WO2000072685A1 - Method for producing bactericide - Google Patents

Abstract

A method for efficiently producing a bactericide which has an excellent bactericidal activity and releases no substances causing health hazard to animals and plants. The bactericide is produced by a method comprising a heat-treating step which heat-treats a substance containing a calcium component at a temperature of 650°C or higher and lower than the melting point thereof for two hours or longer and a crushing step which crushes the heat-treated calcium component-containing substance to a powder having an average particle diameter of 10 νm or less. The aforementioned heat treatment imparts bactericidal activity to the calcium component-containing substance. The crushing of the heat-treated calcium component-containing substance increases an area for the contact with bacteria, resulting in a greater bactericidal effect. It is preferred that a pre-crushing step is carried out to crush the substance containing a calcium component to grains having an average grain diameter of 10 to 20 mm, prior to the heat-treating step. The pre-crushing of the substance allows the heat treatment to proceed uniformly from the surface to the inside of a pre-crushed grain and within a short period of time.

Description

 Description Fungicide manufacturing method Technical field

 The present invention relates to a method for producing a bactericide, and more particularly, to a method for producing a bactericide capable of efficiently producing a bactericide having excellent bactericidal ability. Background art

 Calcium carbonate-containing substances such as pearls, animal bones, and shells have antibacterial and bactericidal properties. For example, Japanese Unexamined Patent Publication No. 7-8239 and Japanese Unexamined Patent Publication No. 9-124816 disclose an antibacterial agent obtained by dissolving these calcium carbonate-containing substances in acetic acid. However, it is described that an increase in the number of bacteria in the food can be suppressed by applying or mixing the antibacterial agent to the food.

 By the way, in recent years, it has been recognized that foods and water to be ingested should be alkaline in view of health. However, when the antibacterial agent is applied or mixed to food, the food shows acidity. This antibacterial agent is produced by dissolving a calcium carbonate-containing substance in acetic acid as described above, and inevitably exhibits acidity. That is, the above-mentioned antibacterial agent has a disadvantage that it is not possible to provide foods which are considered to be favorable for health.

 Japanese Unexamined Patent Publication No. 3-77802 discloses that pearls heat-treated at 700-150 become microbial inhibitors having the ability to inhibit the growth of microorganisms such as bacteria and mold. Is described. However, because pearls are generally expensive, this microbial inhibitor is also expensive. That is, if pearl is used as a raw material, there is an inconvenience that inexpensive microbial inhibitors cannot be supplied.

On the other hand, the present applicant has proposed a bactericide and an antibacterial agent (hereinafter, simply referred to as a bactericide) comprising a baked shell (see Japanese Patent Application Laid-Open No. 11-92424). In fact, when this fungicide is immersed in water, it can kill soil bacteria such as Legionella bacteria, Escherichia coli, Enteritis bacteria, etc., which are present in the water. Sterilize be able to.

 That is, the sterilization of water provided as tap water is usually performed using sodium hypochlorite, but if this sterilizing agent is used as a filter material and the water is filtered, sodium hypochlorite or the like can be obtained. It is possible to sterilize water without using it. When water is sterilized without using sodium hypochlorite, chlorine released from sodium hypochlorite does not exist in the water. Also, since there is no free chlorine, trihalogenated methane (trihalomethane) is not generated in water. In addition, this water shows a strong force.

 Therefore, sterilization of water using the above-mentioned disinfectant does not contain toxic chlorine or trihalomethane, which is a carcinogenic substance, and is alkaline water which is considered to be health-friendly. Can be provided.

 In addition, sterilization of ingredients such as raw vegetables and fruits is generally performed by immersing the ingredients in water and introducing sodium hypochlorite into the water. Since chlorine remains, it becomes a food with chlorine odor. In addition, since chlorine is a toxic substance as described above, it is difficult to say that the food is health-friendly. For this reason, after sterilization, a post-cleaning step is performed to remove residual chlorine. However, if the bactericide is immersed in pure water together with the food, the bacteria in the food can be sterilized without introducing sodium hypochlorite. That is, free chlorine does not remain in the food material, and a post-cleaning step is not required.

