JP3347875B2 - Antibacterial antiviral antifungal agent and its complex - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

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

[0002]

2. Description of the Related Art In recent years, when synthetic resin products are used in a field where hygiene needs to be paid attention, such as kitchen utensils, contamination of the resin surface with bacteria has become a problem.
In addition, there are problems such as bacteria and fungi growing on the surface of the caulking material used as a building material, resulting in poor hygiene and appearance. As a countermeasure, a method has been used in which an antibacterial and antifungal composition is mixed into a synthetic resin, and the composition is eluted on the resin surface to sterilize the resin. Conventionally, an organic antibacterial and antifungal material such as thiabendazole has been used in order to actively elute the antibacterial and antifungal material in the synthetic resin and obtain an antibacterial and antifungal effect on and around the resin surface. As the topical antibacterial agent or antifungal topical agent, various agents are used, for example, an aqueous solution such as silver nitrate, further, carboxylic acid, N-long chain acylamino acid metal, clotrimazole, nitric acid There are topical antibacterial agents containing miconazole, iconon nitrate, tricomycin, and the like in an external base such as cream, liquid, or sol. Further, refrigerators and air purifiers with a deodorant and fungicide unit in which phytoncides extracted from plants are attached to a refrigerator have been proposed. In addition, antibacterial materials generally do not guarantee the permanent and complete antibacterial properties of their surfaces, so that regular surface sterilization can maintain more cleanliness. Generally, a chlorine bleach such as sodium hypochlorite is often used as a surface sterilization method in this case.

[0003]

Since the above-mentioned organic antibacterial and antifungal agent has volatility, if it is contained in a synthetic resin, the surrounding environment of the synthetic resin is contaminated. In addition, since the wastewater in contact with the surface of the synthetic resin contains an antibacterial and antifungal agent, there are problems such as causing environmental pollution of wastewater and affecting activated sludge during sewage treatment. . In the case of a silver-based antibacterial agent using silver ions (Ag ⁺ ), silver ions react with chlorine ions in a chlorine-based bleach to form insoluble silver chloride, and silver chloride has high photoreactivity. Immediately changing to metallic silver or silver oxide not only causes blackening, but also degrades antibacterial performance. In addition, when kneading in a resin, the heating temperature is 200 ° C. or higher, so that the antibacterial material is discolored and a white resin molded product is hardly obtained. Furthermore, the above-mentioned plant extract is an aromatic substance in many cases, and has a volatility. Therefore, when these substances are mixed in a resin, they are evaporated by heating at the time of molding the resin, so that they cannot be mixed. was there.

[0004] In view of the above problems, an object of the present invention is to provide an antibacterial antiviral and antifungal agent which is hardly dissolved 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 that are less likely to cause environmental pollution even when eluted from the resin. Further, another object of the present invention is to provide an antibacterial antiviral and antifungal agent which does not discolor by heat and a complex thereof.

[0005]

The antibacterial, antiviral and antifungal agent of the present invention is obtained by binding a metal having antibacterial properties or its ion to the SH group of cysteine. 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 complex of the present invention is obtained by supporting the above antibacterial antiviral antifungal agent on a carrier selected from the group consisting of porous glass, porous calcium carbonate, and silica gel. The composite preferably has a coating layer on its surface. The coating layer is preferably formed of silicon dioxide generated by hydrolysis of alkoxysilane.

[0006]

[Cyc] 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 incorporated. This inhibits the antibacterial performance of the antibacterial metal and the formation of individual organisms, and exhibits very strong antibacterial performance and the like. The present invention provides an antibacterial metal bonded to the SH group of cysteine,
It is hardly soluble in water.

The antibacterial, antiviral and antifungal complex of the present invention exhibits a stable antibacterial, antiviral and antifungal effect because the antibacterial, antiviral and antifungal agent is supported on a porous carrier. When the metal that binds to cysteine is silver, copper, zinc or nickel, elution from the resin hardly causes environmental pollution. When a coating layer is formed on the outer surface of the composite, the sustained release of the antibacterial antiviral and antifungal agent is further improved. Further, even when used in an atmosphere having a high chlorine concentration, there is no discoloration and no decrease in antibacterial and antiviral properties.

