Metal film piece formation member and manufacturing method thereof

Abstract

To provide a metal film piece formation member forming a trivalent metal film capable of performing an antibacterial property drastically more excellent than a monovalent metal film, and manufacturing method thereof.SOLUTION: In a metal film formation composition, a composition for forming a metal film piece, containing at least one kind selected from a group of a metal complex and a metal salt, and metal precursor liquid having a reaction product to amine, in which a mole ratio of ethylene diamine and / or hexamethylene diamine is 1.49% or more, is adhered to a substrate and dried to form a metal film piece on a surface of the substrate. The composition for forming the metal film piece is adhered to the substrate, and is dried for 12 hours or more. Then, ultraviolet ray with wavelength shorter than 280 nm under an atmosphere with a steam content of 17.0 g / cm3 or less is radiated, so as to form the metal film piece, on which a peak of a trivalent metal ion by an X-ray photoelectron spectroscopy (XPS) is detected higher than that of a metal ion with the other valence, is formed on the surface of the substrate.SELECTED DRAWING: Figure 2

Description

[Technical Field]

[0001] The present invention relates to a metal film piece-formed member formed by forming metal film pieces on the surface of a substrate, and a method for producing the same. [Background technology]

[0002] Generally, methods for forming a metal film on the surface of a substrate include gas phase methods such as sputtering and chemical vapor deposition, and liquid phase methods such as electrolytic plating and electroless plating. However, gas phase methods require large-scale equipment for film formation and impose limitations on the size of the substrate on which the film is formed, while liquid phase methods require heat treatment to improve crystallinity.

[0003] Therefore, a metal film formation method using a molecular precursor method has been proposed in which a metal complex solution is applied to a substrate and then treated with light energy or thermal energy to obtain a metal oxide film (see, for example, Patent Document 1). [Prior art documents] [Patent documents]

[0004] [Patent Document 1] Patent No. 6953006 Summary of the Invention [Problem to be solved by the invention]

[0005] However, in the case of the above-mentioned conventional film-forming methods, for example, when forming a copper metal film, a monovalent copper metal film is usually formed, and no technology has been established for forming a trivalent metal film.

[0006] As a result of extensive research, the inventors have succeeded in establishing a technology for forming a trivalent metal film, and have confirmed that this trivalent metal film exhibits significantly superior antibacterial properties than monovalent metal films. [Means for solving the problem]

[0007] The metal film piece-forming member of the present invention for solving the above-mentioned problems is obtained by adhering a metal film piece-forming composition containing a reaction product of at least one selected from the group consisting of metal complexes and metal salts with an amine in which the molar ratio of ethylenediamine and / or hexamethylenediamine is 1.49% or more to a substrate and then drying the composition to form metal film pieces on the surface of the substrate, and the composition has a water vapor content of 17.0 g / cm after adhering the metal film piece-forming composition to the substrate and drying for 12 hours or more. 3 By irradiating ultraviolet light (UV-C) with a wavelength shorter than 280 nm in the following atmosphere, metal film pieces are formed on the surface of the substrate, in which the peak of trivalent metal ions detected by X-ray photoelectron spectroscopy (XPS) is larger than the peaks of metal ions with other valencies.

[0008] The metal film piece-forming member was cut into pieces of 30 mm × 30 mm, sterilized, and then placed in a sterilized petri dish. NBRC3972 Escherichia coli was added to the dish at a concentration of 9 × 10 5 ~3×10 6 0.05 ml of test bacterial solution prepared to a concentration of cfu / ml is dropped, and after incubation at 35±1°C for 10 minutes, the solution is thoroughly washed out using 5 ml of SCDLP medium, and then serially diluted to 1:10,000 with water. Each diluted bacterial solution is incubated at 35±1°C for 48 hours using the agar plate culture method, and the antibacterial activity value (R) calculated from the resulting viable bacterial count may be 2.0 or more.

[0009] The metal film piece forming member may be one in which the metal is copper (Cu).

[0010] The metal film piece member may have a base material that is a HEPA filter.

[0011] The method for producing a metal film piece-formed member of the present invention for solving the above-mentioned problems is a method for producing a metal film piece-formed member in which metal film pieces, in which the peak of a trivalent metal ion detected by X-ray photoelectron spectroscopy (XPS) is greater than the peaks of metal ions of other valences, are formed on the surface of a substrate, the method comprising the steps of: applying to the substrate a composition for forming metal film pieces, the composition comprising a reaction product of an amine with at least one selected from the group consisting of a metal complex and a metal salt; drying the substrate after the application for 12 hours or more; and heating the substrate after the drying in a water vapor atmosphere with a water vapor concentration of 17.0 g / cm. 3 and irradiating the substrate with ultraviolet light (UV-C) having a wavelength shorter than 280 nm in the following atmosphere.

