JPH06305903A - Antibacterial agent - Google Patents

Abstract

PURPOSE:To provide an antibacterial agent being resistant to discoloration and the deterioration of the antibacterial property and developing the antibacterial property, etc., over a long period even in a severe environment such as the exposure to sunlight or hot atmosphere or contact with an acidic solution. CONSTITUTION:The antibacterial agent is composed of a compound expressed by the general formula nAO2.MaBbSb2O5(OH)2.-mH2O wherein A is at least one kind of tetra-valent metal ion selected from titanium, zirconium and tin; M is at least one kind of metal ion selected from silver, copper, zinc, tin, mercury, lead, iron, cobalt, manganese, etc.; B is at least one kind of ion selected from alkali metal ion, alkaline earth metal ion, ammonium ion and hydrogen ion; (a) and (b) are positive numbers satisfying the formula pa+qb=2; (p) is valence of M; (q) is valence of B; n>0; n<=m<=2(n+1).

Description

Detailed Description of the Invention

[0001]

The present invention relates to at least one fungicide selected from silver, copper, zinc, tin, mercury, lead, iron, cobalt, nickel, manganese, cadmium, chromium and the like.
The present invention relates to an antibacterial agent composed of a specific antimonic acid compound having a metal ion exhibiting antibacterial and antialgal properties (hereinafter referred to as antibacterial property). INDUSTRIAL APPLICABILITY The present invention is used as an antibacterial composition mixed with various binders, or as an antibacterial molded product by supporting it on a carrier such as fiber, film, paper, ceramics and plastic.

[0002]

2. Description of the Related Art Metal ions such as silver, copper, zinc, tin, mercury, lead, iron, cobalt, nickel, manganese, bismuth, barium, cadmium, and chromium are fungicidal, antibacterial, and antialgal. Ions (hereinafter referred to as antibacterial metal ions) have long been known, and in particular, silver ions are widely used as an aqueous silver nitrate solution having a disinfecting action and a sterilizing action. However, the above-mentioned metal ions exhibiting antibacterial properties are often toxic to the human body, and there are various restrictions in usage, storage, disposal, etc., and their applications are also limited.

In recent years, it has become clear that a slight amount of antibacterial metal ions act on an object to exert antibacterial properties, and as the antibacterial agent, the antibacterial metal ions are ion-exchanged. Organic antibacterial agents supported on resins or chelating resins and inorganic antibacterial agents in which antibacterial metal ions are supported on clay minerals, inorganic ion exchangers or porous materials have been proposed.

Among the above-mentioned various antibacterial agents, the inorganic antibacterial agents are generally higher in safety than the organic antibacterial agents, and the antibacterial effect is long lasting and the heat resistance is excellent. As one of the inorganic antibacterial agents, an antibacterial agent is known in which alkali metal ions such as sodium ions in clay minerals such as montmorillonite and zeolite are ion-exchanged with silver ions. However, since the skeletal structure of the clay mineral itself is inferior in acid resistance, for example, silver ions are easily eluted in an acidic solution and the durability of the antibacterial effect is not sufficient. Also,
This silver ion is unstable to heat and light exposure,
Since it is easily reduced to metallic silver, in this case, there is a problem that it is easily colored and lacks long-term stability.

Further, in order to improve the stability of silver ions, it is also known that zeolite is loaded with silver ions and ammonium ions coexisting by ion exchange, but the prevention of coloration is not sufficient in practical use. , A fundamental solution has not been reached. Furthermore, as another inorganic antibacterial agent, there is an antibacterial agent in which an antibacterial metal ion is adsorbed on an activated carbon having an adsorptive property. However, when a soluble antibacterial metal ion is physically adsorbed or attached, Since it is not too much, the antibacterial metal ion is rapidly eluted when it is brought into contact with water, and the antibacterial effect is not durable.

[0006]

SUMMARY OF THE INVENTION The present invention involves exposing to sunlight, high temperature atmosphere, or contact with an acidic solution,
It is an object of the present invention to provide an antibacterial agent that is not colored even in a harsh environment, does not deteriorate in antibacterial property, and can exhibit antibacterial property for a long time.

[0007]

Means for Solving the Problems As a result of intensive studies to solve the above problems, the present inventors have found that a specific antimonic acid compound carrying an antibacterial metal ion has a very excellent chemical and The inventors have found that they have physical stability and antibacterial properties for a long time, and have completed the present invention.

