JP5522428B2 - Antibacterial and antifungal agents - Google Patents

Description

  The present invention relates to an antibacterial / antifungal agent containing a trinuclear complex of Co—Ag—Co. The antibacterial / antifungal agent of the present invention can be widely applied to, for example, paper and fiber products such as paper, fiber, fabric and filter; building material products such as wood and gypsum board, and materials such as film and plastic is there.

  Antibacterial agents are roughly classified into organic antibacterial agents and inorganic antibacterial agents. Among these, the inorganic antibacterial agents are inferior in durability because they are sensitive to light and heat and sensitive to halogens. In addition, titanium oxide, which is attracting attention as a long-life inorganic antibacterial agent, has a problem that it requires light for antibacterial properties and can only be processed in a solid state. Such problems such as durability and processability have seriously hindered the development of antibacterial products in which an inorganic antibacterial agent is supported on a substrate such as paper, fiber, or fabric. In addition, antibacterial products are preferably required to further have antifungal properties, and development of antibacterial and antifungal agents having both antibacterial and antifungal properties is desired.

Silver ions are low in toxicity to the human body and have a broad antibacterial spectrum, and thus are used for antibacterial treatment of various industrial products. For example, Patent Documents 1 to 3 propose silver complex antibacterial agents. The present inventors also be in non-patent document 1 has excellent antibacterial activity against Co-Ag-Co trinuclear complex E. coli _{Y 1090} of the following formula (5) (E. coli strain Y1090 ) Has been reported. This complex is an S-bridged heterotrinuclear complex obtained by the reaction of a monothiolato-cobalt (III) complex and silver (I) ions, in which Ag and Co are bridged with sulfur (S).

JP 2005-263712 A JP 2000-86668 A JP 2002-212444 A

“Application of Co-Ag-Co trinuclear thiolato complexes toward eco-friendly type antimicrobial agent”, T.Yonemura, T.Ama, H.Kawaguchi, Program No.635. 2005 Abstract Viewer, The International Chemical Congress of Pacific Basin Societies

  An object of the present invention is to provide a novel antibacterial and antifungal agent which is excellent in both antibacterial and antifungal properties, and has excellent durability and processability.

  The antibacterial / antifungal agent of the present invention that has solved the above problems has a gist in that it contains a Co-Ag-Co trinuclear complex represented by the following formula (1).

Where
n is an integer of 1 to 3,
R ^{1 to} R ¹² are the same or different and are H or an alkyl group having 1 to 6 carbon atoms;
Any group of R ^{1 to} R ³ bonded to N, any group of R ^{4 to} R ⁶ , any group of R ^{7 to} R ⁹ , and any group of R ^{10 to} R ¹² It may have a crosslink with any group of
R ¹³ is H or an alkyl group having 1 to 6 carbon atoms.

  A preferred antibacterial / antifungal agent of the present invention contains at least one of a Co—Ag—Co trinuclear complex represented by the following formula (2), the following formula (3), and the following formula (4). .

In the formula, n and R ¹³ have the same meaning as before.

  The antibacterial and antifungal agent of the present invention has a wide range of antibacterial and antifungal properties, and is excellent in durability such as light resistance, heat resistance, stability to inorganic salts, and in either a solution or solid state. However, it is excellent in workability, such as being applicable to a substrate. Accordingly, the antibacterial / antifungal agent of the present invention can be applied to various products, for example, paper, fibers / fabrics, filters, building materials such as wood, and materials such as plastics. Can do.

FIG. 1 is a diagram showing the results of X-ray crystal structure analysis. FIG. 2 is a diagram showing the measurement results of the nuclear magnetic resonance (NMR) spectrum. FIG. 3 is a diagram showing a measurement result of a visible-ultraviolet (UV-Vis) absorption spectrum. FIG. 4 is a diagram showing measurement results of infrared (IR) absorption spectra. FIG. 5 is a graph showing the change with time of the UV-Vis absorption spectrum under irradiation with xenon light in the solid state and in the liquid state in Example 2. FIG. 6 is a graph showing the results of absorbance at a wavelength of 650 nm when 0.1% of an inorganic salt is added in Example 3.

