JPH08283113A - Antimicrobial material - Google Patents

Abstract

PURPOSE: To obtain an antimicrobial material which is increased in its antimicrobial power and stability to light, heat and chlorine. CONSTITUTION: This antimicrobial material contains, as active ingredients, both of a silver complex and a zinc complex at a Ag/Zn molar ratio of 1/(1-6) supported by a porous particle carrier such as silica gel and the carrier is coated with a coating material consisting of at least one selected from SiO2 and Na2 O at least on a part of its surface to give the objective antimicrobial material. In addition, a nonvolatile inorganic acid or organic acid is used to adjust the pH in the range from 5 to 8.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an antibacterial material whose antibacterial component is a silver complex and a zinc complex.

[0002]

2. Description of the Related Art In recent years, bacterial contamination has become a problem in fields requiring attention from the viewpoint of hygiene such as synthetic resin products for kitchen appliances. In addition, there is a problem of contamination of building materials with bacteria and mold.

As a countermeasure, a method of mixing an antibacterial material in a synthetic resin and eluting the antibacterial material on the surface of the synthetic resin to sterilize the resin surface is used. In this case, the main antibacterial material has a structure in which a silver salt or a zinc salt as an antibacterial active ingredient is supported on a porous inorganic oxide. Also,
An organic antibacterial and antifungal material such as thiabendazole is used in order to positively elute the antibacterial and antifungal material in the synthetic resin and obtain a bactericidal and fungicidal effect on the resin surface and its surroundings.

Further, since the antibacterial material does not guarantee the permanent and complete sterilization of the surface, periodical surface sterilization can maintain the cleanliness. As the surface sterilization in this case, a chlorine-based bleaching agent such as sodium hypochlorite has generally been used conventionally.

Further, there has been proposed a refrigerator with an odor preventive and mildew proof unit and an air purifier to which phytoncides extracted from plants are attached.

[0006]

The antibacterial agent containing silver as an antibacterial active ingredient has a problem that the antibacterial effect is deteriorated and discolored due to the influence of light and temperature during resin molding. Further, since silver salts have high reactivity with chlorine and the like, which are often present in the environment, there is a problem that the antibacterial effect is deteriorated quickly in actual use. On the other hand, zinc salts are less prone to problems such as discoloration,
There was a problem that the antibacterial effect was weak.

As long as it is an antibacterial material, it naturally has an excellent antibacterial effect. However, a member to which an antibacterial material is applied, specifically, a resin or the like in which the antibacterial material is kneaded, has light, heat, chlorine or the like. It is also important that discoloration does not occur. There is a need for an antibacterial material that satisfies both these antibacterial effects and discoloration resistance.

Since the above-mentioned organic antibacterial and antifungal material has volatility, when it is contained in a synthetic resin, the surrounding environment of this synthetic resin is contaminated and the wastewater in contact with the surface of this synthetic resin is discharged. Since it contains an antibacterial and antifungal material, it causes pollution of drainage environment, and further has a problem that it affects activated sludge during sewage treatment.

Further, since plant extracts are mostly aromatic substances and have volatility, when these substances are mixed with resin, they evaporate due to heating during molding of the resin.
There is a problem that it cannot be mixed.

[0010]

The present invention is an antibacterial material containing both a silver complex and a zinc complex as an antibacterial active ingredient, the molar ratio of which is 1 to 6 zinc to 1 silver.
The active ingredient is supported on the same porous particle carrier which is an inorganic oxide, or after the active ingredient is supported on different inorganic oxide porous particle carriers, the molar ratio of silver is 1 On the other hand, it is an antibacterial material obtained by mixing zinc so as to be 1 to 6.

Also, at least one of a porous particle carrier carrying a silver complex and a zinc compound or a porous particle carrier carrying a zinc compound is mixed, and the molar ratio of the constituent is 1 to 6 of zinc to 1 of silver. Or a porous particle carrier supporting a zinc complex,
This is an antibacterial material in which at least one of a silver compound or a porous particle carrier carrying a silver compound is mixed, and zinc is mixed so that the constituent molar ratio is 1 to 6 of zinc to 1 of silver.

Further, at least a part of the surface of the carrier is
It is coated with a coating material composed of at least one selected from SiO ₂ and Na ₂ O.

