JP5259143B2 - Antibacterial agent - Google Patents

Description

  The present invention relates to an antibacterial agent having excellent discoloration resistance.

  In recent years, nosocomial infections caused by MRSA (methicillin-resistant Staphylococcus aureus) and food poisoning caused by O-157 (pathogenic Escherichia coli) have come to be regarded as problems. It is growing. Under such a background, various antibacterial agents are used for the purpose of preventing bacterial infection and microbial contamination. Antibacterial agents are generally roughly classified into organic antibacterial agents and inorganic antibacterial agents. Recently, inorganic antibacterial agents have attracted attention. This is because inorganic antibacterial agents are superior to organic antibacterial agents in terms of drug stability, safety to the human body, and the like, and are desirable from the viewpoint of environmental considerations. Furthermore, the inorganic antibacterial agent can be expected to have an excellent effect in the sustainability of the antibacterial effect. Inorganic antibacterial agents have antibacterial metal ions such as silver, copper, zinc, arsenic and lead as active species, and these have been used for a long time. Among these, silver ions are attracting the most attention because of their safety and the wide antibacterial spectrum.

However, it is known that antibacterial metal ions such as silver ions are reduced by exposure to heat or light and cause discoloration. As a technique for suppressing such discoloration, a method of supporting silver ions on an inorganic carrier such as zeolite or zirconium phosphate salt (JP-A Nos. 64-24860 and 2000-143420), imidazole, uracil, etc. Such as nitrogen-containing cyclic compounds such as thiol group-containing organic compounds and silver ions (JP-A Nos. 11-246213, 2004-224735, 2002-308708, etc.) are proposed. Has been.
However, antibacterial agents obtained by these methods have problems such as antibacterial metal ions eluting in the medium and causing discoloration, or discoloration due to insufficient stability to light, There is still a problem in terms of long-term stability.

  This invention is made | formed in view of such a problem, and it aims at providing the antibacterial agent which can suppress discoloration over a long term.

JP-A 64-24860 JP 2000-143420 A, etc. Japanese Patent Laid-Open No. 11-246213 JP 2004-224735 A JP 2002-308708 A

  As a result of intensive studies to achieve the above object, the present inventor has found that an antibacterial metal ion (a), an inorganic compound (b) that can serve as a carrier for the antibacterial metal ion, and a bis-form of a nitrogen-containing cyclic compound ( An antibacterial agent containing c) as an essential component was conceived and the present invention was completed.

That is, the present invention has the following characteristics.
1. Antibacterial metal ions (a), the inorganic compound which can be a carrier of the antimicrobial metal ions (b), and bis-a (c) viewed free nitrogen-containing cyclic compound,
An antibacterial agent, wherein the antibacterial metal ion (a) is a silver ion, and the bis-form (c) of the nitrogen-containing cyclic compound is a bistetrazole compound .
2. Reaction products of antimicrobial metal ions (a) and bis-nitrogen-containing cyclic compound (c) is, Ri Na is supported on an inorganic compound which can be a carrier of the antimicrobial metal ions (b),
An antibacterial agent, wherein the antibacterial metal ion (a) is a silver ion, and the bis-form (c) of the nitrogen-containing cyclic compound is a bistetrazole compound .
3. Antibacterial metal ions (a), the inorganic compound which can be a carrier of the antimicrobial metal ions (b), bis-nitrogen-containing cyclic compound (c), and viewed including the medium (d),
An antibacterial agent, wherein the antibacterial metal ion (a) is a silver ion, and the bis-form (c) of the nitrogen-containing cyclic compound is a bistetrazole compound.

  According to the present invention, discoloration caused by antibacterial metal ions can be suppressed, and long-term color stability can be ensured.

  Hereinafter, the best mode for carrying out the present invention will be described.

  The antibacterial agent of the present invention is an antibacterial agent comprising an antibacterial metal ion (a), an inorganic compound (b) that can serve as a carrier for the antibacterial metal ion, and a bis-form (c) of a nitrogen-containing cyclic compound as essential components. .