  The present invention relates to a novel use invention of the Co—Ag—Co trinuclear complex represented by the formula (1). Formula (1) also includes the silver cobalt complex of formula (5) described in Non-Patent Document 1. Specifically, as shown in the examples described later, the silver cobalt complex of the formula (1) is not only excellent in antibacterial activity against (a) Staphylococcus aureus, Escherichia coli, Bacillus subtilis, Klebsiella pneumoniae, etc. It has excellent anti-fungal properties such as Aspergillus, Susbi and Black mold, has a wide range of antibacterial and anti-fungal properties, and (i) stable and durable even in the presence of light, heat and inorganic salts. The present invention has been completed by finding that it is excellent and (c) it can be applied to substrates such as papers and fabrics in either a solution or solid state and is excellent in workability.

  First, the compound of formula (1) used in the present invention will be described.

As shown in the above formula (1), the compound used in the present invention is a silver cobalt complex containing 1 Ag and 2 Co as metal ions, and having a thiolato ligand and an amine ligand as ligands. Specifically, it is a trinuclear complex of Co—Ag—Co having Ag ions as a central nucleus and Ag and Co bridged by S, and (C _1-3 ) —C—NH ₂ is bonded _to each S. It has the structure. Non-Patent Document 1 described above reports antibacterial activity against a specific Escherichia coli (Y ₁₀₉₀ ) for the silver cobalt complex (n = 1, R ¹³ = H) of the formula (2) included in the above formula (1). This compound is excellent in antibacterial activity against general-purpose Escherichia coli and Staphylococcus aureus, and has excellent antifungal activity against various types of molds. Nothing has been reported. As demonstrated in the examples described later, the above compound has an extremely low minimum inhibitory concentration (MIC) of fungi, and has an antifungal activity equivalent to or higher than that of silver ions. It has been found. It is well known that many antibacterial agents do not have an antifungal action, and that the silver-cobalt complex of the above formula (1) not only exhibits a wide range of antibacterial actions but also has an excellent antifungal action. This is a finding first discovered by the present invention.

The complex ion is +5 valent, and examples of the anion include NO ₃ , ClO ₄ , PF ₆ , BF ₄ , and CF ₃ SO _3, and are represented by the following formula.
(NO ₃ ) l (ClO ₄ ) m (PF ₆ ) n (BF ₄ ) o (CF ₃ SO ₃ ) p
In the formula, l, m, n, o, and p are integers of 0 to 5, and l + m + n + o + p = 5.

In the above formula (1), R ^{1 to} R ¹² bonded to N preferably have a crosslink as shown in the above formula (2) to the above formula (4), for example. However, the present invention is not limited to these. The antibacterial / antifungal agent of the present invention can contain at least one compound of formula (2) to formula (4).

  The silver cobalt complex used for this invention can be manufactured with the following method, for example.

  First, a cobalt complex is manufactured. Specifically, as raw materials, (a) a Co ion-containing compound such as cobalt nitrate, and (b) a sulfur-containing amine ligand such as 2-aminoethanethyl and cystamine; D, L-cysteine, D, L -Sulfur-containing ligands such as sulfur-containing amino acid ligands such as penicillamine and 2- or 4-dentate amine ligands such as (U) tris (2-aminoethyl) amine, triethylenetetramine, ethylenediamine in an aqueous solution. And then mixing while adjusting the pH to about 8.0-8.5. What is necessary is just to adjust pH suitably within the said range according to the kind of amine ligand to be used. The ratio of the above-mentioned raw materials (a) to (c) varies depending on the type of amine ligand used, but generally (a): (b): (c) = 1: 1: 1-1. It is preferable to control the ratio (molar ratio) to 1: 1: 2. While maintaining the above pH, the mixture is stirred at room temperature for 90 to 120 minutes. After removing unnecessary substances from the reaction solution by filtration, a cobalt complex crystal is obtained by adding an aqueous sodium perchlorate solution having a molar ratio to Co of about 2.5 to 5 times equivalent.

