JPH07316009A - Antibacterial, antiviral and antifungal agent and its complex - Google Patents

Abstract

PURPOSE:To produce a durable antibacterial, antiviral and antifungal agent or its complex scarcely soluble in aqueous solution and exhibiting stable antibacterial effect, etc., on a resin surface by bonding an antibacterial metal or ion to the SH group of cysteine. CONSTITUTION:This antibacterial, antiviral and antifungal agent is produced by bonding an antibacterial metal or its ion to the SH group of cysteine, thereby making the metal scarcely insoluble in water. The metal is preferably selected from silver, copper, zinc and nickel. An antibacterial, antiviral and antifungal complex is produced by supporting the antibacterial, antiviral and antifungal agent on a carrier selected especially from porous glass, porous calcium carbonate and silica gel. A coating layer is preferably applied to the surface of the complex. The antibacterial, antiviral and antifungal agent or its complex does not cause environmental pollution even if eluted from the resin and is resistant to thermal discoloration. It exhibits strong antibacterial, antifungal and antiviral actions even in the presence of chlorine ion.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an antibacterial and antiviral antifungal agent and an antibacterial and antiviral antifungal complex using cysteine-metal and having a persistent antibacterial and antiviral and antifungal performance.

[0002]

2. Description of the Related Art In recent years, when synthetic resin products are used in fields such as kitchen appliances where hygiene needs to be paid attention to, contamination of resin surfaces by bacteria has become a problem.
In addition, there are problems such as germs and molds on the surface of caulking material used as a building material, resulting in poor hygiene and appearance. As a countermeasure, there is used a method in which an antibacterial and antifungal composition is mixed in a synthetic resin and the composition is eluted on the surface of the resin for sterilization. Conventionally, organic antibacterial and antifungal materials such as thiabendazole have been used in order to positively elute the antibacterial and antifungal material in the synthetic resin and obtain an antibacterial and antifungal effect on the surface of the resin and its surroundings. Various kinds of topical antibacterial agents or antifungal agents have been used, and examples thereof include aqueous solutions such as silver nitrate, carboxylic acid, N-long chain acylamino acid metal, clotrimazole, and nitric acid. There is a topical antibacterial agent containing miconazole, iconazole nitrate, tricomycin, etc. in an external base such as cream, liquid, sol. Furthermore, a refrigerator with an odor preventive and antifungal unit in which a phytoncide extracted from a plant is attached to a refrigerator and an air purifier have been proposed. In addition, antibacterial materials generally do not guarantee permanent and complete antibacterial properties of the surface, so that regular surface sterilization can maintain more cleanliness. In this case, a chlorine-based bleaching agent such as sodium hypochlorite is often used as the surface sterilization method.

[0003]

Since the above-mentioned organic antibacterial and antifungal agent has volatility, when it is contained in a synthetic resin, the environment surrounding the synthetic resin is contaminated. In addition, since the antibacterial and antifungal agent is contained in the effluent that comes in contact with the surface of this synthetic resin, there is a problem that it may cause pollution of wastewater environment or affect activated sludge during sewage treatment. . In the case of a silver-based antibacterial agent using silver ions (Ag ⁺ ), the silver ions react with chlorine ions in the chlorine-based bleaching agent to form insoluble silver chloride, and silver chloride has high photoreactivity. There is a problem that the antibacterial performance is deteriorated as well as blackening due to the immediate change to metallic silver or silver oxide. In addition, when kneading into a resin, the heating temperature is 200 ° C. or higher, so that the antibacterial material is discolored and it is difficult to obtain a white resin molded product. Further, the above-mentioned plant extract is mostly an aromatic substance and has volatility, so that when these substances are mixed in the resin, they are evaporated by the heating during the molding of the resin, so that it cannot be mixed in. was there.

In view of the above problems, it is an object of the present invention to provide an antibacterial antiviral antifungal agent which is difficult to dissolve in an aqueous solution and exhibits a stable antibacterial effect on a resin surface, and a complex thereof. Another object of the present invention is to provide an antibacterial antiviral antifungal agent and a complex thereof which hardly cause environmental pollution even when eluted from the resin. Further, it is an object of the present invention to provide an antibacterial antiviral antifungal agent which does not discolor by heat and a complex thereof.