  Among these, examples of the antibacterial metal ions (a) (hereinafter also referred to as “component (a)”) include silver ions, copper ions, zinc ions, and the like, and among these, silver ions are particularly preferable. Such component (a) can be obtained, for example, from metal salts such as nitrates, sulfates and chlorides of antibacterial metal ions.

The inorganic compound (b) (hereinafter also referred to as “component (b)”) that can serve as a carrier for antibacterial metal ions plays a role of suppressing instantaneous elution of the component (a) and maintaining the antibacterial effect. . Such (b) component should just be what can support (a) component by ion exchange reaction, physical adsorption, or chemical adsorption.
Specific examples of the component (b) include activated carbon, activated alumina, silica gel, zeolite, hydroxyapatite, zirconium phosphate, titanium phosphate, potassium titanate, hydrous bismuth, hydrous zirconium, hydrotalcite, and the like. It is done. Of these, zeolite is particularly preferred in the present invention. Examples of the zeolite include natural zeolites such as chabasite, mordenite, erionite, and clinoptilolite, and synthetic zeolites such as A-type zeolite, X-type zeolite, and Y-type zeolite. Can be used. The particle size of such component (b) is usually about 0.01 to 100 μm.

The bis-form of the nitrogen-containing cyclic compound (hereinafter also referred to as “component (c)”) has a symmetric chemical structure having two nitrogen-containing cyclic structures in one molecule. In the present invention, such a specific chemical structure of the nitrogen-containing cyclic compound is considered to increase the stability of the metal ions in the antibacterial agent and obtain the effect of suppressing discoloration.
The bis-form of the nitrogen-containing cyclic compound is preferably a bistetrazole compound, such as 5,5'-bi (1H-tetrazole), 5,5'-methylenebis (2H-tetrazole), 5,5'-azobis (1H -Tetrazole), 5,5'-diazoaminobis (1H-tetrazole), 5,5 '-(2-butene-1,4-diyl) bis (1H-tetrazole), 5,5'-(1,4 -Phenylene) bis (2H-tetrazole), 5,5 '-(1,3-phenylene) bis (2H-tetrazole), 5,5'-tetramethylenebis (2H-tetrazole), 1,2-bis (1H -Tetrazol-5-yl) hydrazine, 5,5 '-(oxybisethylene) bis (1H-tetrazole), 4,5-bis (1H-tetrazol-5-yl) -2H-imidazo Le, bis (1H-tetrazol-5-yl) amine, and their derivatives (sodium salts, salts such as ammonium salts, etc.).

  It is desirable that a secondary amine and a tertiary amine are mixed in the nitrogen-containing cyclic structure in the bis body of the nitrogen-containing cyclic compound. When such a compound is used, in addition to its symmetric chemical structure, due to the combined action of ions generated by secondary amines and loan pairs possessed by tertiary amines, discoloration resistance and the like are further improved. It is presumed that an excellent effect is exhibited. As the bis-form of the nitrogen-containing cyclic compound in the present invention, 5,5′-bi (1H-tetrazole) (also referred to as “bistetrazole”) and its derivatives are particularly suitable.

The ratio of the component (a) to the component (c) depends on the valence of the antibacterial metal ion and the possible coordination number, the number of secondary amines and tertiary amines contained in the bis-form of the nitrogen-containing cyclic compound, etc. Although it depends, the molar ratio is about 2: 1 to 1: 4.
In the present invention, the total amount of the component (a) and the component (c) is desirably in the range of 0.001 to 20% by weight of the component (b), and in the range of 0.01 to 10% by weight. Is more desirable.

  The antibacterial agent of the present invention can be in the form of powder or liquid. Among these, as the powdery form, a product in which a reaction product of the component (a) and the component (c) is supported on the component (b) is preferable.