  Next, Ag ions are reacted with the cobalt complex thus obtained. Specifically, the above cobalt complex is dissolved in distilled water, and an Ag ion-containing compound such as silver nitrate is generally added at a ratio of Co: Ag = 2: 1 and reacted in an aqueous solution (generally, 30 to 40 ° C.). Let Next, when sodium nitrate, sodium perchlorate, or the like is added in a molar ratio of about 5 times as much as Ag and a molar ratio of about 2.5 times as much as Co, a desired silver-cobalt complex is obtained. In Examples described later, 2-aminoethanethiol was used as the sulfur-containing ligand.

In the examples described later, the experiment was carried out by producing the compound of the formula (5) in which n = 1 and R ¹³ = H in the above formula (2). Therefore, the examples may be referred to for details. . Further, the compounds of the above formula (3) and the above formula (4) can be produced by changing the kind of thiolate ligand or amine ligand and appropriately modifying pH, reaction temperature, and the like.

  The antibacterial / antifungal agent of the present invention may be used in a solid state or in a solution state dissolved in a solvent such as water. The concentration when used in a solution state may be appropriately adjusted so that the desired antibacterial / antifungal action is exhibited, but it is generally adjusted to a concentration of 0.1 to 2.0% by mass. preferable.

  Further, the antibacterial / antifungal agent of the present invention can be used while being supported on a substrate.

  The base material used in the present invention is not particularly limited as long as it is usually used for antibacterial / antifungal products carrying an antibacterial / antifungal agent. For example, paper / fiber products such as paper, fibers, fabrics, filters, etc. Kinds: Building materials such as wood and gypsum board; materials such as films, plastics, metals, and glass. As demonstrated in the examples described later, the silver-cobalt complex used in the present invention is extremely excellent in workability because it can be applied to the substrate in either a solid or liquid state.

  The method for obtaining the molded product (product) by supporting the antibacterial / antifungal agent of the present invention on a substrate is not particularly limited, and a generally used method may be appropriately employed depending on the type of the substrate. For example, after processing a base material into a product, a method of coating the surface of the product with an antibacterial / antifungal agent solution or immersing the product in the product may be used. Or you may employ | adopt methods, such as mixing a base material and an antibacterial and antifungal agent, before processing into a product.

  The blending amount of the antibacterial / antifungal agent supported on the base material may be appropriately controlled appropriately according to the type of the base material to be used and the application. For example, when the antibacterial / antifungal agent of the present invention is used for base materials such as papers and fabrics, it is preferable to add approximately 0.05 to 0.5% by mass with respect to the entire base material.

  As will be described later, the antibacterial / antifungal agent of the present invention has an excellent antibacterial / antifungal action. Examples of applicable bacteria include general-purpose bacteria such as Staphylococus aureus, Staphylococus aureus, Escherichia coli, Bacillus subtilis, Klebsiella pneumoniae subsp. Pneumoniae. Examples of molds include Aspergillus niger, Aspergillus niger, Alternaria alternate, and Black mold Cladosporium cladosporioides that are easy to breed in sanitary processed products such as baths. In addition, if the amount of antibacterial and antifungal agent is appropriately controlled, it can also be applied to blue mold Penicillium citrinum that is easy to reproduce in foods. It is also applicable to yeasts.

  Hereinafter, the present invention will be described in more detail with reference to examples, but the present invention is not limited by the following examples, and can be implemented with modifications within a range that can meet the purpose described above and below. They are all included in the technical scope of the present invention.

  In the following examples, the silver cobalt complex of the above formula (5) was used as a sample, and (a) antibacterial and antifungal properties (Example 1), (b) durability against light and inorganic salts (Examples 2 and 3). ) And (c) Antibacterial and antifungal properties (Example 4) when applied to a fabric were examined.

  The silver cobalt complex used for the present Example was manufactured with the following method.