In the present invention, the hydrogen ion concentration of the aqueous solution of the antibacterial active ingredient is determined by using a nonvolatile inorganic acid or organic acid, specifically boric acid, sulfuric acid, phosphoric acid, citric acid, tartaric acid, succinic acid and adipic acid. It is an antibacterial material prepared so as to fall within the range of 5 to 8.

[0014]

FUNCTION The silver complex is a compound that is more stable to light, heat, chlorine and the like than a silver salt, and exhibits excellent antibacterial properties at an appropriate concentration. The zinc complex is a compound that exhibits stable antibacterial properties, although it is slightly inferior to the silver complex. Furthermore, the zinc complex has 1 to 1 zinc for 1 silver.
The coexistence with the silver complex in a ratio of 6 has an action of contributing to stabilization of dissociation equilibrium under the coexistence of three of silver ions, zinc ions, and a ligand of the complex. The synergistic effect of the coexistence of the silver complex and the zinc complex has an action of enhancing the stability of the antibacterial effect and an action of suppressing discoloration caused by light, heat, chlorine and the like.

The antibacterial effect is exerted by the antibacterial active ingredient being dissolved in water which is a liquid containing bacteria. In general, an antibacterial active ingredient is eluted from an antibacterial material kneaded with a resin or the like into an aqueous solution adhering to the resin to exhibit an antibacterial effect. Specifically, the antibacterial effect is exhibited if it is possible to ensure that the silver complex and the zinc complex, which are the antibacterial active ingredients, coexist in the aqueous solution attached to the resin.

The following antibacterial materials that can ensure the above-mentioned state are considered. (1) An antibacterial material in which a silver complex and a zinc complex coexist at the same time.

(2) An antibacterial material in which a silver complex and a zinc complex are supported on the same porous particle carrier. (3) An antibacterial material in which a silver complex and a zinc complex are supported on different porous particle carriers and are mixed together.

(4) An antibacterial material formed by mixing a porous particle carrier supporting a silver complex and a zinc compound.

(5) An antibacterial material formed by mixing a porous particle carrier supporting a silver complex and a porous particle carrier supporting a zinc compound.

(6) An antibacterial material formed by mixing a zinc complex-supporting porous particle carrier and a silver compound.

(7) An antibacterial material formed by mixing a porous particle carrier supporting a zinc complex and a porous particle carrier supporting a silver compound.

In the above, when the ratio of zinc to silver is 1 to 6, the antibacterial material has stability of antibacterial effect and an effect of suppressing discoloration caused by light, heat and chlorine. .

Further, the synergistic effect of the stability of the complex and the antibacterial effect is extremely stably exhibited when the hydrogen ion concentration is within the range of 5-8.

[0024]

EXAMPLES The present invention will be described in detail below with reference to examples.

(Example 1) Water-soluble silver salt 10 such as silver acetate
0 parts by weight, 300 parts by weight of sodium sulfite, and 600 parts by weight of sodium thiosulfate were added to 1000 parts by weight of purified water and dissolved, and dissolved with sufficient stirring to obtain a silver thiosulfate complex aqueous solution.

In the above aqueous solution, the molar ratio of zinc content to silver content in the solution is 0, 0.5, 1, 2, 3, 4, 5, 6,
Water-soluble zinc salts such as zinc acetate in amounts of 7 and 10 were dissolved and sufficiently stirred to obtain a mixed aqueous solution of silver thiosulfate complex and zinc thiosulfate complex.

Further, a water-soluble zinc salt such as zinc acetate 200
Parts by weight, 300 parts by weight of sodium sulfite, and 600 parts by weight of sodium thiosulfate are added to purified water and dissolved,
It was dissolved with sufficient stirring to obtain a zinc thiosulfate complex aqueous solution.

The pH of the mixed aqueous solution of the silver thiosulfate complex and the zinc thiosulfate complex and the aqueous solution of the zinc thiosulfate complex.
Is between 6.5 and 8.

The carrier used in this example is "JIS Z
B-type silica gel described in "0701 Silica gel desiccant for packaging". This B-type silica gel is a silica gel having a low moisture absorption rate at low humidity, a high moisture absorption rate at high humidity, and a high total moisture absorption rate at high humidity, and its average particle size is about 3 μm.

