JP2888767B2 - Biocide - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a biocide, particularly to a biocide useful for controlling various germs caused by pet manure.

[0002]

2. Description of the Related Art In sandboxes in parks and the like, harmful microorganisms are generated due to excretion of pets, and unpleasant odors caused by the generation of microorganisms pose a problem in environmental hygiene. However, countermeasures against microorganisms generated in a sandbox, for example, are currently being dealt with by replacing all or part of the sand or by spraying an expensive and transient disinfectant, etc., and there is no good method yet. Therefore, a safe and inexpensive biocide which is easy to handle, has a high killing effect, and has a long lasting effect is desired.

[0003]

SUMMARY OF THE INVENTION The present invention has been made in order to meet the above-mentioned demands, and is an economical, sustainable, and safe biocide for harmful microorganisms generated by pet manure and the like. It is intended to provide an agent, a method for producing the same, and a method for using the same.

[0004]

As a result of various studies to achieve the above object, the present inventors have surprisingly found that a lime-based composition which the present inventors have already developed as a flue gas treatment agent has been smoke-treated. It has been found that, after being subjected to, it has bactericidal properties, and that by adsorbing the water solubility of a metal compound which is conventionally known to have bactericidal properties, its activity can be effectively used for a long time. Completed the invention.

That is, the present invention provides: CaO, CaSO ₄ , Al ₂ O ₃ obtained by mixing at least one selected from the group consisting of slaked lime, quick lime, gypsum, and volcanic ash with coal ash and / or used lime-based exhaust gas treating agent the SiO ₂ based cured product obtained by treatment with a gas containing sulfur dioxide biocide 2. CaO, CaSO ₄ , Al ₂ O ₃ obtained by mixing at least one selected from the group consisting of slaked lime, quick lime, gypsum, and volcanic ash with coal ash and / or used lime-based exhaust gas treating agent _{2. A} biocide obtained by treating a cured product of SiO.sub.2 with a gas containing sulfurous acid gas and further treating with an aqueous solution containing at least one of a water-soluble antibacterial metal compound. 3. The biocide according to 2 above, wherein the antibacterial metal compound is a salt of at least one metal selected from silver, copper, zinc, and nickel. CaO, CaSO ₄ , Al ₂ O ₃ obtained by mixing at least one selected from the group consisting of slaked lime, quick lime, gypsum, and volcanic ash with coal ash and / or used lime-based exhaust gas treating agent , SiO ₂ -based cured product is treated with a gas containing sulfur dioxide gas, and a predetermined amount of an aqueous solution containing at least one of a water-soluble antibacterial metal compound is sprayed and absorbed. 4. A method for producing a biocide, characterized by adding water to the mixture and leaving the mixture in the air again. 5. The method for producing a biocide according to 4 above, wherein the antibacterial metal compound is a salt of at least one metal selected from silver, copper, zinc, and nickel; A method for cleaning and maintaining a sand pit, comprising spraying and stirring 5 kg to 50 kg of the biocide described in 1 or 2 above per 1 m ² of surface area of the sand pit.

[0006] The coal ash used in the present invention is generated by burning coal, and there is no particular limitation on the type of coal or the burning method. Here, the used lime-based exhaust gas treating agent includes a used calcium-based desulfurizing agent produced from CaO, Ca (OH) ₂ , CaCO _3, etc., as well as JP-A-61-209038 and JP-A-63-9038. 283745
CaO, Al ₂ O ₃ , SiO ₂ , CaSO ₄
Refers to a used desulfurizing agent comprising a system composition. C
Table 1 shows an example of the names and analytical values of the materials that can be used as raw materials for the desulfurizing agent composed of aO, Al ₂ O ₃ , SiO ₂ , and CaSO ₄ based compositions.

[0007]

[Table 1] A preferred combination of these raw materials is at least one combination selected from the group consisting of coal ash and / or spent lime-based exhaust gas treating agent and slaked lime, quicklime, gypsum and volcanic ash. These materials are mixed and hydrated and hardened (described later)
As a result, a CaO, CaSO ₄ , Al ₂ O ₃ , SiO ₂ cured product is obtained.