[0012] The method for manufacturing the metal film piece-formed member may use copper (Cu) as the metal.

[0013] The method for producing the metal film piece member may use a HEPA filter as the substrate.

[0014] [Composition for forming metal film pieces] The composition for forming the metal film pieces is obtained by reacting at least one selected from the group consisting of metal complexes and metal salts with an amine in a mixed solution of at least one selected from the group consisting of metal complexes and metal salts, an amine having a molar ratio of ethylenediamine and / or hexamethylenediamine of 1.49% or more, and a solvent.

[0015] [At least one selected from the group consisting of metal complexes and metal salts] The at least one selected from the group consisting of the above metal complexes and metal salts may be only one or more types of metal complexes, only one or more types of metal salts, or a mixture containing both one or more types of metal complexes and one or more types of metal salts.

[0016] The metal complex is preferably a reaction product of a metal ion and one or more compounds for forming a metal complex selected from compounds having as a partial structure an NH ligand, an RNH ligand (where R represents an alkylene group), an OH ligand, or a ligand derived from a diamine such as ethylenediamine or hexamethylenediamine, which can form a metal complex. The metal complex may be a metal complex previously formed by the above reaction. The metal in the metal complex may be selected from a metal suitable for the purpose of the metal film to be formed. Examples of metals include silver (Ag), copper (Cu), lithium (Li), nickel (Ni), manganese (Mn), zinc (Zn), and cobalt (Co). Specific examples of metal complexes that are preferred include ethylenediaminetetraacetate copper and tetraammine copper, each containing copper (Cu) as the metal.

[0017] The metal salt is a metal compound that dissociates in a solvent containing water to form metal ions and can form a metal complex. The metal salt refers to a metal salt that is soluble in water at 25°C. "Soluble in water at 25°C" means that the solubility in water at 25°C is 0.1% by mass or more, preferably 1% by mass or more. When a metal salt is soluble in water, it dissociates in a solvent containing water to form metal ions, and the metal ions react with amines contained in the solvent to form a metal complex. Furthermore, if a complex-forming compound (described below) is optionally contained in the solvent, the metal ions may react with the complex-forming compound to form a metal complex. Specific examples of this metal salt include, for example, copper formate tetrahydrate and copper acetate tetrahydrate when the metal is copper (Cu).

[0018] [Amine] The amine may be one or more types of amines. These may be contained as salt compounds. Amines include primary amines, secondary amines, and tertiary amines. Specific examples of amines include alkylamines. These amines act as ligands that react with the metal ions of the metal salts to form metal complexes. It is preferable that these amines contain at least ethylenediamine and / or hexamethylenediamine. It is particularly preferable that the ratio of the number of moles of ethylenediamine and / or hexamethylenediamine to the total number of moles of amines as ligands is 1.49% or more. In this case, examples of amines other than ethylenediamine and / or hexamethylenediamine include propylamine, butylamine, pentylamine, and octylamine.

[0019] [solvent] The solvent is not particularly limited as long as it can dissolve at least one selected from the group consisting of the metal complexes and metal salts described above and the amine described above. For example, an aqueous solvent such as water or a mixture of water and alcohol can be used. It is preferable that the water contains a small amount of impurities, particularly ions other than metal ions. From this perspective, purified water, ion-exchanged water, pure water, etc. are preferably used. Examples of alcohols include monohydric alcohols having 1 to 10 carbon atoms, such as methanol, ethanol, isopropanol, n-propanol, isobutanol, and n-butanol, and polyhydric alcohols, such as ethylene glycol, propylene glycol, diethylene glycol, polyethylene glycol, and glycerin.

[0020] From the viewpoint of solubility and handling, the aqueous solvent is preferably water or a mixture of water and a monohydric alcohol having 1 to 5 carbon atoms, more preferably water or a mixture of water and an alcohol selected from methanol, ethanol, and propanol, and even more preferably water. When a mixture of water and alcohol is used as the solvent, the mixing ratio is appropriately selected depending on the purpose. When a mixture of water and alcohol is used as the solvent, the content of alcohol relative to the total amount of the mixture of water and alcohol is preferably 1% by mass to 60% by mass.

[0021] [Preparation of composition for forming metal film pieces] The composition for forming the metal film pieces can be prepared by adding at least one selected from the group consisting of the metal complexes and metal salts described above and the amine described above to a solvent and thoroughly stirring and mixing them.

[0022] The mixing may be performed at room temperature, or, to promote dissolution, the solvent may be heated to 40° C. to 60° C. The stirring method is not particularly limited, and known stirring methods can be applied, such as a method in which the mixed solution is placed in a container and stirred using a rotor such as a magnetic stirrer, a method in which the mixed solution is stirred with a stirring device equipped with rotary stirring blades such as a paddle, a method in which the solution is placed in a sealable container and stirred by shaking the container, and a method in which ultrasonic waves are irradiated.