  In such a powdery form, a known method is a method for supporting the reaction product of component (a) and component (c) (hereinafter also simply referred to as “reaction product”) on component (b). May be used, and examples thereof include a method of supporting by ion exchange reaction and a method of supporting by physical adsorption or chemical adsorption. In addition, a thin layer of a metal compound is formed on the surface of the inorganic compound by a method of supporting by a binder, a method of supporting a metal compound by implanting it into an inorganic compound, a thin film forming method such as vapor deposition, dissolution and precipitation reaction, and sputtering. It is also possible to adopt a method of carrying by the above.

  Specifically, the powdered antibacterial agent is prepared by mixing and reacting an aqueous solution containing the salt of the component (a) and an aqueous solution containing the component (c), and then mixing the reaction product of (b). It can be produced by a method of adsorbing, followed by filtration, washing, drying and the like. At this time, the pH, concentration and the like of each aqueous solution can be appropriately set. As the salt of the component (a), an antibacterial metal ion nitrate, sulfate, chloride or the like can be used. In addition, after the drying step, operations such as pulverization can be performed as necessary. What is necessary is just to adjust the particle diameter of the powder finally obtained to about 0.01-100 micrometers.

  Any liquid form may be used as long as the medium (d) (hereinafter also referred to as “component (d)”) includes the component (a), the component (b), and the component (c). In this liquid form, the component (a) is desirably supported on the component (b). The component (c) may be in a state of being supported on the component (b) together with the component (a), or may be dissolved or dispersed in the medium (d) separately from the component (b). .

The medium (d) has an action of dissolving or dispersing the components (a) to (c). As the component (d) in the present invention, an aqueous medium containing water as an essential component and containing other water-soluble solvent or the like as appropriate is suitable. Among these, examples of the water-soluble solvent include alcohols, glycols, glycol ethers and the like. (D) A component may contain various additives, such as a thickener, a pH adjuster, a dispersing agent, antiseptic | preservative, and an antifoamer.
In such a liquid form, if the total amount of the component (a), the component (b) and the component (c) is 1 to 80% by weight, and the component (d) is 20 to 99% by weight, Good.

  In the liquid form, the production method is not particularly limited as long as the components (a) to (d) are included as essential components. As an example of a specific production method, the component (b) is mixed with an aqueous solution containing an antibacterial metal ion salt, the component (b) is supported on the component (b), and then filtered and washed ( Examples thereof include a method in which a composite of component a) and component (b) is obtained, and the composite is dispersed in an aqueous solution containing a bis salt of a nitrogen-containing cyclic compound. At this time, pH, concentration and the like of each aqueous solution can be appropriately set, and various additives can be mixed as necessary.

  The antibacterial agent of the present invention can be applied to various materials that require antibacterial properties. Examples of applicable materials include plastic, rubber, adhesive, glue, paint, ink, fiber, nonwoven fabric, wood, building material, paper, synthetic paper, leather, sealing material, concrete, and mortar. In order to incorporate the antibacterial agent of the present invention in these materials, an appropriate method may be selected in consideration of the form of the target material. Specific examples of the method include a mixing method, a melt mixing method, an impregnation method, a spray method, and a dispersion mixing method. The amount of the antibacterial agent used may be appropriately set according to the type and use of the material, but is usually about 0.001 to 10 parts by weight, more preferably 0.01 to 5 parts per 100 parts by weight of each material. About parts by weight. The antibacterial agent of the present invention can impart antibacterial properties to the materials as described above, and can also provide functions such as antifungal, deodorizing, deodorizing, decomposing, and purifying. In addition, when the antibacterial agent of the present invention is used for an aqueous paint, the discoloration suppressing effect is remarkable, which is preferable. This discoloration suppressing effect has an advantage that it is hardly affected by pH, halogen, and the like. The antibacterial agent of the present invention can be used in combination with other drugs (organic antibacterial agents and the like).

  Examples are given below to clarify the features of the present invention.