First, 28 mmol of Co (NO ₃ ) ₂ · 6H ₂ O was dissolved in 200 cm ³ of water, and 50 cm ³ of a 28 mmol aqueous solution of 2-aminoethanethiol (abbreviated as “aet”) was added thereto. Furthermore, a 50 cm ³ aqueous solution of 28 mmol of tris (2-aminoethyl) amine (abbreviated as “tren”) was gradually added while adjusting the pH to 8.0. The mixture was stirred at room temperature for 90 minutes while maintaining the pH at 8.0. The reaction solution was naturally filtered to remove unnecessary substances. After filtration, 140 mmol of NaClO ₄ aqueous solution was added and left in the refrigerator overnight to deposit reddish purple crystals. The filtrate was separated by suction filtration, washed with 50 cm ³ of a mixed solvent of methanol and water (1: 1), and dried with acetone to obtain a cobalt complex [Co (aet) (tren)] (ClO ₄ ) ₂ . It was.

Next, 2.4 mmol of the produced [Co (aet) (tren)] (ClO ₄ ) ₂ was dissolved in 60 cm ³ of distilled water, and 1.2 mmol of AgNO ₃ dissolved in a small amount of distilled water was added thereto, and 30 ° C. For 5 hours. After filtering the reaction solution, 6 mmol of NaClO ₄ dissolved in a small amount of distilled water was added to precipitate red crystals or powder. This was subjected to suction filtration to collect crystals or powder, and then washed with cold water to obtain a compound of formula (5) which is a desired silver cobalt complex.

  In order to clarify the three-dimensional structure of the compound thus obtained, X-ray crystal structure analysis and nuclear magnetic resonance (NMR) spectrum measurement were performed. FIG. 1 shows the result of X-ray crystal structure analysis, and FIG. 2 shows the result of NMR spectrum. Further, visible-ultraviolet (UV-Vis) and infrared (IR) absorption spectra were measured, and spectroscopic characteristics were examined. The results are shown in FIGS.

Example 1 Antibacterial / Antifungal Test of Silver Cobalt Complex In this example, an antibacterial / antifungal test was performed as follows using the silver cobalt complex obtained by the above method.
(1) Preparation of sample solution used in test The above-described silver cobalt complex was dissolved in water to obtain a sample solution having a concentration of 1000 ppm. This solution was diluted in a series of 2 to prepare 500 ppm, 250 ppm, 125 ppm, 63 ppm, 32 ppm, 16 ppm, 8 ppm, 4 ppm, and 2 ppm concentrations. For comparison, silver ions (silver nitrate AgNO ₃ ) were used to prepare the same concentrations as described above.
(2) Antibacterial test
(2-1) Preparation of test bacterial solution As test bacteria, Staphylococus aureus, Escherichia coli, Bacillus subtilis, Bacillus subtilis Klebsiella pneumoniae subsp. Pneumoniae was used.

After inoculating each of the above bacteria on a normal agar medium (NA, Nissui), culturing at 35 ° C. for 24 hours, and using physiological saline to prepare a bacterial count of 10 ⁸ / mL A test bacterial solution was used.

(2-2) Test Method 0.1 mL of the test bacterial solution was inoculated into the sample solution of each concentration obtained as described above, and cultured at 35 ° C. for 24 hours. After culturing, the presence or absence of bacterial growth was observed with the naked eye, and MIC (ppm) was determined.

(3) Antifungal test
(3-1) Preparation of test spore solution As test mold, Aspergillus niger, Susukabi Alternaria alternate
The black mold, Cladosporium cladosporioides, was used.

Each mold is inoculated on a potato dextrose agar medium, cultured at 25 ° C. for 7 days, and then the number of spores is 10 ⁸ / mL using 0.05% tween 80 solution (surfactant Poly (Oxyethylene) sorbitan monooleate). The test spore solution was prepared as follows.

(3-2) Test Method Each sample solution obtained as described above was inoculated with 0.1 mL of the test spore solution and cultured at 25 ° C. for 7 days. After culturing, the presence or absence of mold growth was observed with the naked eye, and MIC (ppm) was determined.

  These results are shown in Tables 1-7. The smaller the MIC, the better the antibacterial / antifungal properties.

  From these tables, it can be considered as follows.

  First, when antibacterial properties are examined, it can be seen that the inventive examples are particularly superior in antibacterial properties against Staphylococcus aureus as compared with silver ions. It was also confirmed that the antibacterial action against other bacteria was generally good.