[0023] A simple method is to use a stirring device equipped with a stirring blade. The rotation speed of the rotor blade can be 300 rpm (revolutions / minute: the same applies hereinafter) to 800 rpm, preferably 400 rpm to 600 rpm. Stirring is preferably carried out until the reaction between at least one selected from the group consisting of the metal complexes and metal salts described above and the amine described above has sufficiently progressed. When stirring is carried out at room temperature using the stirring device equipped with a rotor blade described above, stirring is preferably carried out for about 30 to 90 minutes, more preferably for about 50 to 80 minutes.

[0024] The above-mentioned composition for forming metal film pieces may be prepared by applying a known molecular precursor method. While the known precursor method can be used to prepare the composition for forming metal film pieces as described above, it is preferable to include the following electrolysis step in order to obtain a composition for forming metal film pieces with higher purity. Specifically, this electrolysis step involves a reaction apparatus including a pair of electrolyte tanks connected via a flow path equipped with a filter that is impermeable to metal ions but permeable to hydrogen ions, storing an amine-containing electrolyte in each of the pair of electrolyte tanks, and arranging a pair of metal electrodes in positions where at least a portion of the electrodes are in contact with the electrolyte, connecting the pair of electrodes via a DC power source. Finally, a voltage is applied between the pair of electrodes from the DC power source to react the metal ions derived from the metal electrode with the electrolyte in the electrolyte tank in which the anode electrode is immersed, thereby obtaining a composition for forming metal film pieces.

[0025] In general, it is difficult to measure the content of a specific metal compound relative to the total amount of a composition for forming metal film pieces. However, the physical properties of the metal film pieces formed from the composition for forming metal film pieces depend on the metal content in the composition for forming metal film pieces. From the viewpoint of forming stable metal film pieces, the metal content relative to the total amount of the composition for forming metal film pieces is preferably 0.8 mmol / g or more, and more preferably in the range of 0.8 mmol / g to 1 mmol / g. By ensuring that the metal content is within the above range, the structure of the metal film pieces formed from the composition for forming metal film pieces becomes more uniform, allowing for the formation of stable metal film pieces.

[0026] The metal content in the composition for forming metal film pieces can be measured, for example, by the method described in "Basics of Coordination Chemistry: Werner Complexes and Organometallic Complexes" (KS Chemistry Specialist: Kodansha, 1989).

[0027] [Base material] The substrate is not particularly limited as long as it can be used to form metal film flakes using the metal film flake-forming composition. It may be made of inorganic materials such as glass, metal, ceramics, etc.; natural materials such as wood and plant fibers; synthetic materials such as plastics and synthetic fibers; or composite materials of these. The substrate may be a hard material such as a glass plate or metal plate, or a flexible or bendable material such as a film, sheet, paper, thread, woven fabric, or nonwoven fabric. Furthermore, the substrate may be formed into a planar shape such as a plate or sheet, a linear shape such as a thread or rod, or a three-dimensional shape such as a thick nonwoven fabric or a HEPA filter.

[0028] In particular, various air filters can be used to remove dust and other particles from the air and produce purified air. Specific examples of such filters include HEPA filters, which have a particle collection rate of 99.97% or more for particles with a particle size of 0.3 μm at a rated airflow rate and an initial pressure drop of 245 Pa or less. However, in addition to HEPA filters, other filters may be used, such as semi-HLPA filters, which have a particle collection rate of 95-99% for particles with a particle size of 0.3 μm at a rated airflow rate and an initial pressure drop of 245 Pa or less, MEPA filters, which have a particle collection rate of 50-95% or more for particles with a particle size of 0.4 μm and 0.7 μm, or even low-grade coarse dust filters. These filters capture dust and other particles by blocking their flow lines with the filter paper that constitutes the filter. The fiber filaments that make up this filter paper may be inorganic fibers such as glass fibers, or organic fibers such as polyethylenes such as PET, low-density polyethylene (LDPE), and high-density polyethylene (HDPE), polycarbonate (PC), polyvinyl chloride (PVC), polystyrene, acrylic resins such as polymethyl methacrylate (PMMA), polyamides such as nylon 6, phenolic resins, melamine resins, urethane resins, and carbon fibers, or natural fibers such as silk, cotton, cellulose, and hemp.

[0029] [Manufacturing of metal film forming parts] To produce the metal film piece-forming member, the metal film piece-forming composition is first applied to the substrate. The method for applying the metal film piece-forming composition to the substrate may involve immersing the substrate in the metal film piece-forming composition, or applying the metal film piece-forming composition to the substrate. For application, known methods such as spraying, roll coating, flow coating, and spin coating can be used.