That is, the present invention relates to an antibacterial agent comprising a compound represented by the following general formula [1]. nAO ₂ · M _a B _b Sb ₂ O ₅ (OH) ₂ · mH ₂ O [1] (A is at least one tetravalent metal ion selected from titanium, zirconium and tin, M is silver, copper,
At least one metal ion selected from zinc, tin, mercury, lead, iron, cobalt, nickel, manganese, barium, cadmium and chromium, and B is an alkali metal ion, an alkaline earth metal ion, an ammonium ion and a hydrogen ion. It is at least one kind of ion selected from, a and b are both positive numbers, and are numbers satisfying pa + qb = 2. However, p is the valence of M, q is the valence of B, and both n and m are positive numbers.

Compound represented by the above general formula [1] [also referred to as compound (1). ] Is an amorphous or crystalline antimonic acid compound. The metal "M" in the above general formula [1] is a specific antibacterial metal ion listed above. Each of the metal ions listed above is useful as a metal exhibiting antifungal, antibacterial and antialgal properties, and among them, silver ions are preferred. This is because it has excellent safety and antibacterial properties.

The amount of the metal "M" supported [the value of a in the above general formula [1]] is preferably large from the viewpoint of exerting antibacterial properties, but usually the value of a is 0.0.
It is 01 to 0.5 (more preferably 0.01 to 0.5). If it is less than 0.001, it may be difficult to exert the antibacterial property for a long time, and if it exceeds 0.5, it is not preferable in terms of economy. In particular, this is 0.01-
The range of 0.5 is more preferable because the antibacterial property and the economical efficiency are excellent.

The coefficient n of the compound (1) may be any positive number, but in order to exert sufficient antibacterial property,
It is preferable to adjust the number to be a positive number of 10 or less.
The following are preferred specific examples of the general formula [1]. 3.1 TiO ₂ · Ag _0.005 H _1.995 Sb ₂ O ₅ (OH) ₂
・ 6.2H ₂ O 6.0TiO ₂・ Ag _0.01 H _1.99 Sb ₂ O ₅ (OH) ₂・
_{14H 2 O 6.0TiO 2 · Ag 0.2} H 1.8 Sb 2 O 5 (OH) 2 · 1
4H ₂ O 1.1SnO ₂ · Ag _0.05 H _1.95 Sb ₂ O ₅ (OH) ₂ ·
2.2 H ₂ O 4.0 ZrO ₂ · Ag _0.2 H _1.8 Sb ₂ O ₅ (OH) ₂ ·
The amount of Ag in each of the above formulas was adjusted to Zn, Mn, Ni, Pb, Hg, Sn and Cu while the amount of charge was 8.0 H ₂ O and the amount of silver ion per mol of the compound.
Compounds substituted with at least one selected from

The antibacterial agent of the present invention is usually prepared by immersing a powder of a tetravalent antimonic acid metal salt such as titanium antimonate in an aqueous solution of the antibacterial metal salt and an aqueous solution containing the above B ion to cause an ion exchange reaction. Is obtained by However, since the antimonic acid tetravalent metal salt is a compound having ion-exchangeable hydrogen ions, in order to obtain an antibacterial agent carrying only hydrogen ions as B ions, antimonic acid tetravalent metal salt powder is used as an antibacterial agent. It suffices to carry out the ion exchange reaction by immersing it in an aqueous solution of a metallic salt. The tetravalent antimonic acid metal salt can be obtained by various synthetic methods, but is usually obtained by wet synthesis. The crystallinity of the product varies depending on the type of synthesis method. As the tetravalent metal antimonate salt used in the present invention, it is preferable to use a salt having high crystallinity because it is less discolored when exposed to sunlight.

The antibacterial agent of the present invention is usually obtained in the form of powder and can be used as it is, but its use form is not particularly limited, and various resin components, etc. may be used depending on the application.
It can be appropriately mixed with other components or can be mixed with other materials such as fibers, films, papers, ceramics and plastics. For example, it can be used in various forms such as powder, powder-containing dispersion liquid, powder-containing particles, powder-containing coating material, powder-containing fiber, powder-containing paper, powder-containing film, powder-containing aerosol, etc. It can also be used in combination with various additives or materials such as odorants, flame retardants, anticorrosion, fertilizers and building materials.