[0008]

The preferred antibacterial and antiviral antifungal agent of the present invention will be described in more detail. This antibacterial and antiviral antifungal agent dissolves D or L-cysteine in pure water and adds 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-mentioned metal such as a silver thiosulfato complex salt. Next, to produce the composite,
A carrier is added to the solution of the antibacterial antiviral antifungal agent, and the carrier is adsorbed or impregnated with the antibacterial antiviral antifungal agent, and then dried to carry the antibacterial antiviral antifungal agent on the carrier.

As this carrier, silica gel, porous glass or porous calcium carbonate is used. Porous glass includes (1) sintering of fine glass powder, (2) hydrolysis of inorganic salts, metal alkoxides, and the like (silica gel can also be obtained by this method, but is not included here in a narrow sense).
(3) Obtained by a method such as phase separation of glass.
(1) is a method in which 2% of a carbonate is added as a foaming agent to powder glass obtained by wet-grinding SiO ₂ —CaO—Na ₂ O-based glass for 10 hours, and the resulting mixture is calcined at 850 ° C. for 100 seconds to form foam. Glass is made and this granular foam glass (5-20
(Volume% water absorption) for 4 days in hot water at 70 ° C. to remove soluble alkali components, and to provide an opening in the surface layer of foam glass and in closed cells.
As a result, a product having a water absorption of 20 to 50% by volume is obtained. (3) is to heat-treat the SiO ₂ —Na ₂ O—B ₂ O ₃ —Al ₂ O ₃ system glass at 500 to 650 ° C. to separate phases, and to add a phase rich in B ₂ O ₃ —Na ₂ O in acid water. Is manufactured. As a glass composition system, 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 -
B is ₂ O ₃ over CaO-MgO over Al ₂ O ₃ -TiO ₂ system like also. In the porous glass obtained in (1) to (3), the pore diameter can be arbitrarily selected from a wide range of 40 Å to 40 μm. Porous calcium carbonate having a pore diameter of 1.5 to 2.0 μm is commercially available (for example, Formuse P manufactured by Tsuneka Chemical Industry Co., Ltd.).

[0010] The coating layer formed on the outer surface of the composite,
Silicon dioxide formed by hydrolyzing an alcohol solution of alkoxysilane by a sol-gel method is preferable. This coating layer allows for the adjustment of the duration of the antibacterial and virus-suppressing pharmacological effects of the complex. That is, the sustainability of the antibacterial, antiviral, and antifungal effects can be controlled by the area and thickness of the coating layer. The alkoxysilane for forming this coating layer has 1 to 4 carbon atoms in the alkoxyl group, and the alcohol has 1 carbon atom in the alcohol.
~ 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 a 1N nitric acid solution. On the other hand, L-cysteine methyl ester 0.17
g was dissolved in 15 ml of a 1N nitric acid solution. Subsequently, these two solutions were mixed and allowed to stand at 4 ° C., after which the precipitate was collected by filtration and dried at 60 ° C. under reduced pressure. About the thus obtained antibacterial antifungal antiviral agent (hereinafter abbreviated as antibacterial agent),
The following antibacterial, antifungal and antiviral tests were performed.

Antifungal test: A halo test method based on a mold resistance test for textile products in a 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). Evaluation was performed 14 days later. Antibacterial test: Escherichia cole
i), Staphylococcus aureus (Staphylococcu
s aureus) and Bacillus subtilli
s) and according to the dropping method. The evaluation was performed after 24 hours at 37 ° C. Antiviral test: Herpes simplex virus type 2, measles virus, and AIDS virus were used at an infectious titer of 10 ⁴ TCID ₅₀ , and Vero was used.
The determination was based on the presence or absence of infection to the cells. In either case,
The test results were represented by the following criteria. ◎: 100% inhibition, ：: 90% inhibition, Δ: 80% inhibition,
X: 50% suppression

The test results are shown in Table 1. Antimicrobial agent concentration 1
At 00 ppb, a growth inhibitory effect on bacteria, molds and viruses was observed. Although L-cysteine methyl ester was used in the above example, the same result was 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 may be used in a mixture.
One mole was dissolved in 15 ml of a 1N nitric acid solution. next,
0.01 mol of L-cysteine methyl ester was dissolved in 15 ml of 1N nitric acid solution. Subsequently, these two solutions were mixed, left at 4 ° C., and the precipitate was collected and dried to obtain an antibacterial agent. These antibacterial agents were subjected to the same antibacterial, antifungal and antiviral tests as in Example 1. The test results are shown in Table 2. As a result, strong antibacterial, antifungal and antiviral effects were also observed for copper, zinc and nickel. In the above examples, L-cysteine methyl ester was used,
The same result was obtained with the D-form.