[0008] In the present invention, hydration hardening refers to hydration and hardening by adding water to a raw material mixture, and specifically includes the following processes. The hydration treatment is described in, for example,
As disclosed in 4-38130, it refers to a treatment necessary for advancing the hydration reaction between the above-mentioned various substances (raw materials), and includes, for example, wet curing, hot water curing, steam curing, and the like. The treatment promotes the bonding between the material particles by reducing the mixing ratio (solid-liquid ratio) of the raw materials and water to, for example, 1: 0.2 to 1: 0.99 to obtain a cured product. It can be performed in two stages if necessary. The moisture curing in the hardening hydration treatment is performed at a temperature of 10C to 40C.
A relative humidity of 50% to 100% is preferable for several minutes or tens of days, and steam curing is performed at a temperature of 40 ° C to 180 ° C.
Several minutes to several days at 100% relative humidity are preferred.

The cured product thus obtained can be dried, conditioned, pulverized or further shaped.
Crushing of wet or dried hardened material, compression molding of pulverized material and dried material of slurry-like material are commonly used in mullerizers, disk pelletizers, briquette machines, tableting machines, extrusion machines, and others. It can be performed by a pressure-formable device.

The biocide of the present invention can be obtained by treating the above-mentioned cured product with a gas containing sulfur dioxide (abbreviated as SO ₂ treatment). SO ₂ treatment is performed by adding SO ₂ to 10
A gas containing 80 ppm to 500 ° C. containing 0 ppm to 90%,
SV5~50,000h cured 1Kg per SO ₂ ^-1 may be sufficient time processing to at least 1 mole contact.

CaO, CaSO ₄ , Al ₂ O ₃ , SiO ₂
The respective component ratios in the system cured product and the cured product after SO ₂ treatment are CaO 2 to 8% CaSO ₄ 0.1 to 70% Al ₂ O ₃ 5 to 70% SiO ₂ 5 to 80%. The cured product after SO ₂ treatment was subjected to an acute oral toxicity test, an acute dermal toxicity test, a skin irritation test, an ocular mucosal irritation test, and the like to confirm safety.

Since the cured product of the present invention before the SO ₂ treatment has a composition of a known lime-based exhaust gas treating agent, it has a desulfurizing ability. Therefore, this cured product is used as a desulfurizing agent, and is then killed. Not only can it be used as a biological agent, but also can be used as a deodorant as disclosed in JP-A-4-176466. Therefore, in this case, a very economical biocide having both deodorizing ability can be provided.

The biocide of the present invention can be used in the form of powders, granules, or molded products by known methods, depending on the application.

The nematicidal property is obtained by treating the cured product subjected to SO ₂ treatment with an aqueous solution containing an antibacterial metal ion dissociated from salts of at least one metal selected from silver, copper, zinc and nickel. And the effect can be maintained. It was also found that the cured product subjected to the aqueous solution treatment had a deodorizing effect similarly to the cured product before the treatment.

The treatment with the above-mentioned aqueous solution includes the following steps: 1. a method in which a cured product is immersed in an aqueous solution having a certain concentration, and then dried by heating or left in air. Spread a given amount of liquid at a certain concentration evenly on the cured product, leave it in the air and dry it. Then, let the water dry until the surface becomes dry (water fills the internal space of the cured product but does not adhere to the surface). And drying in air, and the latter method is preferred for adding a calculated amount of antibacterial metal. When the biocide of the present invention is used in a sandbox such as a park, it can be handled in the same manner as general sand, and is used by mixing with sand. Although the amount used varies depending on the degree of sand contamination, the amount that can be used without giving a sense of incongruity is about 5 kg to about 50 kg per 1 m ² of area (sand depth of about 3 kg).
0 to 1% by weight).