[I] Test Example 1
(Example 1-1)
A 0.1M silver nitrate aqueous solution was prepared by mixing silver nitrate with distilled water.
On the other hand, bistetrazole diammonium was mixed with distilled water, and the pH was adjusted to 11 with sodium hydroxide to prepare a 0.2M bistetrazole aqueous solution.
The aqueous bistetrazole solution thus obtained was mixed with an aqueous silver nitrate solution (a molar ratio of silver ions to bistetrazole of 1: 1), and the A-type zeolite powder (average particle size) was adjusted so that the amount of silver ions supported was 2% by weight. The mixture was stirred and dispersed for 3 hours. Next, the dispersion was filtered, washed with water, dried in an atmosphere at 50 ° C. for 24 hours, and pulverized to obtain a powdery antibacterial agent 1-A.
The antimicrobial agents obtained by the above methods were subjected to the following tests.

(1) Storage stability For 200 parts by weight of the acrylic resin emulsion, 130 parts by weight of white pigment (titanium dioxide), 100 parts by weight of extender pigment (heavy calcium carbonate), 5 parts by weight of dispersant, 5 parts by weight of thickener, A water-based paint was prepared by uniformly mixing 2 parts by weight of an antifoaming agent and 5 parts by weight of the antibacterial agent 1-A by a conventional method.
This water-based paint is applied on white paper with a film applicator with a clearance of 150 μm and dried for 48 hours under light-shielding conditions in a standard state (temperature 23 ° C., relative humidity 50%) to obtain a paper. Were measured with a spectrophotometer to calculate L ^{* 1} , a ^{* 1} , and b ^{* 1} .
Next, the water-based paint is sealed in a container, shielded from light, and stored at a predetermined temperature (5 ° C, 23 ° C, 50 ° C) for 50 days, then a coated paper is prepared in the same manner and measured with a spectrophotometer. , L ^{* 2} , a ^{* 2} and b ^{* 2} were calculated.
From the value obtained by the above method, the color difference (ΔE) before and after storage was calculated according to the following formula. Evaluation criteria were as follows: ：: Color difference of less than 0.5, ◯: Color difference of 0.5 or more and less than 1.0, Δ: Color difference of 1.0 or more and less than 2.0, x: Color difference of 2.0 or more.
^{△ E = {(L * 2} -L * 1) 2 + (a * 2 -a * 1) 2 + (b * 2 -b * 1) 2} 0.5

(2) Water resistance test The slate plate previously coated with a sealer was spray-coated with the coating material prepared in (1) above at a coating amount of 0.3 kg / m ² , and then in a standard condition under light-shielding conditions for 14 days. The dried sample was used as a test specimen. The color of this test body was measured with a spectrophotometer, and L ^{* 1} , a ^{* 1} , and b ^{* 1} were calculated.
Next, after immersing a test body in 23 degreeC water for 6 hours, it measured by the spectrophotometer again, and calculated L ^{* 2} , a ^{* 2} , b ^{* 2} .
From the value obtained by the above method, the color difference before and after the water immersion was calculated and evaluated according to the same evaluation criteria as in (1) above.

(3) Light resistance test A slate plate coated with a sealer in advance is spray-coated with the coating material prepared in (1) above at a coating amount of 0.3 kg / m ² , and then under standard conditions under light-shielding conditions for 14 days. The dried sample was used as a test specimen. The color of this test body was measured with a spectrophotometer, and L ^{* 1} , a ^{* 1} , and b ^{* 1} were calculated.
Next, the surface of the test specimen was irradiated with a 22 W fluorescent lamp at a distance of 15 cm for 50 days, and then again measured with a spectrophotometer to calculate L ^{* 2} , a ^{* 2} and b ^{* 2} .
From the values obtained by the above method, the color difference before and after irradiation was calculated, and evaluation was performed according to the same evaluation criteria as in (1) above.