  Next, the antifungal property was examined. The present invention example was particularly superior in antifungal property against black mold as compared with silver ion, and other fungi were confirmed to have the same effect as silver ion.

  Thus, it turned out that the example of this invention is more useful as an antibacterial and antifungal agent than silver ion in that it has a particularly wide antifungal spectrum.

Example 2 Light Resistance Test In this example, the stability to light (ultraviolet light) in a solid state and a liquid state was examined using the silver cobalt complex obtained by the above method. Both the solid sample and the liquid sample were prepared using the powder of the silver cobalt complex.

(1) Light resistance test on solid sample First, 5.25 × 10 ⁻⁵ mol of a sample (powder) was weighed, and the time change of the UV-Vis absorption spectrum when irradiated with 200 W xenon light was measured. Here, an “L3451-01 type” ultraviolet irradiation device (200 W mercury-xenon lamp) manufactured by Hamamatsu Photonics was used. The distance from the light exit of the light guide was fixed at 15 cm. 7.5 × 10 ⁻⁶ mol was weighed at 0, 2 and 40 hours after irradiation to prepare a 1.5 mmol · dm ⁻³ aqueous solution using a 5 ml volumetric flask, and UV-Vis absorption spectrum (650 to 350 nm). Area).

(2) Light resistance test with solution sample A sample (powder) was weighed in 7.5 × 10 ⁻⁵ mol, and a 1.5 mmol · dm ⁻³ solution was prepared using a 50 ml volumetric flask. This was transferred to a beaker, irradiated with ultraviolet light in the same manner as in (1) above, and UV-Vis absorption spectrum (650 to 350 nm region) was measured after 0, 30, 60, 90 and 120 minutes.

  These results are shown in FIG. As shown in FIG. 5, in the solid state, almost no change in the spectrum was observed even under light irradiation for a long time of 40 hours. In the aqueous solution state, a slight change in the spectrum was observed when the irradiation time was lengthened, but no significant change was observed. Therefore, it was confirmed that the examples of the present invention are excellent in light stability both in the solid state and in the liquid state.

Example 3 Influence of inorganic salt In this example, in order to investigate the influence of coexisting salt ions, E. coli when various alkali metal salts and alkaline earth metal salts were added to the silver-cobalt complex obtained by the above method. The antibacterial effect on was investigated.

First, 0.5 mL (the concentration was 2000 ppm) of the sample solution obtained as described above was prepared. Also, E. coli Y ₁₀₉₀ (E. Coli strain Y1090) is dissolved in 1 L of water in LB (Luria-Bertani) liquid medium (bacto tryptone: 10 g, bacto yeast extract: 5 g, NaCl: 10 g, 5N NaOH: 0.2 ml). Prepared), cultured at 35 ° C. for 24 hours, and diluted 20-fold with LB liquid medium to obtain a test bacterial solution.

  0.5 mL of the above sample solution was added to 4.5 mL of the test bacterial solution to prepare a solution having a sample concentration of 200 ppm. A solution was prepared by adding various alkali metal salts and alkaline earth metal salts shown in FIG. 6 to a concentration of 1000 ppm (0.1%), and the effects of various inorganic salts on antibacterial activity were prepared. Evaluation was performed as follows.

  Specifically, the solution obtained as described above is placed in a test tube, cultured with shaking at 37 ° C. for 18 hours, and the absorbance at a wavelength of 650 nm using a visible-ultraviolet (UV-Vis) spectrophotometer ( Turbidity) was measured. For comparison, an inorganic salt and a sample to which no sample was added were prepared, and the absorbance was measured in the same manner as described above.

  The result when the concentration of the inorganic salt is 0.1% is shown in FIG.

  From this figure, it was found that the addition of 0.1% of alkali metal and alkaline earth metal chlorides, nitrates, sulfates and carbonates did not affect the antibacterial activity. Furthermore, even when chloride was used, silver turbidity of silver chloride was not observed, and it was also found that it was resistant to halide ions.