[0016]

EXAMPLES The present invention will be described below with reference to examples.
The present invention is not limited to this. Parts and% in the text are based on weight. Example 1 To 25 parts by weight of coal ash B shown in Table 1, 35 parts by weight of slaked lime and 40 parts by weight of a used lime-based exhaust gas treating agent were powder mixed, and 40 parts by weight of water was added to 100 parts by weight of solids. After kneading and molding, steam curing was performed for about 15 hours as a hydration treatment, followed by drying to prepare a cured product having a diameter of 6 mm and a length of 10 mm. This was contacted with the exhaust gas at a superficial velocity of 400 h ^{-1 for} about 300 hours, and then sized to a particle size of 0.1 to 1.0 mm to obtain the biocide of the present invention.

The composition of the used exhaust gas is SO ₂ 400p
_{pm, NO X 150ppm, O 2} 5%, CO 2 14%,
8% residual water content was N _2. In this exhaust gas treatment, about 80% of Ca in the raw slaked lime was converted to CaSO ₄ . To confirm the biocidal activity, tests on bacteria and tests on nematodes were performed. In the test for bacteria, first, 100 mg and 1 g of the above biocide were weighed, mixed with 10 ml of a heated and dissolved agar medium, and poured into a 9 cm petri dish to prepare an agar plate. Next, Escherichia coli (E. coli Sankyo strain) and Bacillus subtilis (B. subtilis ATCC 6633 strain) were placed on the agar plate.
Were streaked, and after culturing at 27 ° C. for 24 hours, the presence or absence of growth was visually observed. The results are shown in Table 2. In the test against nematodes, 100 mg of the above biocide was added to a sample bottle.
And 1 g weighed, and a suspension (500 heads / 10 ml) of nematode as an indicator organism for nematodes such as roundworms and hookworms that may be contaminated by feces such as pets was poured and allowed to stand. Twenty-four hours later, nematode survival in the test solution was observed with a stereoscopic microscope, and the nematode mortality was calculated. The results are shown in Table 3. As indicated, only the bactericidal activity was observed in the biocide of this example.

Example 2 The sized hardened product after SO ₂ treatment obtained in Example 1 was replaced with silver nitrate 5
% Aqueous solution for 1 hour and then left in the air for 7 days to obtain the biocide of the present invention. The activity of this biocide against bacteria and nematodes was examined in the same manner as in Example 1 and is shown in Tables 2 and 3, respectively.

Example 3 Example 2 except that the concentration of the aqueous solution of silver nitrate was changed to 10%.
The biocide of the present invention was obtained in the same manner as described above, and the same tests as in Example 1 were conducted. The results are shown in Tables 2 and 3.

Example 4 The cured sieved product obtained in Example 1 after SO ₂ treatment was treated with 5 of silver nitrate.
The aqueous solution was dispersed and absorbed so as to contain 10% aqueous solution in the agent, left in the air for 1 day, then added with water until the surface became dry, and allowed to stand for 7 days to obtain the biocide of the present invention. The activities of this biocide on bacteria and nematodes were examined in the same manner as in Example 1 and are shown in Tables 2 and 3, respectively.

Example 5 Example 4 except that the concentration of the aqueous solution of silver nitrate was changed to 10%.
The biocide of the present invention was obtained in the same manner as in Example 1, and the same test as in Example 1 was performed. The results are shown in Tables 2 and 3.

[0022]

[Table 2]

[0023]

[Table 3] Example 6 The elution rate of silver ions by passing the biocide obtained in Examples 2 to 5 by passing water was examined over time. In the water passage test, an acrylic column having an inner diameter of 15 mm was filled with 10 ml of the biocide, and the thickness of the filled agent was 55 mm. The ion elution amount was measured. Table 4 shows the analysis values of the biocides of Examples 2 to 5, and Table 5 shows the results of the water flow test.

Comparative Examples 1 and 2 The same operation as in Example 2 was carried out except that natural zeolites and sand, which had been similarly sized, were used in place of the sized hardened product, and natural zeolite impregnated with an aqueous silver nitrate solution and sand were used. Then, the same water flow test as in Example 6 was performed, and Comparative Example 1 and Comparative Example 2 were performed.
And Table 4 shows the analysis values of the water flow test samples of Comparative Examples 1 and 2, and Table 5 shows the results of the water flow test.