[0014]

[Function] The antibacterial agent is nAO ₂ · M _a B _b Sb ₂ O ₅ (O
H) ₂ · mH ₂ O As it can be seen that it has an antimonic acid compound as the skeleton, the structure and composition do not change by heating below 500 ° C, and the skeleton structure changes even in an acidic solution. I can't see it. Further, in the present antibacterial agent, a specific antibacterial metal ion is firmly supported on the skeleton composed of the antimonic acid compound. Therefore,
This antibacterial metal ion does not easily elute even in an acidic solution.

From the above, the present antibacterial agent is stable to acid, heat and light, and does not cause any discoloration even in a severe environment such as exposure to sunlight, high temperature atmosphere, or contact with acidic solution. , The weather resistance and antibacterial property do not deteriorate even after long-term use. Therefore, this antibacterial agent is processed and preserved when obtaining various molded products, and like conventional antibacterial agents,
There is no restriction such as heating temperature or light shielding condition during use.

[0016]

EXAMPLES In the following examples and comparative examples, the following predetermined antibacterial agents were prepared and subjected to weathering test, antibacterial property test and acid resistance test. Example 1 (1) Preparation of antibacterial agent a First, crystalline titanium antimonate was prepared as follows. That is, to 63 g of 70% antimony pentachloride heated to 60 ° C. in a constant temperature bath, 105 g of 70% titanium tetrachloride heated to 60 ° C. was poured with stirring, and subsequently 60 ° C.
It is poured into 3500 g of pure water that has been heated to 0, and a hydrolysis reaction is carried out. Thereafter, the precipitate is aged at 60 ° C. for 24 hours with stirring. After completion of the aging, the slurry was filtered and washed with water, then the cake was dried at 60 ° C., and then this was crushed to obtain crystalline titanium antimonate. The chemical composition was determined by fluorescent X-ray analysis to find the ratio of the antimony and titanium contents in the compound, and estimated their composition. Regarding the silver content, the silver content remained in the filtrate after substitution. It is estimated from the amount of silver. The same applies to the following.

Next, this titanium antimonate powder 20 is used.
g, 0.944 g of silver nitrate and 100 g of pure water were placed in a polyethylene sample bottle and shaken at 40 ° C. for 2 hours. Then, the slurry was filtered, washed with water, dried and pulverized to obtain an antibacterial agent a having the composition formula (a) below. 6.0 TiO ₂ · Ag _0.2 H _1.8 Sb ₂ O ₅ (OH) ₂ · 14H ₂ O (a)

(2) Performance Evaluation The above antibacterial agent a was subjected to the following weather resistance test, antibacterial property test and acid resistance test, and the results are shown in Table 1.

[0019]

[Table 1]

Weather resistance test A commercially available polyethylene resin was contained in an amount of 5% by weight to prepare a plate having a thickness of 3 mm, and the plate was used as a test piece for a weather resistance test. In this test, one cycle consists of a step of irradiating ultraviolet rays at 60 ° C. for 1 hour and then leaving it at 40 ° C. for 1 hour at 90% humidity, and three cycles were repeated. And the color before and after the test (L, a,
b) Colorimeter [Nippon Denshoku Industries Co., Ltd. colorimeter "SZ-Σ
80 "] to evaluate the weather resistance.

Antibacterial Test The minimum inhibitory concentration of the above antibacterial agent against Escherichia coli (MIC: minimum concentration of the antibacterial agent capable of inhibiting the growth of the subject) was measured by the standard method of the Japanese Society of Chemotherapy. Acid resistance test 10% of various antibacterial agents in 4% by weight acetic acid aqueous solution (pH 3)
After adding 4% by weight, the mixture was allowed to stand for 4 hours, the antibacterial agent was filtered off, and the elution amount of silver ions in the filtrate was measured by an atomic absorption photometer.

Example 2 (Antibacterial agent b obtained by firing antibacterial agent a)
Preparation of) The antibacterial agent a obtained in Example 1 was baked at 700 ° C. for 4 hours,
An antibacterial agent b was prepared, and a weather resistance test, an antibacterial property test and an acid resistance test were conducted on the antibacterial agent b in the same manner as in Example 1, and the results are also shown in Table 1.