[0005]

The antibacterial and antiviral antifungal agent of the present invention comprises an SH group of cysteine to which an antibacterial metal or its ion is bound. Here, the metal having antibacterial properties is preferably at least one selected from the group consisting of silver, copper, zinc and nickel. The antibacterial / antiviral / antifungal composite of the present invention comprises a carrier selected from the group consisting of porous glass, porous calcium carbonate and silica gel, which carries the antibacterial / antiviral and antifungal agent. This composite preferably has a coating layer on its surface. Further, the coating layer is preferably formed of silicon dioxide produced by hydrolysis of alkoxysilane.

[0006]

[Function] Cysteine is closely related to the three-dimensional structure of the proteins forming the individual organism. In other words, it is an essential amino acid for living organisms and is easily taken up. This inhibits the antibacterial performance and the like of the antibacterial metal and the formation of biological solids, and exerts a very strong antibacterial performance and the like. In the present invention, by binding an antibacterial metal to the SH group of cysteine,
It is sparingly soluble in water.

The antibacterial and antiviral antifungal complex of the present invention has a stable antibacterial and antiviral antifungal effect because the antibacterial and antiviral antifungal agent is carried on a porous carrier. Further, when the metal binding to cysteine is silver, copper, zinc or nickel, it is unlikely to cause environmental pollution even if it is eluted from the resin. Further, when a coating layer is formed on the outer surface of the composite, the sustained release property of the antibacterial antiviral antifungal agent is further improved. Further, even when used in an atmosphere with a high chlorine concentration, there is no discoloration or deterioration of the antibacterial antiviral antifungal performance.

[0008]

EXAMPLES The preferred antibacterial and antiviral antifungal agent of the present invention will be described in more detail. This antibacterial and antiviral antifungal agent is prepared by dissolving D or L-cysteine in pure water and adding silver, copper, zinc and It is obtained by adding a salt of a metal selected from the group consisting of nickel and binding the metal or its ion to the SH group of cysteine. The metal salt used here may be a complex salt of the above metal such as a thiosulfato silver complex salt. Next, to produce the composite,
A carrier is added to the solution of the antibacterial and antiviral antifungal agent, the carrier is adsorbed or impregnated with the antibacterial and antiviral antifungal agent, and then dried to allow the antibacterial and antiviral antifungal agent to have antibacterial properties.

As the carrier, silica gel, porous glass or porous calcium carbonate is used. Porous glass includes (1) sintering of fine-particle glass powder, (2) hydrolysis of inorganic salts and metal alkoxides (silica gel can be obtained by this method, but it is not included here in a narrow sense).
(3) Obtained by a method such as phase separation of glass.
(1) is a powder obtained by wet-milling SiO ₂ —CaO—Na ₂ O-based glass for 10 hours, adding and mixing 2% of carbonate as a foaming agent, and granulating the mixture to burn at 850 ° C. for 100 seconds. Make glass and use this granular foam glass (5-20
(Water absorption of volume%) is immersed in warm water of 70 ° C. for 4 days to remove soluble alkali components, and openings are formed in the surface layer of foam glass and closed cells.
As a result, a water absorption of 20 to 50% by volume is obtained. (3) is a phase rich in B ₂ O ₃ —Na ₂ O in acid water, which is obtained by heat treating SiO ₂ —Na ₂ O—B ₂ O ₃ —Al ₂ O ₃ type glass at 500 to 650 ° C. to cause phase separation. To be manufactured. As the composition system of glass, other than the above, SiO ₂ —B ₂ O ₃ —Z
rO ₂ -Na ₂ O-ZnO-based or SiO ₂ chromatography Na ₂ O-P ₂ O ₅
System, SiO ₂ -B ₂ O ₃ over CaO-Al ₂ O ₃ system, SiO ₂ -
There is also a B ₂ O ₃ —CaO—MgO—Al ₂ O ₃ —TiO ₂ system. In the porous glass obtained in (1) to (3), the pore diameter can be arbitrarily selected from a wide range of 40 angstrom to 40 μm. In addition, porous calcium carbonate having a pore size of 1.5 to 2.0 μm is commercially available (for example, Phomuse P manufactured by Kowa Chemical Industry Co., Ltd.).