The above silica gel was dried at 180 ° C. for 2 hours or more. The silica gel was added to the mixed aqueous solution of the silver thiosulfate complex and the zinc thiosulfate complex in an amount of 100 parts by weight with respect to 2 parts by weight of silver, and the mixture was sufficiently stirred. Then, the water absorbed in the carrier was promptly removed, and this was pulverized to a particle size of 5 μm to obtain an antibacterial active ingredient-supported silica gel. In addition, a zinc thiosulfate complex-supporting silica gel was obtained by the same method using a zinc thiosulfate complex aqueous solution.

100 parts by weight of silica gel carrying an antibacterial active ingredient was dispersed in a solution prepared by diluting and mixing 100 parts by weight of tetraethoxysilane as a reactive organosilicon compound with 100 parts by weight of ethyl alcohol, and then 20 parts by weight of pure water was added thereto. Is added to hydrolyze tetraethoxysilane, and at least a part of the surfaces of the silica gel supporting antibacterial active ingredient and the silica gel supporting zinc thiosulfate complex is coated with a tetraethoxysilane hydrolyzate and dried at 60 ° C. for 2 hours to prepare an antibacterial material. Got

An antibacterial property test was conducted using a polypropylene (hereinafter abbreviated as PP) resin containing 1% by weight of the antibacterial material produced by this method. The strain used in the test was E. coli.
IFO3301) and S. aureus IFO 127
32) and the test method was the dropping method.

The dropping method will be briefly described below. (1) Make 10 ⁴ cells / ml in a normal broth medium having a concentration of 1/100 of the standard concentration to prepare an inoculum solution.

(2) Put an antibacterial resin sample in a petri dish,
0.2 ml of the inoculum solution of 1 is dropped on the sample.

(3) Put (2) in a 37 ° C. incubator and incubate for 18 hours. (4) The inoculum solution on the sample is collected in a petri dish, and ordinary agar medium having a temperature of about 40 ° C. is poured into the dish to mix and allow to cool and solidify.

(5) Put (4) in a 37 ° C. incubator and incubate for 24 hours. (6) Count the colonies in the petri dish in (5).

The results of the antibacterial test in this example are shown below.

[0038]

[Table 1]

The above antibacterial test results show that the antibacterial effect is exhibited when the mixing molar ratio of silver and zinc, which are antibacterial active ingredients, is silver: zinc = 1: 1 to 6.

In the material for preparing the antibacterial active ingredient in this example, even if sodium bisulfite, potassium sulfite, or potassium bisulfite is used in addition to sodium sulfite, the mixing molar ratio of silver and zinc as the antibacterial active ingredient is Silver:
It was confirmed that the antibacterial effect was exhibited when zinc = 1: 1 to 6. Further, it can be confirmed that even if potassium thiosulfate is used in addition to sodium thiosulfate, the antibacterial effect is exhibited when the mixing molar ratio of silver and zinc, which is the antibacterial active ingredient, is silver: zinc = 1: 1-6. It was

Further, similar results were obtained by using zeolite, porous glass, zirconia, porous calcium carbonate, etc., in addition to silica gel as the porous particle carrier.

Example 2 Water-soluble silver salt 10 such as silver acetate
0 parts by weight, 300 parts by weight of sodium sulfite, and 600 parts by weight of sodium thiosulfate were added to 1000 parts by weight of purified water and dissolved, and dissolved with sufficient stirring to obtain a silver thiosulfate complex aqueous solution.

Next, 200 parts by weight of a water-soluble silver salt such as zinc acetate, 300 parts by weight of sodium sulfite, and 600 parts by weight of sodium thiosulfate were added to purified water and dissolved, and dissolved with sufficient stirring to form a zinc thiosulfate complex. An aqueous solution was obtained.

To the above-mentioned silver thiosulfate complex solution, 100 parts by weight of the same silica gel as in Example 1 was added to 4 parts by weight of silver, and the mixture was sufficiently stirred. Then, the water absorbed in the carrier was promptly removed, and this was pulverized to a predetermined particle size to obtain a silver thiosulfate complex-supported silica gel. In addition, 1 part to 12 parts by weight of zinc was added to the zinc thiosulfate complex solution.
The silica gel was added in an amount of 00 parts by weight and sufficiently stirred. Then, the water absorbed in the carrier was promptly removed, and this was pulverized to a particle size of 5 μm to obtain zinc thiosulfate-supported silica gel.