 As shells that are the raw materials of such a fungicide, wastes such as the shells of pearl oysters after pearls have been collected, the edible oysters, or the shells of oyster shells can be used. At present, these shells are collected and left undisturbed, but by using them as raw materials for fungicides, shells can be recycled as an effective resource. In other words, waste can be reduced, and the burden on the environment is reduced.

 Shells, which are waste, are inexpensive and abundant. Therefore, it is possible to supply a large amount of a disinfectant that uses shells as a raw material at a low cost and in a large amount, so that it is possible to reduce costs required for disinfecting foods.

By the way, according to the above-mentioned Japanese Patent Application Laid-Open No. 11-92444, the above-mentioned bactericide is produced as follows. That is, after crushing shells such as oysters to about 10 mm, First, bake at 350 for 30 minutes, then bake at 500 for 15 minutes, and then bake at 850-; After that, the shell is once taken out of the heating furnace, crushed to about 5 m, and finally refired at 845 for 48 hours.

 However, in this method, the shells must be removed after the furnace cools down before re-firing. In addition, when re-firing the shell that has been subjected to the second grinding, the heating furnace must be heated slowly. If the heating furnace is forcibly cooled or heated rapidly, the heating element may be damaged due to thermal shock.

 After all, in the production method according to the prior art, it takes a long time to produce the disinfectant. However, the consumption and distribution of foodstuffs is increasing year by year, and in order to cope with this, it is necessary to realize a large-scale and stable supply of disinfectants with better sterilization ability. That is, it is necessary to establish a production method capable of obtaining a germicide having better bactericidal ability in a shorter time.

 The present invention has been made in view of such problems, and it is an object of the present invention to efficiently produce a bactericide having excellent bactericidal ability using a substance containing a calcium component such as calcium or a calcium compound as a raw material. The purpose of the present invention is to provide a manufacturing method capable of performing the above. Disclosure of the invention

 In order to achieve the above object, a method for producing a bactericide according to the present invention includes a heat treatment step of heat-treating a calcium component-containing substance at a temperature of 65 O or more and less than the melting point for 2 hours or more, and the heat-treated calcium component. A pulverizing step of pulverizing the contained material to an average particle size of 10 m or less.

 By performing the heat treatment, the bactericidal ability is exerted on the calcium-containing substance. In addition, since the area of contact with the bacteria is increased by crushing the heat-treated calcium component-containing substance, a more excellent bactericidal effect can be obtained.

The disinfectant according to the present invention does not exert a disinfecting action by a chemical. In other words, the bactericide mentioned here encompasses the concept of “a material that performs bactericidal action (bactericidal material)”. Before the heat treatment step, it is preferable to include a preliminary pulverization step of pulverizing the calcium component-containing substance to an average particle diameter of 100 / m to 20 mm. In the pre-ground particles, the heat treatment proceeds uniformly and in a short time from the surface to the inside in the heat treatment step.

 As the calcium component-containing substance, at least one of a calcium carbonate-containing substance and a calcium carbonate-containing mineral of an animal can be used. That is, at least one selected from the group consisting of shells, eggshells, crustacean shells, bones, corals, and pearls, and limestone can be used.

 Calcium carbonate-containing substances in such animals are originally waste. Calcium carbonate-containing minerals such as limestone are natural products. Therefore, the raw materials can be procured at a low price, and the disinfectant can be provided at a low cost.

 In particular, the use of oyster shells as shells is preferable because it can provide a fast-acting bactericide having excellent bactericidal ability.

 When shells are used as raw materials, it is preferable to use shells that have passed two years or more after the living body parts of the shells have been removed. The organic matter adhering to the surface of the shell is spontaneously removed by causing efflorescence or deliquesce, etc. Further, the scaffolds and the like remaining at the time of removing the living body part also decay and fall off. Becomes unnecessary. Also, no odor is generated during the heat treatment process.

 When the calcium carbonate-containing substance possessed by the animal is used as a raw material, a washing step of washing the calcium component-containing substance is performed before the heat treatment step or the preliminary pulverization step. It is preferable to remove them. Without a cleaning step, residues from these sources may remain in the disinfectant and, as a result, excellent disinfection performance may not be achieved. In addition, an odor is generated during the heat treatment process. Further, the heating element of the heat treatment apparatus may be damaged in a short period of time. BRIEF DESCRIPTION OF THE FIGURES

 FIG. 1 is a flowchart of the manufacturing method according to the present embodiment.