(4) Antibacterial test For antibacterial activity, the minimum growth inhibitory concentration was evaluated by the solid medium method.
A 2-fold dilution series diluted solution was prepared so that the drug concentration was changed from 100 μg / ml to 6.5 μg / ml, and mixed with a standard agar medium sterilized with an antibacterial agent, which was cooled to harden the agar. The material was a solid medium. On the other hand, Staphylococcus aureus was suspended in sterile water to prepare a bacterial suspension having a concentration of 10 ⁶ CFU / ml. This bacterial suspension was streaked into a solid medium aseptically with a platinum loop and cultured for 24 hours in an incubator set at 37 ° C. After culturing, among the solid media having 5 or less colonies grown on the media, the one with the lowest drug concentration was defined as the minimum growth concentration.
The evaluation criteria were as follows: ◎: less than 500 ppm, ◯: 500 ppm or more and less than 1000 ppm, Δ: 1000 ppm or more and less than 2000 ppm, ×: 2000 ppm or more.

  The test results are shown in Table 1. In Example 1-1, excellent results could be obtained in any test.

(Example 1-2)
Copper sulfate was mixed with distilled water to prepare a 0.1 M aqueous copper sulfate solution.
On the other hand, bistetrazole diammonium was mixed with distilled water, and the pH was adjusted to 11 with sodium hydroxide to prepare a 0.2M bistetrazole aqueous solution.
The aqueous bistetrazole solution thus obtained was mixed with an aqueous copper sulfate solution (a molar ratio of copper ions to bistetrazole of 1: 1), and A type zeolite powder (average) so that the amount of copper ions supported was 2% by weight. Particle size 75 μm) was mixed and stirred for 3 hours. Next, this dispersion was filtered, washed with water, dried in an atmosphere at 50 ° C. for 24 hours, and pulverized to obtain a powdery antibacterial agent 1-B.
For antibacterial agent 1-B, various tests were conducted in the same manner as in Example 1-1. The test results are shown in Table 1.

(Comparative Example 1-1)
A 0.1M silver nitrate aqueous solution was prepared by mixing silver nitrate with distilled water.
The obtained aqueous silver nitrate solution was mixed with A-type zeolite powder (average particle size 75 μm) so that the supported amount of silver ions was 2% by weight, and stirred and dispersed for 3 hours. Next, this dispersion was filtered, washed with water, dried in an atmosphere at 120 ° C. for 6 hours, and pulverized to obtain a powdery antibacterial agent 1-C.
For antibacterial agent 1-C, various tests were conducted in the same manner as in Example 1-1. The test results are shown in Table 1.

(Comparative Example 1-2)
Except that 1H-imidazole was used instead of bistetrazole diammonium, a powdery antibacterial agent 1-D was obtained according to the method of Example 1-1, and various tests were performed. The test results are shown in Table 1.

(Comparative Example 1-3)
Except that 5-phenyl-1H-tetrazole was used in place of bistetrazole diammonium, powdered antibacterial agent 1-E was obtained according to the method of Example 1-1, and various tests were performed. The test results are shown in Table 1.

(Comparative Example 1-4)
Except that 5-methyl-1H-tetrazole was used instead of bistetrazole diammonium, powdered antibacterial agent 1-F was obtained according to the method of Example 1-1, and various tests were performed. The test results are shown in Table 1.

[II] Test example 2

(Example 2-1)
A 0.1M silver nitrate aqueous solution was prepared by mixing silver nitrate with distilled water. A type A zeolite powder (average particle size 75 μm) is mixed and dispersed in this silver nitrate aqueous solution and stirred for 3 hours. The dispersion is then filtered, washed with water, and dried in an atmosphere at 120 ° C. for 6 hours. By pulverizing, composite powder (silver ion loading amount 2% by weight) was obtained.
On the other hand, bistetrazole diammonium was mixed with distilled water, and the pH was adjusted to 11 with sodium hydroxide to prepare a 0.2M bistetrazole aqueous solution.
10 g of the composite powder was mixed and dispersed in 10 g of this bistetrazole aqueous solution to obtain a liquid (slurry) antibacterial agent 2-A.
The antimicrobial agents obtained by the above methods were subjected to the following tests.