[0025]

[Table 4]

[0026]

[Table 5] Example 7 The sand (thickness 30 cm) of the sandbox actually used is taken,
1% by weight of the biocide of the present invention obtained in Examples 1 to 5 was sprayed and mixed, and after 24 hours, sand was collected and washed with sterilized water. Table 6 shows the results of observation of the growth of bacteria and larvae in the washing water with a stereoscopic microscope.

[0027]

[Table 6] +: Survival-: death As is clear from the above examples, CaO, Ca
The agent obtained by treating SO ₄ , Al ₂ O ₃ , and SiO ₂ cured products with SO ₂ not only has a bactericidal property, but when it is treated with an aqueous solution of an antibacterial metal compound, nematicidal properties are imparted. In addition, the active ingredient (metal ion) from the metal compound, when this biocide is applied to a sandbox or the like, does not easily run off in rainwater or urine, etc., and is retained for a long time and used effectively. You can see that.

[0028]

As described above, according to the present invention, a lime-based spent flue gas treating agent is used, which has not only a biocidal effect but also a deodorizing effect, and has a stable effect over a long period of time. Agent can be provided.

Continuation of the front page (51) Int.Cl. ⁶ Identification symbol FI (A01N 59/06 59:16) (72) Inventor Kunihiro Mori 4-9-9-chome, Miigaoka, Toyohira-ku, Sapporo, Hokkaido Hokkaido Electric Power Company Inside the research institute (72) Inventor Tsutomu Ueno 2-1, 9-9, Migaoka, Toyohira-ku, Sapporo, Hokkaido Hokkaido Electric Power Co., Inc. No. 1 Hokkaido Electric Power Company Research Institute (72) Inventor Yukio Seki 7-chome Kita 2-Jo Higashi, Chuo-ku, Sapporo, Japan Inside Nihon System Equipment Co., Ltd. No. 1-2-14, Econics Co., Ltd. (56) References JP-A-6-87715 (JP, A) (58) Fields investigated (Int. Cl. ⁶ , DB name) A01N 59/06-59/20 WPI / L (QUESTEL)

Claims (6)

(57) [Claims] 1. CaO, CaSO ₄ obtained by mixing at least one selected from the group consisting of slaked lime, quick lime, gypsum, and volcanic ash with a coal ash and / or spent lime-based exhaust gas treating agent, and hydrating and hardening the mixture. , Al ₂ O _3, a SiO ₂ based cured product, biocides obtained by treating with a gas containing sulfur dioxide. 2. CaO, CaSO ₄ obtained by mixing at least one selected from the group consisting of slaked lime, quicklime, gypsum, and volcanic ash with coal ash and / or spent lime-based exhaust gas treating agent, and hydrating and hardening the mixture. , Al a ₂ O _3, SiO ₂ based cured product, biocides obtained by treating with an aqueous solution containing at least one treated with gas containing sulfurous acid gas, further water-soluble antimicrobial metal compound. 3. The biocide according to claim 2, wherein the antibacterial metal compound is a salt of at least one metal selected from silver, copper, zinc and nickel. _4. CaO, CaSO ₄ obtained by mixing at least one selected from the group consisting of slaked lime, quick lime, gypsum, and volcanic ash with coal ash and / or used lime-based exhaust gas treating agent, and hydrating and hardening the mixture. , Al ₂ O ₃ , SiO ₂ -based cured product is treated with a gas containing a sulfurous acid gas, and a predetermined amount of an aqueous solution containing at least one water-soluble antibacterial metal compound is sprayed and absorbed and left in the air. Thereafter, water is added until the surface is dried, and the mixture is allowed to stand in the air again. 5. The method for producing a biocide according to claim 4, wherein the antibacterial metal compound is a salt of at least one metal selected from silver, copper, zinc and nickel. 6. A method for cleaning and maintaining a sand pit, comprising spraying and stirring 5 kg to 50 kg of the biocide according to claim 1 or ² per 1 m ² of the surface area of the sand pit.