[0030] After the metal film flake forming composition is applied to the substrate, a drying step is performed in which the composition is dried for at least 12 hours. Drying can be performed by conventional methods such as natural drying, heat drying, and air drying. Natural drying involves leaving the composition at room temperature for at least 12 hours. Heat drying can be performed by appropriately selecting and applying a known heating method. Examples of heating methods include contacting the substrate with a heating means such as a plate heater or heat roll from the back side, passing the substrate through a heating zone such as an electric furnace, irradiating the substrate with energy rays such as infrared rays or microwaves, and blowing hot air. The heating temperature during heat drying is not particularly limited. However, when considering the formation of a trivalent metal film, taking into consideration drying efficiency and minimizing the impact on the substrate, the heating temperature can be in the range of 30°C or higher but lower than 80°C, with a range of 30°C to 70°C being preferred. The drying time during heat drying is not particularly limited as long as it is at least 12 hours, but drying for longer than 12 hours is not particularly effective, so a range of 12 to 24 hours is preferred. In the case of blow drying, air under the ambient atmosphere may be blown to dry the film, or hot air may be blown onto the film as described above.

[0031] When the composition for forming metal film pieces is applied and dried, the solvent contained in the composition for forming metal film pieces evaporates, leaving metal film pieces attached to the substrate. In this case, the amount of metal film pieces attached can be adjusted by adjusting the immersion concentration in the case of an immersion treatment, the application concentration in the case of a coating treatment, or by repeating the coating and drying process.

[0032] After drying the substrate, a water vapor concentration of 17.0 g / cm was applied to fix the metal film pieces attached to the substrate. 3 The process of irradiating ultraviolet light (UV-C) with a wavelength shorter than 280 nm is carried out in the following atmosphere. At this time, the amount of water vapor is 17.0 g / cm. 3 There are no particular limitations as long as it is below 10.6 g / cm 3 If the water vapor content is less than 10.6 g / cm, adhesion will decrease. 3 or more, preferably with a water vapor content of 12.1 g / cm3 ~Water vapor content 13.6g / cm 3 The wavelength of ultraviolet light is important, and as long as ultraviolet light (UV-C) with a wavelength shorter than 280 nm is irradiated, the irradiation energy is not particularly limited. The ultraviolet light (UV-C) with a wavelength shorter than 280 nm should be in the range of 4 to 10 mW / cm. 2 It is preferable to irradiate with an irradiation energy of about 1000 W / m.

[0033] The metal film piece-forming member of the present invention thus constructed can be obtained by applying the metal film piece-forming composition to a substrate, drying the composition for forming the metal film piece for 12 hours or more without applying excessive heat, and then irradiating the composition with ultraviolet light (UV-C) having a wavelength shorter than 280 nm at a predetermined atmospheric humidity to fix the metal film piece adhered to the substrate, thereby forming metal film pieces on the surface of the substrate in which the peak of trivalent metal ions is detected as being larger than the peaks of metal ions of other valences. This can be confirmed by analyzing the metal film piece-forming member by X-ray photoelectron spectroscopy (XPS).

[0034] A metal film piece-formed member having trivalent metal film pieces formed thereon exhibits significantly superior antibacterial properties compared to a metal film piece-formed member having divalent or monovalent metal film pieces. Specifically, the antibacterial activity value of 2.0 or higher is achieved by a standard agar plate culture method using NBRC3972 Escherichia coli according to the film adhesion method (in accordance with JIS Z 2801:2010). This is even more superior than the antibacterial properties of the metal itself that constitutes the metal film pieces. Furthermore, because such excellent antibacterial properties are achieved by forming metal film pieces on a substrate, even in cases where the substrate is flexible or pliable, the substrate can be used without impairing its flexibility. Furthermore, even a small amount of metal film pieces formed by simply attaching and drying metal film pieces to a substrate and fixing them with ultraviolet light exhibits excellent antibacterial properties. Therefore, the formation of metal film pieces results in minimal color change in the metal film piece-formed member, and does not impair the design of the metal film piece-formed member. Furthermore, such a metal film piece forming member can have superconductivity. [Effects of the Invention]

[0035] As described above, according to the present invention, a composition for forming metal film pieces, which contains a reaction product of at least one selected from the group consisting of a metal complex and a metal salt with an amine, is applied to a substrate, and then dried for 12 hours or more, and the water vapor amount is 17.0 g / cm. 3 By irradiating ultraviolet light (UV-C) with a wavelength shorter than 280 nm in the following atmosphere, it is possible to obtain a metal film piece formed on the surface of a substrate, in which the peak of trivalent metal ions detected by X-ray photoelectron spectroscopy (XPS) is larger than the peaks of metal ions of other valences, and thus a metal film piece-formed member in which trivalent metal ions are selectively formed can be constructed.Furthermore, a metal film piece-formed member in which trivalent metal ions are selectively formed in this way can exhibit excellent antibacterial properties. [Brief explanation of the drawings]