As a reactive organosilicon compound, 100 parts by weight of tetraethoxysilane was diluted and mixed with 100 parts by weight of ethyl alcohol, and the resulting solution was mixed with silver thiosulfate-supported silica gel 1.
After dispersing 00 parts by weight, 20 parts by weight of pure water is added to this to hydrolyze tetraethoxysilane, and then 60 ° C.
After drying for 2 hours, at least a part of the surface of the silica gel supporting silver thiosulfate was coated. The same coating was applied to silica gel supporting zinc thiosulfate.

Each of the coated silver thiosulfate-supporting silica gel and zinc thiosulfate-supporting silica gel was coated with a molar ratio of silver to zinc of 0.5, 1, 2, 3,
4, 5, 6, 7 and 10 were mixed to obtain an antibacterial material. In addition, the following tests were performed on only the silver thiosulfate-supported silica gel and the zinc thiosulfate-supported silica gel only.

PP containing 1 wt% of antibacterial material produced by this method
The resin was subjected to an antibacterial property test, and the same molar ratio as the antibacterial active ingredient silver and zinc, which was the same as in Example 1, was silver:
The result showing the antibacterial effect was obtained when zinc = 1: 1 to 6.

(Example 3) Water-soluble silver salt 10 such as silver acetate
0 parts by weight, 300 parts by weight of sodium sulfite, and 600 parts by weight of sodium thiosulfate were added to 1000 parts by weight of purified water and dissolved, and dissolved with sufficient stirring to obtain a silver thiosulfate complex aqueous solution.

To the above-mentioned silver thiosulfate complex solution, 100 parts by weight of the same silica gel as in Example 1 was added to 4 parts by weight of silver, and the mixture was sufficiently stirred. Next, the water absorbed in the carrier was promptly removed, and this was crushed to a particle size of 5 μm to obtain a silica gel carrying silver thiosulfate complex.

As a reactive organic silicon compound, 100 parts by weight of tetraethoxysilane was diluted and mixed with 100 parts by weight of ethyl alcohol, and the solution was mixed with silver thiosulfate-supported silica gel 1.
After dispersing 00 parts by weight, 20 parts by weight of pure water was added thereto to hydrolyze tetraethoxysilane, and at least one part of the surface of the silica gel supporting silver thiosulfate was coated with the tetraethoxysilane hydrolyzate. An antibacterial material was obtained by drying at 2 ° C for 2 hours.

The coated silica gel supporting silver thiosulfate and zinc acetate were contained in a molar ratio of silver of 1 to silver of 0.
5, 1, 2, 3, 4, 5, 6, 7 and 10 were mixed to obtain an antibacterial material. Further, the following tests were carried out on only silica gel supporting silver thiosulfate and only zinc acetate.

PP containing 1 wt% of antibacterial material produced by this method
The resin was subjected to an antibacterial property test, and the same molar ratio as the antibacterial active ingredient silver and zinc, which was the same as in Example 1, was silver:
The result showing the antibacterial effect was obtained when zinc = 1: 1 to 6.

(Example 4) Water-soluble silver salt 10 such as silver acetate
0 parts by weight, 300 parts by weight of sodium sulfite, and 600 parts by weight of sodium thiosulfate were added to 1000 parts by weight of purified water and dissolved, and dissolved with sufficient stirring to obtain a silver thiosulfate complex aqueous solution.

To the above-mentioned silver thiosulfate complex solution, 100 parts by weight of the same silica gel as in Example 1 was added to 4 parts by weight of silver, and the mixture was sufficiently stirred. Next, the water absorbed in the carrier was promptly removed, and this was crushed to a particle size of 5 μm to obtain a silica gel carrying silver thiosulfate complex.

Next, 10 parts by weight of zinc acetate was added to 100 parts of purified water.
0 part by weight was added and dissolved, and 100 parts by weight of the same silica gel as in Example 1 was added to 104 parts by weight of zinc, and the mixture was sufficiently stirred. Then, the water absorbed in the carrier is promptly removed to obtain a predetermined particle size of 5 μm.
It was pulverized to obtain silica gel supporting zinc acetate.