[0016]

[Table 2]

Example 3 1.7 g of AgNO ₃ was dissolved in 15 ml of a 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 size 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 or impregnated on the carrier is dried at a normal pressure and a temperature of 4 to prevent the silver compound from decomposing.
0 ° C. Thus, a composite in which a silver compound was supported on a carrier was obtained. Table 3 shows the antibacterial, antifungal and antiviral test results of this complex. Complex concentration 1000 pp
m, a growth inhibitory effect on bacteria, fungi and viruses was observed.

[0018]

[Table 3]

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

[0020]

[Table 4]

Comparative Example 1 An antibacterial composite was prepared in the same manner as in Example 3 except that commercially available silica glass powder (not porous) was used. Elution rate is 25000
It was confirmed that the compound exhibited extremely low sustained release at ppm / h.

Example 4 1 g of a complex supporting the silver compound of Example 3 was added to a solution obtained by adding 1 ml of tetraethoxysilane to 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 the generated silicon dioxide on the surface of the composite.

Example 5 1 g of the complex supporting the silver compound of Example 3 was added to a solution obtained by adding 1 ml of a silicone resin solution to 1 ml of chloroform, mixed well, dried under reduced pressure, and dried at 100 ° C. for 7 hours. Heat for a time to cure the silicone resin film. Thus, the surface was coated with the silicone resin. Table 5 shows the results obtained by examining the elution rate of silver ions for the antibacterial antiviral antifungal complexes of Examples 4 and 5 in the same manner as in Example 3. Ag ⁺
It has been found that the ion elution rate becomes 1/10 to 1/200 by forming the coating layer, when the coating layer is 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 during molding of a polypropylene resin to obtain a resin molded body. Was. This resin molded article was subjected to the same antifungal test and antibacterial test as in Example 1. Table 6 shows the results. Those having a deterrent effect of 90% or more were indicated as "effective". From Table 6, the antibacterial and antifungal complex of this example is
It turns out that it has practical antibacterial and antifungal performance.

[0026]

[Table 6]

[0027]

As described above, the antibacterial antifungal antiviral agent and the complex of the present invention have practical antibacterial antifungal antiviral properties and exhibit stable antibacterial effects on the resin surface. In addition, since it has low volatility, it is hardly eluted from the resin, and even if it is eluted, it hardly causes environmental pollution. Furthermore, it exerts a strong antibacterial, antifungal and antiviral effect even in the presence environment of chloride ions. Further, it has heat resistance up to about 240 ° C., and can prevent discoloration of the resin when it is dispersed and molded into the resin.

──────────────────────────────────────────────────続 き Continued on the front page (72) Inventor Yasuo Mizuno 1006 Kadoma Kadoma, Kadoma City, Osaka Prefecture Inside Matsushita Electric Industrial Co., Ltd. (56) References JP-A-48-58133 (JP, A) JP-A-2-11501 (JP, A) JP-A-64-16703 (JP, A) JP-A-61-227520 (JP, A) JP-A-61-145108 (JP, A) JP-A-60-16904 (JP, A) JP-A-49-126155 (JP, A) JP-A-3-111436 (JP, A) JP-A-62-7747 (JP, A) JP-A-5-912 (JP, A) JP-A-5-155725 (JP, A) JP-A-6-306082 (JP, A) JP-A-6-313266 (JP, A) Kaihei 1-125301 (JP, U) US Patent 4847049 (US, A) EL-NAGG AR, A. M. , Et. al. , "Synthesis and Antimicrobia (58) Fields investigated (Int. Cl. ⁷ , DB name) A01N 25/08 A01N 25/26 A01N 59/20 A01N 59/16 CA (STN) REGISTRY (STN) JICST file (JOIS )

Claims (1)

(57) [Claims] (1) porous glass, porous calcium carbonate,
And a carrier selected from the group consisting of silica gel and silica gel , carrying an antibacterial antiviral antifungal agent having an antibacterial metal or an ion thereof bonded to the SH group of cysteine.
An irs antifungal complex, the surface of which
Antimicrobial, antiviral, and antifungal compound having a silicon coating layer
Coalescing.