[0036] [Figure 1] 1 shows X-ray diffraction data of a metal film piece-formed member according to the present invention and a metal film piece-formed member according to a comparative example, with respect to differences in humidity when preparing the metal film piece-formed member. [Figure 2] 1 shows analytical data by X-ray photoelectron spectroscopy of a metal film piece-formed member according to the present invention and a metal film piece-formed member according to a comparative example, depending on the humidity used when preparing the metal film piece-formed member. [Figure 3] 1 shows X-ray diffraction data of a metal film piece-formed member according to the present invention and a metal film piece-formed member according to a comparative example, with respect to differences in drying time when preparing the metal film piece-formed member. [Figure 4] 1 shows analytical data by X-ray photoelectron spectroscopy of a metal film piece-formed member according to the present invention and a metal film piece-formed member according to a comparative example, with respect to differences in drying time when preparing the metal film piece-formed member. [Figure 5] 1 is a graph showing the relationship between the absorption coefficient measured by a photoelectric colorimeter and the bacterial concentration of NBRC3972 (Escherchia coli). DETAILED DESCRIPTION OF THE INVENTION

[0037] [Examples 1 to 4, Comparative Examples 1 to 3] (Preparation of composition for forming metal film pieces) To 5,000 g of dehydrated ethanol were added 0.990 g of propylamine, 0.500 g of ethylenediamine, and 1.890 g of a metal salt, copper formate tetrahydrate, and the mixture was stirred at room temperature at 500 rpm for 1 hour to synthesize a first liquid.

[0038] To 5,000 g of dehydrated ethanol, 2,200 g of propylamine and 2,100 g of copper formate tetrahydrate (metal salt) were added, and the mixture was stirred at room temperature at 500 rpm for 1 hour to synthesize a second liquid.

[0039] The first liquid and the second liquid were mixed in a mass ratio of 1:8, and then stirred and mixed at room temperature for 120 minutes to obtain a composition for forming metal film pieces with a copper (Cu) concentration of 1.00 mmol / g.

[0040] (Preparation of metal film piece-forming member) A 30mm x 30mm non-alkali glass substrate was ultrasonically cleaned with water and 2-propanol, and then treated with ozone to remove organic contaminants from the surface. 0.13ml of the metal film forming composition obtained above was then dripped onto the glass substrate using a micropipette, and spin-coated using a double-step method. In the double-step method, the glass plate onto which the metal film forming composition had been dripped was rotated at 1000 rpm for 10 seconds, followed by spinning at 2000 rpm for 30 seconds, thereby coating the glass substrate with the metal film forming composition.

[0041] A plurality of glass substrates coated with this composition for forming metal film pieces were prepared and dried at 70°C for 24 hours to evaporate the solvent in the composition for forming metal film pieces, leaving the metal film pieces attached to the surface of the substrate. After that, the substrates were dried at a temperature of 30°C and a humidity of 40% (water vapor content of 12.1 g / cm). 3 ) atmosphere, 10mW / cm 2 , 8mW / cm 2 , 6mW / cm 2 , 4mW / cm 2The test pieces of Examples 1 to 4 were prepared by fixing the metal film pieces to the glass substrates by irradiating the glass substrates with ultraviolet light (UV-C) having a wavelength shorter than 280 nm for 4 hours.

[0042] Test pieces according to Comparative Examples 1 to 3, in which metal film pieces were fixed to glass substrates, were obtained by preparing in the same manner as in Examples 2 to 4 above, except that the humidity was set to 60 Rh%.