As a reactive organosilicon compound, 100 parts by weight of tetraethoxysilane was diluted and mixed with 100 parts by weight of ethyl alcohol, and the resulting solution was mixed with silver thiosulfate-supported silica gel 1.
After dispersing 00 parts by weight, 20 parts by weight of pure water was added thereto to hydrolyze tetraethoxysilane, and at least one part of the surface of the silica gel supporting silver thiosulfate was coated with the tetraethoxysilane hydrolyzate. An antibacterial material was obtained by drying at 2 ° C for 2 hours.

As a reactive organic silicon compound, 100 parts by weight of tetraethoxysilane was added to 100 parts of ethyl alcohol.
100 parts by weight of silica gel supporting zinc acetate was dispersed in a solution diluted with 1 part by weight, and then 20 parts by weight of pure water was added thereto to hydrolyze tetraethoxysilane, and at least 1 part of the surface of the silica gel supporting zinc acetate was dispersed. A part was coated with a tetraethoxysilane hydrolyzate and dried at 60 ° C. for 2 hours to obtain an antibacterial material.

The coated silver thiosulfate-supported silica gel and the zinc acetate-supported silica gel were mixed so that the molar ratio of zinc was 0.5, 1, 2, 3, 4, 5, 6, 7 and 10 with respect to silver. Then, an antibacterial material was obtained. In addition, the following tests were performed only on the silver thiosulfate-supported silica gel and the zinc acetate-supported silica gel only.

PP containing 1 wt% of antibacterial material produced by this method
The resin was subjected to an antibacterial property test, and the same molar ratio as the antibacterial active ingredient silver and zinc, which was the same as in Example 1, was silver:
The result showing the antibacterial effect was obtained when zinc = 1: 1 to 6.

(Example 5) 200 parts by weight of a water-soluble zinc salt such as zinc acetate, 300 parts by weight of sodium sulfite, and 600 parts by weight of sodium thiosulfate were added to 1000 parts by weight of purified water and dissolved, and dissolved with sufficient stirring. Then, a zinc thiosulfate complex aqueous solution was obtained.

To the above-mentioned zinc thiosulfate complex solution, 100 parts by weight of the same silica gel as in Example 1 was added to 8 parts by weight of zinc, and the mixture was sufficiently stirred. Then, the water absorbed in the carrier was promptly removed, and the carrier was pulverized to have a particle size of 5 μm to obtain a zinc thiosulfate complex-supported silica gel.

100 parts by weight of silica gel supporting zinc thiosulfate was dispersed in a solution prepared by diluting 100 parts by weight of tetraethoxysilane as a reactive organosilicon compound in 100 parts by weight of ethyl alcohol, and then 20 parts by weight of pure water was added thereto. Was added to hydrolyze the tetraethoxysilane, and at least a part of the surface of the silica gel supporting zinc thiosulfate was coated with the hydrolyzate of tetraethoxysilane, and dried at 60 ° C. for 2 hours to obtain an antibacterial material.

The coated silica gel supporting zinc thiosulfate and silver acetate were contained in a molar ratio of silver of 1 to silver of 0.
5, 1, 2, 3, 4, 5, 6, 7 and 10 were mixed to obtain an antibacterial material. In addition, the following tests were carried out on only silica gel supporting zinc thiosulfate and only silver acetate.

PP containing 1 wt% of antibacterial material produced by this method
The resin was subjected to an antibacterial property test, and the same molar ratio as the antibacterial active ingredient silver and zinc, which was the same as in Example 1, was silver:
The result showing the antibacterial effect was obtained when zinc = 1: 1 to 6.

(Example 6) Water-soluble silver salt 2 such as zinc acetate
00 parts by weight, 300 parts by weight of sodium sulfite, and 600 parts by weight of sodium thiosulfate were added and dissolved in 1000 parts by weight of purified water, and dissolved with sufficient stirring to obtain a zinc thiosulfate complex aqueous solution.