Example 4 Antibacterial / Antifungal Test after Light Irradiation after Applying Silver Cobalt Complex to Fabric In this example, the silver cobalt complex obtained as described above was applied to a fabric (base material), and light resistance was obtained. Antibacterial and antifungal properties were examined after the test.

(1) Preparation of test bacterial solution In this example, Staphylococus aureus, Escherichia coli, Bacillus subtilis, and Klebsiella pneumoniae subsp. Pneumoniae were used as test bacteria.

The above test bacteria were inoculated on a normal agar medium (NA, Nissui) and cultured at 35 ° C. for 24 hours. An ordinary bouillon diluted 20 times was used to prepare a test bacterial solution prepared so that the number of bacteria was on the order of 10 ⁵ / mL.

(2) Preparation of test spore solution In this example, as a test mold, Susukabi Alternaria alternate and Black mold Cladosporium cladosporioides were used.

Each mold is inoculated on a potato dextrose agar medium, cultured for 7 days at 25 ° C., and then the number of spores is on the order of 10 ⁵ / mL using a 20-fold diluted glucose peptone medium (Glucose Peptone Broth). What was prepared in this way was used as a test spore solution.

(3) Substrate In this example, a spunlace nonwoven fabric (KP9380 manufactured by Sansho Paper Industry Co., Ltd.) was used.

(4) Preparation of test specimen First, water was added to the silver-cobalt complex obtained as described above to prepare a concentration of 4000 ppm. Subsequently, this solution was apply | coated to the base material and the silver cobalt complex impregnation base material was obtained. A sprayer was used for application. The coating concentration on the substrate was adjusted so that the concentration was 3000 ppm from the weight change before and after coating.

The silver-cobalt complex-impregnated substrate thus obtained was irradiated for 100 hours at 28 ° C. and an irradiation illuminance of 550 W / m ² (this corresponds to irradiation for about one year under direct sunlight). The substrate after irradiation was cut aseptically and then 0.4 g in a sterile ampoule bottle was used as a test sample.

(5) Antibacterial activity after light resistance test The test specimen thus obtained was inoculated with 4 mL of the test bacterial solution and cultured at 35 ° C. for 24 hours. After culturing, the sample washed with 10 mL of sterilized water was used as a test solution and diluted with water to prepare a 10-fold diluted solution.

  This diluted solution was inoculated into SCDLP (Soybean Casein Digest Agar with Lecithin, Polysobate 80), an agar medium containing an inactivation agent, and cultured at 35 ° C. for 48 hours. After culturing, the formed colonies were counted, the number of viable bacteria (cells / mL) was counted, and antibacterial properties were evaluated. Thereby, the antibacterial action of the example of the present invention in an environment where light irradiation is performed for a long time can be confirmed.

  For comparison, an experiment similar to the above was performed on a silver-cobalt complex-impregnated base material (control) before the light resistance test. Thereby, the antibacterial action of the example of the present invention under a normal environment where no light irradiation is performed can be confirmed.

(6) Antifungal property after light resistance test Each of the test specimens thus obtained was inoculated with 4 mL of each test spore solution and cultured at 25 ° C. for 24 hours. After culturing, it was washed with 10 mL of sterilized water and diluted with water to obtain a 10-fold diluted solution.

  The diluted solution thus obtained was inoculated on GPLP (inactivating agent-containing fungal count measuring medium, Glucose Peptone Broth with Lecithin, Polysorbate 80) agar medium and cultured at 25 ° C. for 5 days. After culturing, the formed colonies were counted, the number of spores (number / mL) was counted, and the antifungal property after the light resistance test was evaluated. Thereby, the antifungal action of the example of the present invention in an environment where light irradiation is performed for a long time can be confirmed.

  For comparison, an experiment similar to the above was performed on a silver cobalt impregnated base material (control) before the light resistance test. Thereby, the anti-fungal action of the example of the present invention in a normal environment where no light irradiation is performed can be confirmed.

  These results are shown in Tables 8 to 13 (coating concentration on the base material of 3000 ppm).

  First, antibacterial properties (see Tables 8 to 11) will be considered.