The coating layer formed on the outer surface of the composite is
Silicon dioxide produced by hydrolyzing an alcohol solution of alkoxysilane by the sol-gel method is preferable. This coating layer enables adjustment of the duration of the antibacterial and virus-suppressing drug treatment effect of the complex. That is, it is possible to control the duration of antibacterial, antiviral and antifungal effects by controlling the area and thickness of the coating layer. The alkoxysilane for forming this coating layer has an alkoxyl group having 1 to 4 carbon atoms, and the alcohol has 1 carbon atoms.
Those of up to 4 are suitable.

Example 1 Silver nitrate was used as a silver salt. 1.7 g of AgNO ₃ was dissolved in 15 ml of 1N nitric acid solution. On the other hand, L-cysteine methyl ester 0.17
g was dissolved in 15 ml of 1N nitric acid solution. Subsequently, these two solutions were mixed and allowed to stand at 4 ° C., and then the precipitate was collected by filtration and dried under reduced pressure at 60 ° C. About the antibacterial antifungal antiviral agent thus obtained (hereinafter, abbreviated as antibacterial agent),
The following antibacterial and antifungal and antiviral tests were conducted.

Anti-mildew test: According to the halo test method based on the mildew-proof test for textiles in the mold resistance test (JIS Z 2911) of Japanese Industrial Standards. The mold used was Cladosporium cladosporioid.
es), Chaetomium globosu
m), Penicillium citrinu
m) and Asperigillus nige
r). The evaluation was carried out 14 days later. Antibacterial test: Escherichia col
i), Staphylococcu aureus
s aureus), Bacillus subtilli
s) was used according to the dropping method. The evaluation was carried out at 37 ° C. and after 24 hours. Anti-virus test: Herpes simplex virus type 2, measles virus and AIDS virus were used as viruses with an infectious titer of 10 ⁴ TCID ₅₀ , and Vero was used.
It was judged by the presence or absence of infection of cells. In either case,
The test results are shown below. ◎: 100% suppression, ○: 90% suppression, △: 80% suppression,
X: 50% suppression

The test results are shown in Table 1. Antibacterial agent concentration 1
At 00 ppb, a growth inhibitory effect against bacteria, fungi and viruses was observed. Although L-cysteine methyl ester was used in the above examples, the same results were obtained with the D-form.

[0014]

[Table 1]

Example 2 Copper acetate, zinc chloride and nickel acetate were used as metal salts. These metal salts 0.
1 mol was dissolved in 15 ml of 1N nitric acid acidic solution. next,
0.01 mol of L-cysteine methyl ester was dissolved in 15 ml of 1N nitric acid acidic solution. Subsequently, these two solutions were mixed and allowed to stand at 4 ° C., and then the precipitate was recovered and dried to obtain an antibacterial agent. The same antibacterial and antifungal and antiviral tests as in Example 1 were conducted on these antibacterial agents. The test results are shown in Table 2. As a result, strong antibacterial, antifungal and antiviral effects were observed even with copper, zinc and nickel. Although L-cysteine methyl ester was used in the above examples,
The same results were obtained with the D-form.

[0016]

[Table 2]

Example 3 1.7 g of AgNO ₃ was dissolved in 15 ml of nitric acid solution. Next, 1.7 g of L-cysteine methyl ester was dissolved in 15 ml of a nitric acid solution. Subsequently, these two solutions were mixed to obtain a silver compound solution.
Next, this silver compound solution was adsorbed on porous glass or porous calcium carbonate having an average particle diameter of 10 μm of the carrier so that the silver compound had a concentration of 3% with respect to the carrier, and dried. The silver compound solution adsorbed on or impregnated on the carrier is dried at a normal pressure and a temperature of 4 to prevent decomposition of the silver compound.
It was set to 0 ° C. In this way, a composite having the silver compound supported on the carrier was obtained. The antibacterial, antifungal and antiviral test results of this complex are shown in Table 3. Concentration of complex 1000pp
In m, a growth inhibitory effect against fungi, mold and virus was observed.