To the above zinc thiosulfate complex solution, 100 parts by weight of the same silica gel as in Example 1 was added to 8 parts by weight of zinc, and the mixture was sufficiently stirred. Then, the water absorbed in the carrier was promptly removed, and the carrier was pulverized to have a particle size of 5 μm to obtain a zinc thiosulfate complex-supported silica gel.

Next, 10 parts by weight of silver acetate was added to 1000 parts of purified water.
In addition to 10 parts by weight of silver, 100 parts by weight of the same silica gel as in Example 1 was added and dissolved therein. Then, the water absorbed in the carrier was promptly removed, and this was crushed to a predetermined particle size of 5 μm to obtain silver acetate-supported silica gel.

100 parts by weight of silica gel supporting zinc thiosulfate was dispersed in a solution prepared by diluting 100 parts by weight of tetraethoxysilane as a reactive organosilicon compound in 100 parts by weight of ethyl alcohol, and then 20 parts by weight of pure water was added thereto. Was added to hydrolyze the tetraethoxysilane, and at least a part of the surface of the silica gel supporting zinc thiosulfate was coated with the hydrolyzate of tetraethoxysilane, and dried at 60 ° C. for 2 hours to obtain an antibacterial material.

As the reactive organosilicon compound, 100 parts by weight of tetraethoxysilane was added to 100 parts of ethyl alcohol.
100 parts by weight of silica gel supporting zinc acetate was dispersed in a solution diluted to 1 part by weight, and then 20 parts by weight of pure water was added thereto to hydrolyze tetraethoxysilane to obtain at least 1 part of the surface of the silica gel supporting zinc acetate. A part was coated with a tetraethoxysilane hydrolyzate and dried at 60 ° C. for 2 hours to obtain an antibacterial material.

The coated zinc thiosulfate-supported silica gel and the silver acetate-supported silica gel were mixed so that the molar ratio of zinc was 0.5, 1, 2, 3, 4, 5, 6, 7 and 10 with respect to silver. Then, an antibacterial material was obtained. In addition, the following tests were performed only on the silica gel supporting zinc thiosulfate and the silica gel supporting silver acetate.

PP containing 1 wt% of antibacterial material produced by this method
The resin was subjected to an antibacterial property test, and the same molar ratio as the antibacterial active ingredient silver and zinc, which was the same as in Example 1, was silver:
The result showing the antibacterial effect was obtained when zinc = 1: 1 to 6.

Example 7 First, an antibacterial active ingredient-supporting silica gel was prepared in the same manner as in Example 1.

25 parts by weight of sodium silicate was added to 75 parts of purified water.
100 parts by weight of the silica gel supporting the antibacterial active ingredient is dispersed therein, and then at least one part of the surface of the silica gel supporting the antibacterial active ingredient is coated by evaporating water at 80 ° C. for 2 hours. Obtained antibacterial material.

PP containing 1 wt% of antibacterial material produced by this method
The resin was subjected to an antibacterial property test, and the same molar ratio as the antibacterial active ingredient silver and zinc, which was the same as in Example 1, was silver:
The result showing the antibacterial effect was obtained when zinc = 1: 1 to 6.

(Example 8) Water-soluble silver salt 10 such as silver acetate
0 parts by weight, 300 parts by weight of sodium sulfite, and 600 parts by weight of sodium thiosulfate were added to 1000 parts by weight of purified water and dissolved, and dissolved with sufficient stirring to obtain a silver thiosulfate complex aqueous solution.

In the above aqueous solution, a water-soluble zinc salt such as zinc acetate in an amount such that the molar amount of zinc is 4 with respect to the amount of silver 1 in the solution is dissolved and sufficiently stirred to obtain a silver thiosulfate complex and thiol sulfate. A mixed aqueous solution of a zinc sulfate complex was obtained.

A mixed aqueous solution of the silver thiosulfate complex and the zinc thiosulfate complex had pH values of 4, 5, 6, 7, 8, and 9.
Citric acid was added so that

After that, an antibacterial material was obtained in the same manner as in Example 1. The antibacterial test results of the PP resin containing 1 wt% of the antibacterial and antifungal agent produced by this method are shown below. The test method was the same as in Example 1.

[0079]

[Table 2]

The above antibacterial test results show the pH of the antibacterial active ingredient.
It shows that an antibacterial effect is exhibited when the value is 5 to 8.