[0043] (Antibacterial evaluation) The test pieces obtained in Examples 1 to 4 and Comparative Examples 1 to 3 were subjected to the following antibacterial activity test. The test bacteria used in the antibacterial activity test were NBRC3972 (Escherchia coli) obtained from the National Institute of Technology and Evaluation. The concentration of the bacterial solution was 9 x 10 5 ~3×10 6 The solution was prepared using a phosphate buffer solution so that the concentration of bacteria was 0.065 and 0.170 cfu / ml. Based on past experience, the relationship between the absorption coefficient (Abs) measured using a photoelectric colorimeter (AP-120 manufactured by APEL Co., Ltd.) and the bacterial concentration (cfu / ml) has been shown in Figure 5. Therefore, the solution was prepared so that the absorption coefficient was 0.065 and 0.170 (9 × 10 7 ~3×10 8 cfu / ml), and by dividing this by 1 / 100, the 5 ~3×10 6 A bacterial solution of cfu / ml was prepared. The test piece was cut into a size of 30 mm x 30 mm and sterilized on both sides by ultraviolet irradiation. The sterilized test piece was placed in a sterilized petri dish and the above 9 x 10 5 ~3×10 6 0.05 ml of test bacterial solution prepared to a concentration of cfu / ml was dropped onto the plate. After culturing at 35±1° C. for 20 minutes, the test pieces were thoroughly washed out using 5 ml of SCDLP medium (manufactured by Nippon Pharmaceutical Co., Ltd.). The viable bacterial count was confirmed using the agar plate culture method, and serial dilutions were performed up to a 1:10,000 dilution. 1 ml of each diluted bacterial solution was taken into a 90 mm diameter sterile dish, and standard agar medium (manufactured by Nippon Pharmaceutical Co., Ltd.) prepared at approximately 48°C was poured over it. After stirring and solidifying, the mixture was cultured in an incubator at 35°C ± 1°C for 48 hours. From each dilution ratio, a petri dish suitable for measurement (with the number of developed colonies of approximately 30 to 300 cfu) was selected, and the number of colonies was measured. The number of viable bacteria was determined from the measured colony count, and the antibacterial activity value (R) was calculated. In addition, since the evaluation standard for antibacterial testing in JIS Z 2801 is an antibacterial activity value of 2.0 or more, whether or not a measured antibacterial activity value of 2.0 or more was used as the criterion for determining whether or not a product has antibacterial properties. The results are shown in Table 1.

[0044] [Table 1]

[0045] In Table 1, the antibacterial activity value (R) was calculated using the following formula. [Live bacteria count] N=C×D×V N: Number of live bacteria, C: Number of colonies in the dish, D: Dilution ratio, V: Volume of SCDLP medium [Antibacterial activity value] R=(U t -U0)-(At-U0) R: Antibacterial activity value U0: Mean logarithm of viable bacteria count immediately after inoculation of untreated test specimens U t : Average logarithm of viable bacteria count after 20 minutes on untreated test pieces A t : Average logarithm of viable bacteria count after 20 minutes on antibacterial treated test piece

[0046] The results in Table 1 confirm that changes in ultraviolet irradiation energy do not have much effect on the strength of antibacterial activity. Furthermore, when the humidity was 40% Rh, good antibacterial properties were obtained, but when the humidity was 60% Rh, good antibacterial properties were not obtained.

[0047] [Example 2, Examples 5 to 12, Comparative Example 1, Comparative Example 4] Test pieces according to Examples 5 to 12, in which metal film pieces were fixed to a glass substrate, were prepared in the same manner as in Example 2 above, except that the temperature and humidity of Example 2 were changed to the various conditions shown in Table 2. For comparison, Comparative Example 1, Comparative Example 1, and a test piece according to Comparative Example 4, in which metal film pieces were fixed to a glass substrate, were prepared in the same manner as in Comparative Example 1 above, except that the temperature and humidity of Comparative Example 1 were changed to the conditions shown in Table 2. The antibacterial properties of each of these test pieces were evaluated in the same manner as above. The results are shown in Table 2.

[0048] [Table 2]

[0049] From the results in Table 2, the water vapor content is 10.6 g / cm 3 More than 17.0g / cm 3 It was confirmed that good antibacterial properties were obtained under the following conditions.

[0050] (Regarding adhesion status) Among the above examples, for each of the test pieces in Examples 5, 2, 7, 9, and Comparative Example 1, in which the humidity parameter was changed at a temperature of 30°C to produce different amounts of water vapor, X-ray diffraction was performed on the glass substrate with metal film pieces attached. As shown in Figure 1, diffraction peaks of CuO (cuprous oxide) were confirmed in all of the test pieces. Furthermore, when the glass substrates with the metal film pieces attached to each of the above test pieces were analyzed by X-ray photoelectron spectroscopy, as shown in FIG. 2, the test pieces of Examples 5, 2, 7, and 9 according to the present invention contained Cu. 3+ From this result, it was found that Cu 3+ It was confirmed that excellent antibacterial properties were obtained for each of the test pieces of Examples 5, 2, 7, and 9 according to the present invention, in which a copper peak was confirmed.

[0051] [Example 2, Examples 13-14, Comparative Examples 5-13] In the antibacterial test of Example 2 above, the incubation time was changed from 20 minutes to 15 minutes (Example 13), 10 minutes (Example 14), and 5 minutes (Comparative Example 5), and the respective antibacterial activity values ​​were determined in the same manner as in Example 2. For comparison, the antibacterial activity values ​​were also determined for samples incubated for the same time on glass substrates only (Comparative Examples 6 to 9) and copper plates only (Comparative Examples 10 to 13). Note that in none of Comparative Examples 6 to 13 was the ultraviolet irradiation step carried out to fix the metal film pieces. The results are shown in Table 3.