  First, the results of “spun lace nonwoven fabric before light resistance test” in each table are referred to. When the number of viable bacteria after 48 hours is reduced compared to the initial number of bacteria, it can be said that the silver-cobalt complex of the example of the present invention has an antibacterial action under a normal environment where no light irradiation is performed. Referring to Tables 8 to 11, the number of viable bacteria after 48 hours was reduced for all the bacteria compared to the initial number of bacteria, and it was confirmed that the examples of the present invention have a wide range of antibacterial effects. In particular, for Staphylococcus aureus (Table 8) and Bacillus subtilis (Table 11), the viable count after 48 hours was less than 10 cells / mL, and an extremely strong antibacterial action was confirmed.

Next, the results of “Spunlaced nonwoven fabric after light resistance test” in each table are referred to. When the number of viable bacteria after 48 hours is reduced compared with the initial number of bacteria, the silver-cobalt complex of the present invention example is subjected to light irradiation for a long time (in an environment corresponding to irradiation for about one year under direct sunlight). It can be said that it has an antibacterial action. Referring to Tables 8 to 11, the number of viable bacteria after 48 hours decreased for all the bacteria compared to the initial number of bacteria, and the present invention example maintained a wide range of antibacterial effects even after the light resistance test. Was confirmed. In particular, for Staphylococcus aureus (Table 8) and Bacillus subtilis (Table 11), the number of viable bacteria after 48 hours was reduced to ¹⁰ 3 to 10 ² cells / mL order very strong antibacterial effect was confirmed .

  Next, antifungal properties (see Tables 12 and 13) will be considered. The anti-fungal test of this example is to measure the number of spores (the number of viable cells described in each table) in which the mold spores used grow in the order of spores → mycelium → spores. This is a test for quantitatively evaluating the antifungal property as compared with the fungus resistance test described in Z2911 (a qualitative test for evaluating only the growth of mycelia from mold spores). According to this anti-fungal test, if the number of viable bacteria after 5 days is not significantly greater than the initial bacterial count (the number of initial spores), it can be evaluated as “anti-fungal”.

  First, the results of “spun lace nonwoven fabric before light resistance test” in each table are referred to. For black mold, as shown in Table 12, the number of viable bacteria after 5 days was significantly reduced compared with the number of the first bacteria, and an excellent antifungal action was confirmed. In addition, as shown in Table 13, the effect on fungi was slightly inferior to that of black mold, but a significant increase in the number of viable bacteria after 5 days was not recognized, and an antifungal action was confirmed.

  Next, the results of “Spunlaced nonwoven fabric after light resistance test” in each table are referred to. The same tendency as described above was observed even in an environment where light irradiation was performed for a long time. Specifically, for black mold, as shown in Table 12, the number of viable bacteria after 5 days was significantly reduced compared to the number of initial bacteria, and an excellent antifungal action was confirmed even after the light resistance test. . In addition, as shown in Table 13, no significant increase in the number of viable bacteria was observed after 5 days, and antifungal activity was confirmed even after the light resistance test.

  From the above experimental results, it was confirmed that the silver-cobalt complex of the present invention has a good antibacterial and antifungal action, and the above action is sufficiently maintained even after the light resistance test.

Claims (3)

An antibacterial and antifungal agent excellent in both antibacterial and antifungal properties, comprising a Co-Ag-Co trinuclear complex represented by the following formula (1).

Where
n is an integer of 1 to 3,
R ^{1 to} R ¹² are the same or different and are H or an alkyl group having 1 to 6 carbon atoms;
Any group of R ^{1 to} R ³ bonded to N, any group of R ^{4 to} R ⁶ , any group of R ^{7 to} R ⁹ , and any group of R ^{10 to} R ¹² It may have a crosslink with any group of
R ¹³ is H or an alkyl group having 1 to 6 carbon atoms. The antibacterial / antifungal agent according to claim 1, comprising at least one of Co-Ag-Co trinuclear complexes represented by the following formula (2), the following formula (3), and the following formula (4).



In the formula, n and R ¹³ have the same meaning as before. The antibacterial and antifungal agent according to claim 1 or 2, which has excellent durability against light and inorganic salts.