Comparative Example 1 (Preparation of Antibacterial Zeolite) An antibacterial zeolite according to Comparative Example 1 was prepared as follows, and the weather resistance test, antibacterial test and acid resistance test were carried out in the same manner as in Example 1. The results were also shown in Table 1. Type A zeolite (composition: 0.94 Na ₂ O.
The _{Al 2 O 3 · 1.92SiO 2 ·} xH 2 O), was added to the aqueous silver nitrate solution, and the mixture was stirred for 5 hours at room temperature, the slurry is filtered, washed with water, dried, ground and having the following composition formula (c) Antibacterial agent c was obtained. 0.03Ag ₂ O ・ 0.8Na ₂ O ・ Al ₂ O ₃・ 1.9SiO ₂・ xH ₂ O (c)

Comparative Example 2 (Preparation of antibacterial agent d by firing antibacterial zeolite) The antibacterial agent c obtained in Comparative Example 1 was fired at 700 ° C. for 4 hours,
The antibacterial agent d was prepared, and an antibacterial property test was conducted on the antibacterial agent d in the same manner as in Example 1, and the results are also shown in Table 1.

(3) Effects of Examples and Comparative Examples According to the results shown in Table 1, the antibacterial agent c of Comparative Example 1 showed a large color change (coloring was observed) before and after the weather resistance test. In the antibacterial agents a and b of Examples 1 and 2 according to the present invention, the change is remarkably small as compared with Comparative Example 1, and it is shown that the weather resistance is remarkably excellent. In addition, the baked product (Example 2) has a smaller change than the unbaked dried product (Example 1), indicating that the weather resistance is further improved by the baking.

Regarding the antibacterial property, the minimum inhibitory concentration (MIC) against E. coli was 125 ppm for both the antibacterial agents a and b (Examples 1 and 2 respectively).
And antibacterial agents c and d (250 ppm and 250, respectively)
(0 ppm or more) is very excellent. In particular, the antibacterial property of the baked antibacterial agent d of Comparative Example 2 (MIC: 2500
(above ppm) is extremely bad. However, in Examples 1 and 2, almost the same performance was shown, and even if high temperature heating was performed, there was no deterioration in performance, indicating that it is more stable to heating than the comparative example. Furthermore, regarding acid resistance, the results of Examples 1 and 2 were also used.
With the antibacterial agents a and b, the acid was hardly eluted, but with the antibacterial agent of Comparative Example 1, it was as large as 5 ppm, indicating that the stability due to the acid was poor.

As described above, the baked product and the unbaked product (dried product) are the products of the present invention (Examples 1 and 2).
In Comparative Example 1, the weather resistance, antibacterial property and acid resistance were almost the same or slightly changed, and unlike Comparative Examples, there was almost no deterioration in performance even when high temperature heating was performed.
Therefore, it is considered that in Examples 1 and 2, the structure (skeleton) and the composition did not change due to the heating, while in the Comparative Example, some change occurred.

[0028]

Since the antibacterial agent of the present invention is chemically and physically stable, it can be exposed to sunlight, high temperature atmosphere, or contact with an acidic solution even under severe environment.
Without coloring, antibacterial property is not deteriorated, and mildew proof,
It is possible to exert antibacterial and antialgal properties for a long time. Therefore, this antibacterial agent is used for work clothes, medical clothes, medical bedding, sports clothes, bandages, fishing nets, curtains, carpets,
Underwear, fibers such as air filters, plastic moldings, paper such as wallpaper, food packaging films, medical films, synthetic leather films, sterilizer wall paints, antiseptic paints, antifungal paints, etc. , It is extremely useful for applications such as powders for agricultural soil and liquid compositions such as shampoo.

 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Hideki Kato 1-1 Funami-cho, Minato-ku, Nagoya-shi, Aichi Toagosei Chemical Industry Co., Ltd. Nagoya Research Institute

Claims (1)

[Claims] 1. An antibacterial agent comprising a compound represented by the following general formula [1]. nAO ₂ · M _a B _b Sb ₂ O ₅ (OH) ₂ · mH ₂ O [1] (A is at least one tetravalent metal ion selected from titanium, zirconium and tin, M is silver, copper,
At least one metal ion selected from zinc, tin, mercury, lead, iron, cobalt, nickel, manganese, barium, cadmium and chromium, and B is an alkali metal ion, an alkaline earth metal ion, an ammonium ion and a hydrogen ion. It is at least one kind of ion selected from, a and b are both positive numbers, and are numbers satisfying pa + qb = 2. However, p is the valence of M, q is the valence of B, and both n and m are positive numbers.