[0052] [Table 3]

[0053] From the results in Table 3, it was confirmed that the metal film piece-formed members according to the examples had better antibacterial properties than the copper plate if the incubation time was 10 minutes or more.

[0054] [Example 2, Examples 15-16, Comparative Examples 14-16] In Example 2 above, the drying time, which was 24 hours at 70°C, was changed to 18 hours (Example 15), 12 hours (Example 16), 8 hours (Comparative Example 14), 6 hours (Comparative Example 15), and 3 hours (Comparative Example 16), and the adhesion status of the metal film pieces was confirmed. As shown in FIG. 3, when X-ray diffraction was performed, diffraction peaks of Cu2O (cuprous oxide) were confirmed in all test pieces. Furthermore, as shown in FIG. 4, when analyzed by X-ray photoelectron spectroscopy, the test pieces of Examples 2, 15, and 16 according to the present invention were found to contain Cu. 3+ The copper peak is Cu 2+ Copper or Cu + It was confirmed that the peak of Cu was detected larger than that of Cu. However, for the test pieces according to Comparative Examples 14 to 16, the drying time of which was less than 8 hours, 2+ Copper or Cu + The copper peak is Cu 3+It was confirmed that the peak detected was larger than the peak of copper with a valence of 1.

[0055] [Examples 17 to 19, Comparative Examples 17 to 18] The copper (Cu) concentration of the metal film piece-forming composition when preparing the test pieces was 1.00 mmol / g (Example 17), 0.90 mmol / g (Example 18), 0.80 mmol / g (Example 19), 0.70 mmol / g (Comparative Example 17), and 0.60 mmol / g (Comparative Example 18). The amount of copper formate tetrahydrate, a metal salt, was changed to prepare each metal film piece-forming composition. Each test piece was prepared in the same manner as in Example 2. The antibacterial properties of each test piece obtained in this manner were measured in the same manner as in Example 2. The results are shown in Table 4.

[0056] [Table 4]

[0057] From the results in Table 4, it was confirmed that the test pieces of Examples 17 to 19 according to the present invention all had excellent antibacterial activity values ​​(R) of 4.0 or more. Note that Example 17 is substantially the same as Example 2, but the antibacterial activity value (R) is 4.7, which is higher than the antibacterial activity value (R) of Example 2, which was 4.3, but this is within the range of preparation error and measurement error.

[0058] [Examples 20 to 21, Comparative Example 19] In Example 2 above, the Escherichia coli used in the antibacterial test was changed to Staphylococcus aureus, and the other procedures were the same as in Example 2. The antibacterial activity value (R) was determined for two test pieces (Example 20 and Example 21). In addition, for comparison, the antibacterial activity value (R) was also determined for a glass substrate alone (Comparative Example 19). The results are shown in Table 5.

[0059] [Table 5]

[0060] From the results in Table 5, it was confirmed that the test pieces of Examples 20 and 21 according to the present invention also had excellent antibacterial properties against Staphylococcus aureus.

[0061] [Example 22] An antibacterial test was carried out in the same manner as in Example 2, except that the metal salt copper formate tetrahydrate was changed to copper acetate tetrahydrate. The results are shown in Table 6.

[0062] [Table 6]

[0063] The results in Table 6 confirm that even when the metal salt was changed to copper acetate tetrahydrate, excellent antibacterial properties were maintained.

[0064] [Example 2, Examples 23-29, Comparative Examples 20-23] Test pieces according to Examples 23-29 and Comparative Examples 20-23 were obtained in the same manner as in Example 2, except that the mixing ratio of the first liquid and the second liquid was changed to change the ratio of ethylenediamine (en) to propylamine (Pr). The concentration of en in the ligand was calculated as the molar ratio in the ligand in the mixture of the first and second liquids from [en / (en+Pr)]×100. For example, in Example 2, Cu in the first liquid 2+ The mole numbers for en = 1, Pr = 2, Cu in the second liquid 2+ The number of moles of Pr relative to the ligand was 4, and the mixing ratio of the first liquid to the second liquid was 1:8. Therefore, the Pr in the second liquid was multiplied by 8 to obtain Pr = 32. Applying this to the above formula, we obtain [1 / (1 + 34)] × 100 = 2.857%. For each test piece according to Example 2, Examples 23-29, and Comparative Examples 20-23, the molar proportion of en in the ligand was altered by changing the ratio of ethylenediamine (en) to propylamine (Pr), as shown in Table 7. Each test piece thus obtained was subjected to an antibacterial test similar to that of Example 2. The results are shown in Table 7.

[0065] [Table 7]

[0066] From the results in Table 7, it was confirmed that when the molar ratio of ethylenediamine in the ligand is 1.49% or more, excellent antibacterial properties are obtained.