[0018]

[Table 3]

Next, Table 4 shows the relationship between the pore size of the porous glass used as the carrier and the elution rate of Ag ⁺ ions in water at room temperature. The amount of glass is 10m of water
The amount was 1 g per liter and the dissolution rate per hour was shown.
The elution rate when using porous calcium carbonate having a pore size of 1.5 to 2.0 μm as a carrier was 1350 pp.
It was m / h.

[0020]

[Table 4]

Comparative Example 1 An antibacterial composite was prepared in the same manner as in Example 3 except that a commercially available silica glass powder (not porous) was used. Elution rate is 25,000
It was confirmed that it showed extremely low sustained-release property at ppm / h.

Example 4 1 g of the complex carrying the silver compound of Example 3 was added to a solution of 1 ml of tetraethoxysilane in 1 ml of ethyl alcohol and mixed well.
Tetraethoxysilane was hydrolyzed by dropping about 0.2 ml of pure water to form a coating layer of silicon dioxide on the surface of the composite.

[Example 5] To a solution prepared by adding 1 ml of a silicon resin solution to 1 ml of chloroform, 1 g of the complex carrying the silver compound of Example 3 was added, mixed well, dried under reduced pressure, and then dried at 100 ° C for 7 hours. The silicon resin film is cured by heating for a time. In this way, the surface was coated with silicone resin. With respect to the antibacterial / antiviral / antifungal complexes of Examples 4 and 5, the elution rate of silver ions was examined in the same manner as in Example 3 and the results are shown in Table 5. Ag ⁺
It was found that the ion elution rate was 1/10 to 1/200 when the coating layer was not formed, when the coating layer was not formed.

[0024]

[Table 5]

[Example 6] The antibacterial composites of Examples 4 and 5 were uniformly dispersed at a ratio of 1.5 parts by weight to 100 parts by weight of a resin when molding a polypropylene resin to obtain a resin molded product. It was This resin molded product was subjected to the same antifungal test and antibacterial test as in Example 1. The results are shown in Table 6. Those having a deterrent effect of 90% or more were expressed as "effective". From Table 6, the antibacterial and antifungal composite of this example is
It can be seen that it has a practical antibacterial and antifungal performance.

[0026]

[Table 6]

[0027]

INDUSTRIAL APPLICABILITY As described above, the antibacterial and antifungal antiviral agent and the complex of the present invention have practical antibacterial and antifungal and antiviral properties, and exhibit stable antibacterial and other effects on the resin surface. Further, since it has low volatility, it is less likely to be eluted than in the resin, and even if it is eluted, it is unlikely to cause environmental pollution. Furthermore, it exerts a strong antibacterial antifungal and antiviral effect even in the presence of chloride ions. Further, it has heat resistance up to about 240 ° C., and discoloration of the resin can be eliminated during dispersion molding into the resin.

 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Yasuo Mizuno 1006 Kadoma, Kadoma City, Osaka Prefecture Matsushita Electric Industrial Co., Ltd. (72) Atsushi Nishino 1006 Kadoma, Kadoma City, Osaka Prefecture Matsushita Electric Industrial Co., Ltd.

Claims (4)

[Claims] 1. An antibacterial, antiviral and antifungal agent in which a metal having an antibacterial property or its ion is bound to the SH group of cysteine. 2. The antibacterial and antiviral antifungal agent according to claim 1, wherein the metal is at least one selected from the group consisting of silver, copper, zinc and nickel. 3. An antibacterial and antiviral antifungal composite comprising a carrier selected from the group consisting of porous glass, porous calcium carbonate and silica gel and carrying the antibacterial and antiviral and antifungal agent according to claim 1. 4. The antibacterial / antiviral / antifungal composite according to claim 4, which has a coating layer on its surface.