereafter, the suspension was diluted to 10 ⁵ / mL with a 0.9% NaCl solution to prepare a bacterial suspension.

  Put 400 μL of the above bacterial suspension on a test piece (5 × 5 cm) (hereinafter referred to as “test piece”) of a carbon steel plate on which a Sn—Cu alloyed plating thin film is formed, and immediately sterilize a polyethylene film (4 × 4 cm) with bacteria. It was put on the suspension.

  Thereafter, each test piece was transferred into a sterilized petri dish and maintained at 35 ° C. for 24 hours in an environment with a relative humidity of 99% or more. Bacteria attached to the polyethylene film and the test piece were added with 10 mL of 0.9% NaCl containing 0.2% Tween 80, and then rinsed with a pipette into a plastic petri dish.

100 μL of the washed bacterial suspension was inoculated on a plate-like agar medium and spread using a glass spreader. After holding at 35 ° C. overnight, the number of bacterial colonies was counted.
Table 1 shows the result of the antibacterial test of the unheated thin film (comparative example) just by laminating the Sn—Cu layer by the film adhesion method. Table 2 shows the results of the antibacterial test of the Sn—Cu heat-treated alloyed plated thin film (Example) after heat treatment by the film adhesion method.

According to these results, as shown in Table 1, the thin film according to the comparative example in which only the Sn—Cu layer is laminated has an antibacterial effect because Sn is merely laminated on the outer layer of the plating. There wasn't.
In contrast, as shown in Table 2, the heat-treated Sn-Cu heat-treated alloyed plated thin film produced Cu ₆ Sn ₅ and Cu ₃ Sn in the outer layer of plating by heat treatment. Therefore, a remarkable antibacterial effect was recognized.

(Example 2)
After forming a 10 μm Cu layer on a carbon steel plate, an Sn layer was formed to a layer thickness of 1 μm, 5 μm, and 10 μm. These test pieces were heat-treated at 200 ° C., 250 ° C., 300 ° C., and 350 ° C. for 5 hours, then cooled at a cooling rate of 30 ° C./min, and the vicinity of the surface layer was subjected to fluorescent X-ray analysis. And analyzed.
The analysis results are shown in FIG. 4 to FIG. 6 for each Sn layer thickness. 4 to 6, the horizontal axis indicates each heat treatment temperature, and the vertical axis indicates the concentration (mass%) near the surface of Fe, Cu, and Sn.

  FIG. 4 is a graph showing an analysis result of the fluorescent X-ray analysis for the test piece having the smallest Sn layer thickness of 1 μm. As shown in FIG. 4, even when the heat treatment temperature was varied, a large difference in the Fe, Cu, Sn concentration ratio was not recognized.

  On the other hand, FIG. 5 is a graph showing the result of X-ray fluorescence analysis of a test piece having a Sn layer thickness of 5 μm. As shown in FIG. 5, at 200 ° C. to 250 ° C., Cu diffuses to the surface, and Sn diffuses inward, resulting in a decrease in Sn concentration and an increase in Cu concentration.

And FIG. 6 is a graph which shows the analysis result of the fluorescent X ray analysis with respect to the test piece whose layer thickness of Sn layer is 10 micrometers thickest. As shown in FIG. 6, it was found that the change in Cu and Sn concentrations proceeded more severely than in FIG. It can also be seen that the melting progresses as the master and slave of Sn and Cu are reversed when the heat treatment temperature is around 220 ° C. This means that Cu ₆ Sn ₅ and Cu ₃ Sn can be generated by containing a sufficient and appropriate amount of Sn and Cu and performing heat treatment under appropriate heat treatment conditions.

  In addition, since this analysis result used the fluorescent X ray analysis whose analysis limit in the depth direction of a thin film is about 20 micrometers, some Fe is detected in the analysis result. This reflects the Fe constituting the substrate. Therefore, as shown in FIG. 6, in the analysis result of the test piece, which has a layer thickness of about 20 μm when the Sn layer and the Cu layer are combined, the Fe concentration is very small. This also means that a certain antibacterial property can be provided if the thickness of the thin film is about 20 μm.

  As described above, the best mode for carrying out the manufacturing method of the Sn—Cu alloy thin film, the Sn—Cu alloy thin film formed product and the Sn—Cu alloy thin film formed product of the present invention, and the examples thereof will be described specifically. However, the contents of the present invention are not limited to these descriptions, and can be widely changed and modified without departing from the spirit of the invention.

  For example, in the description of the manufacturing method of the Sn—Cu alloy thin film-formed product, the Cu layer formation and the Sn layer formation order can be interchanged.

  In addition, the Cu layer forming step and the Sn layer forming step of the manufacturing method of the Sn-Cu alloy thin film-formed product can be formed by the same kind of plating treatment, sputtering treatment, and vapor deposition treatment. Not. For example, the Cu layer forming process can be performed by a plating process, and the Sn layer forming process can be performed by a different process such as a vapor deposition process.

  In addition, as long as the functions of the Sn—Cu alloy thin film of the present invention are not impaired, commonly used surfactants and complexing agents, brighteners, semi-brighteners, antioxidants, smoothing agents, pH adjusters, conductivity It is possible to add or apply various additives such as salts, preservatives, and antifoaming agents.

It is an X-ray diffraction pattern of the plating surface performed after forming a Sn-Cu heat-treatment alloying plating thin film and heating at 250 degreeC for 5 hours. (A) and (b) are diagrams showing a surface coating composition when the heat treatment of the various alloy thin film formed samples changed thickness of the Sn layer at various temperatures. (A) and (b) are diagrams showing a surface coating composition when the heat treatment of the various alloy thin film formed samples changed thickness of the Sn layer at various temperatures. It is a graph which shows the analysis result of the fluorescent X ray analysis with respect to the test piece whose layer thickness of Sn layer is 1 micrometer. It is a graph which shows the analysis result of the fluorescent X ray analysis with respect to the test piece whose layer thickness of Sn layer is 5 micrometers. It is a graph which shows the analysis result of the fluorescent X ray analysis with respect to the test piece whose layer thickness of Sn layer is 10 micrometers.

Claims (2)

A Cu layer forming step of forming a Cu layer having a layer thickness of 1 to 50 μm on the substrate substrate;
An Sn layer forming step of forming an Sn layer having a thickness of 1 to 50 μm on the Cu layer;
The base material on which the Cu layer and the Sn layer are formed is heated under conditions of 250 to 400 ° C. and 1 to 5 hours, the Cu content is 10 to 90 [atomic%], and Cu ₆ Sn ₅ and Cu An alloy thin film forming step for forming an alloy thin film of Sn and Cu , wherein at least one of ₃ Sn is formed ;
A cooling step of heating the base material on which the alloy thin film is formed at a rate of 400 ° C./hour to 50 ° C./minute to form a Sn—Cu alloy thin film formed product;
The manufacturing method of the Sn-Cu alloy thin film formation article which has antimicrobial property which comprises this.   2. The antibacterial Sn − according to claim 1, wherein the Cu layer forming step and the Sn layer forming step are each laminated as a single layer by plating, sputtering, or vapor deposition. A method for producing a Cu alloy thin film-formed product.

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