(1) Change in appearance of slurry The antibacterial agent was sealed in a container, shielded from light, and the appearance after storage for 50 days in an atmosphere at 50 ° C. was visually confirmed. In this test, the evaluation was made in four stages (＞>○>Δ> ×) where “◎” indicates no discoloration and “×” indicates no significant discoloration.

(2) Storage stability For 200 parts by weight of acrylic resin emulsion, 130 parts by weight of white pigment (titanium dioxide), 100 parts by weight of extender pigment (heavy calcium carbonate), 5 parts by weight of dispersant, 5 parts by weight of thickener, A water-based paint was prepared by uniformly mixing 2 parts by weight of an antifoaming agent and 10 parts by weight of the antibacterial agent 2-A by a conventional method.
This water-based paint is applied on white paper with a film applicator with a clearance of 150 μm and dried for 48 hours under light-shielding conditions in a standard state (temperature 23 ° C., relative humidity 50%) to obtain a paper. Were measured with a spectrophotometer to calculate L ^{* 1} , a ^{* 1} , and b ^{* 1} .
Next, the water-based paint is sealed in a container, shielded from light, and stored at a predetermined temperature (5 ° C, 23 ° C, 50 ° C) for 50 days, then a coated paper is prepared in the same manner and measured with a spectrophotometer. , L ^{* 2} , a ^{* 2} and b ^{* 2} were calculated.
From the value obtained by the above method, the color difference (ΔE) before and after storage was calculated according to the following formula. Evaluation criteria were as follows: ：: Color difference of less than 0.5, ◯: Color difference of 0.5 or more and less than 1.0, Δ: Color difference of 1.0 or more and less than 2.0, x: Color difference of 2.0 or more.
^{△ E = {(L * 2} -L * 1) 2 + (a * 2 -a * 1) 2 + (b * 2 -b * 1) 2} 0.5

(3) Water resistance test The slate plate previously coated with a sealer was spray-coated with the coating material prepared in (2) above at a coating amount of 0.3 kg / m ² , and then under standard conditions under light-shielding conditions for 14 days. The dried sample was used as a test specimen. The color of this test body was measured with a spectrophotometer, and L ^{* 1} , a ^{* 1} , and b ^{* 1} were calculated.
Next, after immersing a test body in 23 degreeC water for 6 hours, it measured by the spectrophotometer again, and calculated L ^{* 2} , a ^{* 2} , b ^{* 2} .
From the value obtained by the above method, the color difference before and after water immersion was calculated and evaluated according to the same evaluation criteria as in (2) above.

(4) Light resistance test The paint prepared in (2) above was spray-coated at a coating amount of 0.3 kg / m ² on a slate plate previously coated with a sealer, and then in a standard state under light-shielding conditions for 14 days. The dried sample was used as a test specimen. The color of this test body was measured with a spectrophotometer, and L ^{* 1} , a ^{* 1} , and b ^{* 1} were calculated.
Next, the surface of the test specimen was irradiated with a 22 W fluorescent lamp at a distance of 15 cm for 50 days, and then again measured with a spectrophotometer to calculate L ^{* 2} , a ^{* 2} and b ^{* 2} .
From the value obtained by the above method, the color difference before and after irradiation was calculated, and evaluation was performed according to the same evaluation criteria as in (2) above.

(5) Antibacterial test For antibacterial activity, the minimum growth inhibitory concentration was evaluated by the solid medium method.
Prepare a 2-fold dilution series dilution so that the drug concentration is from 4000 μg / ml to 250 μg / ml, pour it in a standard agar medium sterilized with an antibacterial agent, cool it, and harden the agar. A solid medium was used. On the other hand, Staphylococcus aureus was suspended in sterile water to prepare a bacterial suspension having a concentration of 10 ⁶ CFU / ml. This bacterial suspension was streaked into a solid medium aseptically with a platinum loop and cultured for 24 hours in an incubator set at 37 ° C. After culturing, among the solid media having 5 or less colonies grown on the media, the one with the lowest drug concentration was defined as the minimum growth concentration.
The evaluation criteria were ◎: less than 1000 ppm, ◯: 1000 ppm or more and less than 2000 ppm, Δ: 2000 ppm or more and less than 4000 ppm, and x: 4000 ppm or more.