As a reagent for adjusting the hydrogen ion concentration, in addition to citric acid, boric acid, sulfuric acid, phosphoric acid, adipic acid,
Similar results were obtained using succinic acid, tartaric acid and the like.

However, with acetic acid and hydrochloric acid, which are volatile, the components volatilize at a high temperature due to molding and the hydrogen ion concentration changes, so that no antibacterial effect was observed.

Example 9 By the same method as in Examples 1 and 4, the molar ratio of zinc to silver was 0, 0.5,
An antibacterial material having a pH value of 1, 2, 3, 4, 5, 6, 7, 10 and a pH value of 4, 5, 6, 7, 8, 9 was prepared.

P containing 1 wt% of antibacterial and antifungal agent produced by this method
The results of antibacterial test of P resin are shown below. The notation standard of ○ and × is 1/1000 with respect to the number of bacteria of resin with no antibacterial material added
Those having a bacterial count of less than were rated as ◯, and those having a bacterial count of 1/1000 or more were rated as x.

P containing 1 wt% of antibacterial and antifungal agent produced by this method
The results of antibacterial test of P resin are shown below. The test method was the same as in Example 1.

[0086]

[Table 3]

From the above antibacterial test results, the matrix having the optimum molar ratio of silver and zinc and the optimum pH as the antibacterial material is silver: zinc = 1: 1 to 6 and pH = 5 to 8.

[0088]

INDUSTRIAL APPLICABILITY The present invention can provide an antibacterial material that is stable against light, heat, chlorine and the like, because the silver complex and the zinc complex are antibacterial active ingredients. The silver complex and the zinc complex have a molar ratio of 1 to 1 of zinc to 1 of silver.
The coexistence of 6 exhibits an antibacterial effect and an effect of enhancing stability against light, heat, chlorine and the like.

Further, by setting the hydrogen ion concentration within the range of 5 to 8, it is possible to provide an antibacterial material having extremely high antibacterial efficacy and environmental stability.

Claims (12)

[Claims] 1. An antibacterial material characterized by containing a silver complex and a zinc complex as an antibacterial active ingredient, and containing a molar ratio of zinc to silver of 1 to 6. 2. A silver complex and a zinc complex, which are antibacterial active ingredients,
The antibacterial material according to claim 1, which is carried on the same porous particle carrier. 3. A silver complex and a zinc complex, which are antibacterial active ingredients, are supported on separate porous particle carriers, respectively, and then mixed so that the molar ratio is 1 to 6 of zinc to 1 of silver. The antibacterial material according to claim 1. 4. A porous particle carrier carrying a silver complex and at least one of a zinc compound and a porous particle carrier carrying a zinc compound are mixed, and the molar ratio of the constituent is 1 to 6 of zinc to 1 of silver. An antibacterial material characterized by being mixed so that 5. A porous particle carrier supporting a zinc complex and at least one of a silver compound or a porous particle carrier supporting a silver compound are mixed, and a molar ratio of silver is 1.
On the other hand, an antibacterial material, characterized in that zinc is mixed in an amount of 1 to 6. 6. The ligand according to claim 4 or 5, wherein the ligand forming a complex with silver ion or zinc ion is at least one selected from thiosulfate ion, ammonium ion and chloride ion. Antibacterial material. 7. The antibacterial material according to claim 1, wherein the silver complex is a silver thiosulfate complex and the zinc complex is a zinc thiosulfate complex. 8. The antibacterial material according to claim 2, wherein at least a part of the surface of the porous particle carrier carrying the antibacterial active ingredient is coated with a coating material. 9. The porous particle carrier is an inorganic oxide particle,
9. The antibacterial material according to claim 8, wherein the coating material is composed of at least one selected from SiO ₂ and Na ₂ O. 10. The antibacterial material according to claim 9, wherein the inorganic oxide particles are silica gel particles. 11. The antibacterial material according to claim 1, 4 or 5, wherein the aqueous solution of the antibacterial active ingredient has a hydrogen ion concentration within the range of 5 to 8. 12. The acid for adjusting the hydrogen ion concentration is
The antibacterial material according to claim 11, wherein the antibacterial material is at least one of a nonvolatile inorganic acid and an organic acid, and the acid coexists with the antibacterial active ingredient.