[0067] [Examples 30-35] In the above Examples 2, 24, and 26, propylamine was changed to butylamine, and test pieces according to Examples 30 to 32 were prepared so that the molar ratio of en in the ligand was the same as in Examples 2, 24, and 26. Furthermore, in the above-mentioned Example 2, propylamine was changed to pentylamine (Example 33) or octylamine (Example 34), and test pieces according to Examples 33 and 34 were obtained, which were prepared so that the molar ratio of ethylenediamine (en) in the ligand was the same as that of Example 2. Furthermore, in Example 2, ethylenediamine (en) was changed to hexamethylenediamine (hmd), and a test piece according to Example 35 was obtained, which was prepared so that the molar ratio of hexamethylenediamine (hmd) in the ligand was the same as that of Example 2. Each test piece thus obtained was subjected to an antibacterial test in the same manner as in Example 2. The results are shown in Table 8.

[0068] [Table 8]

[0069] The results in Table 8 confirm that even combinations of various amines have excellent antibacterial properties.

[0070] [Example 36] A test piece for Example 36 was obtained in the same manner as in Example 2, except that the substrate was changed from 30 mm x 30 mm alkali-free glass to a 30 mm x 30 mm HEPA filter (Iris Ohyama PM2.5 Watcher PMMS-DCHF). However, the HEPA filter was cut into 30 mm x 30 mm pieces and treated with ozone to remove organic contaminants from the surface. The HEPA filter was then immersed in the same metal film piece forming composition as in Example 2 for 1 minute to coat the metal film piece forming composition on the HEPA filter. Each test piece thus obtained was subjected to an antibacterial test in the same manner as in Example 2. The results are shown in Table 9.

[0071] [Table 9]

[0072] The results in Table 9 confirm that excellent antibacterial properties can also be imparted to HEPA filters.

[0073] It should be noted that the present invention can be embodied in various other forms without departing from its spirit or essential features. Therefore, the above-described embodiments are merely illustrative in all respects and should not be interpreted as limiting. The scope of the present invention is defined by the claims and is not limited in any way by the text of the specification. Furthermore, all modifications and variations that fall within the scope of the claims are within the scope of the present invention.

Claims

1. A composition for forming metal film flakes, which contains a metal precursor liquid having a reaction product of at least one selected from the group consisting of metal complexes and metal salts with an amine having a molar ratio of ethylenediamine and / or hexamethylenediamine of 1.49% or more, is applied to a substrate and then dried to form metal film flakes on the surface of the substrate; The composition for forming metal film pieces was applied to the substrate, and after drying for 12 hours or more, the water vapor amount was 17.0 g / cm ３ By irradiating ultraviolet light with a wavelength shorter than 280 nm in the following atmosphere, A metal film piece-forming member characterized in that a metal film piece is formed on the surface of a substrate, in which the peak of a trivalent metal ion detected by X-ray photoelectron spectroscopy (XPS) is larger than the peaks of metal ions of other valencies.

2. The mixture was cut into pieces of 30 mm x 30 mm, sterilized, and then placed in a sterilized petri dish. NBRC3972 E. coli was added to the dish at a concentration of 9 x 10 ５ ~3 x 10 ６ 0.05 ml of a test bacterial solution prepared to a concentration of 10000 cfu / ml is dropped onto the member, and the member is incubated at 35±1°C for 10 minutes. After thorough washing with 5 ml of SCDLP medium, the member is serially diluted to 1:10,000 diluted water. Each diluted bacterial solution is incubated at 35±1°C for 48 hours by the agar plate culture method. The antibacterial activity value (R) calculated from the resulting viable bacterial count is 2.0 or more.

3. 3. The metal film piece-formed member according to claim 1, wherein the at least one metal selected from the group consisting of metal complexes and metal salts is copper (Cu).

4. 3. The metal film piece member according to claim 1, wherein the substrate is a HEPA filter.

5. A method for manufacturing a metal film piece-formed member, in which metal film pieces are formed on the surface of a substrate, in which the peak of a trivalent metal ion detected by X-ray photoelectron spectroscopy (XPS) is larger than the peaks of metal ions of other valences, comprising: A step of depositing a metal film piece forming composition containing a metal precursor liquid having a reaction product of at least one selected from the group consisting of a metal complex and a metal salt with an amine onto a substrate; drying the substrate after the application for 12 hours or more; The dried substrate was subjected to a water vapor concentration of 17.0 g / cm ３ Irradiating ultraviolet light having a wavelength shorter than 280 nm in the following atmosphere; A method for manufacturing a metal film piece-formed member, comprising:

6. 6. The method for producing a metal film piece-formed member according to claim 5, wherein copper (Cu) is used as the at least one metal selected from the group consisting of metal complexes and metal salts.

7. 7. The method for producing a metal film piece-formed member according to claim 5 or 6, wherein a HEPA filter is used as the substrate.

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