  The test results are shown in Table 2. In Example 2-1, excellent results could be obtained in any test.

(Example 2-2)
Copper sulfate was mixed with distilled water to prepare a 0.1 M aqueous copper sulfate solution. A type A zeolite powder (average particle size 75 μm) is mixed and dispersed in this copper sulfate aqueous solution and stirred for 3 hours. The dispersion is then filtered, washed with water, and dried in an atmosphere at 120 ° C. for 6 hours. By pulverizing, composite powder (copper ion carrying amount 2% by weight) was obtained.
On the other hand, bistetrazole diammonium was mixed with distilled water, and the pH was adjusted to 11 with sodium hydroxide to prepare a 0.2M bistetrazole aqueous solution.
A liquid (slurry) antibacterial agent 2-B was obtained by mixing and dispersing 10 g of the composite powder to 10 g of this bistetrazole aqueous solution.
Various tests were performed in the same manner as in Example 2-1, using the antibacterial agent 2-B instead of the antibacterial agent 2-A. The test results are shown in Table 2.

(Comparative Example 2-1)
A 0.1M silver nitrate aqueous solution was prepared by mixing silver nitrate with distilled water.
A-type zeolite powder (average particle size 75 μm) was mixed and dispersed in the obtained silver nitrate aqueous solution and stirred for 3 hours. Next, this dispersion was filtered, washed with water, dried in an atmosphere at 120 ° C. for 6 hours, and pulverized to obtain a composite powder (silver ion loading 2% by weight).
Antibacterial agent 2-C was obtained by mixing and dispersing 10 g of this composite powder in 10 g of distilled water.
Various tests were conducted in the same manner as in Example 2-1, using the antibacterial agent 2-C instead of the antibacterial agent 2-A. The test results are shown in Table 2.

(Comparative Example 2-2)
Except for using 1H-imidazole instead of bistetrazole diammonium, antibacterial agent 2-D was obtained according to the method of Example 2-1, and various tests were performed. The test results are shown in Table 2.

(Comparative Example 2-3)
Except for using 5-phenyl-1H-tetrazole instead of bistetrazole diammonium, antibacterial agent 2-E was obtained according to the method of Example 2-1, and various tests were performed. The test results are shown in Table 2.

(Comparative Example 2-4)
Except for using 5-methyl-1H-tetrazole instead of bistetrazole diammonium, antibacterial agent 2-F was obtained according to the method of Example 2-1, and various tests were performed. The test results are shown in Table 2.

Claims (3)

Antibacterial metal ions (a), the inorganic compound which can be a carrier of the antimicrobial metal ions (b), and bis-a (c) viewed free nitrogen-containing cyclic compound,
An antibacterial agent, wherein the antibacterial metal ion (a) is a silver ion, and the bis-form (c) of the nitrogen-containing cyclic compound is a bistetrazole compound . Reaction products of antimicrobial metal ions (a) and bis-nitrogen-containing cyclic compound (c) is, Ri Na is supported on an inorganic compound which can be a carrier of the antimicrobial metal ions (b),
An antibacterial agent, wherein the antibacterial metal ion (a) is a silver ion, and the bis-form (c) of the nitrogen-containing cyclic compound is a bistetrazole compound . Antibacterial metal ions (a), the inorganic compound which can be a carrier of the antimicrobial metal ions (b), bis-nitrogen-containing cyclic compound (c), and viewed including the medium (d),
An antibacterial agent, wherein the antibacterial metal ion (a) is a silver ion, and the bis-form (c) of the nitrogen-containing cyclic compound is a bistetrazole compound .