FIG. 2 is a table showing the components contained in each of the shells of the pearl oyster, the pokeweed mussel, and the ikiki, and the proportions of the components. FIG. 3 is a table showing a comparison of the bactericidal activity of bactericides produced by variously changing the temperature and time in the heat treatment step.

 FIG. 4 is a table showing the change over time in the number of Escherichia coli (K-112) in water to which no fungicide has been added.

 FIG. 5 is a table showing the time-dependent change in the number of E. coli (K-12) in water into which shells that have not been subjected to heat treatment have been introduced.

 FIG. 6 is a table showing the change over time in the number of E. coli (K-12) bacteria in water into which a bactericide produced by the production method according to the prior art has been added.

 FIG. 7 is a table showing a comparison of the bactericidal ability of bactericides using various calcium component-containing substances as raw materials.

 FIG. 8 is a table showing a comparison of the bactericidal activity of a bactericide using oyster shells as a raw material and a bactericide using pearls as a raw material. BEST MODE FOR CARRYING OUT THE INVENTION

 Hereinafter, preferred embodiments of a method for producing a bactericide according to the present invention will be described in detail with reference to the accompanying drawings.

 FIG. 1 shows a flowchart of the method for producing a disinfectant according to the present embodiment. As shown in FIG. 1, this production method includes a preliminary pulverizing step S10 for pulverizing a calcium component-containing substance to 100 m to 20 mm, and a heat treatment step S2 for heat-treating the calcium component-containing substance. 0, and a pulverizing step S30 for pulverizing the heat-treated calcium component-containing substance to 10 / m or less. The preliminary pulverizing step S10 may be performed as necessary, and is shown in FIG.

First, in the preliminary pulverizing step S10, the calcium component-containing substance is pulverized to an average particle diameter of 100 tm to 20 mm. By crushing to such a particle size, the particles of the calcium component-containing substance are uniformly and quickly heat-treated from the surface to the inside in a heat treatment step S20 described later. If it is crushed to less than 10, handling at the stage becomes difficult since moisture in the shell has not been removed yet, such as particles adhering to the inner wall of the heat treatment equipment. On the other hand, when pulverization is larger than 20 mm, a long time is required in the heat treatment step S20 in order to uniformly perform the heat treatment. Here, the calcium component-containing substance refers to a substance containing calcium or a calcium compound such as calcium oxide, calcium phosphate, calcium carbonate, calcium lactate, and calcium hydroxide.

 The calcium component-containing substance is not particularly limited, but the calcium carbonate-containing substance possessed by animals, that is, shells, eggshells such as birds and buffaloes, shells of crustaceans such as crabs, vertebrate bones, and coral Preferred examples include at least one selected from the group consisting of: All of these are originally available as waste, so they are available at low cost. And there are abundant. Therefore, the disinfectant can be manufactured at low cost, and in the end, the disinfectant can be supplied inexpensively and in large quantities. Also, because waste is reduced, the burden on the environment can be reduced.

 Although not a waste, pearls may be used as the calcium carbonate-containing substance. In this case, the use of inferior pearls, which cannot be provided as decorative articles, can produce a disinfectant at low cost.

 Of the above-mentioned calcium carbonate-containing substances, it is more preferable to use shells, in particular, oyster shells, as a raw material, since they become fungicides having excellent sterilizing ability.

 Other examples of the calcium component-containing substance include a calcium carbonate-containing mineral, that is, limestone. Since limestone is a natural product, it can be used to produce fungicides at low cost.

 Further, as the calcium component-containing substance, a commercially available calcium oxide reagent, phosphoric acid calcium reagent, calcium carbonate reagent, calcium lactate reagent or calcium hydroxide reagent may be used. These may be used as a mixture.

Here, when a fungicide is manufactured using the calcium carbonate-containing substance contained in the animal as described above as a calcium component-containing substance, as shown by a broken line in FIG. Step S5 is preferably performed. If the cleaning step S5 is not performed, an odor is generated in the heat treatment step S20. Also, residues originating from meat pieces and organic substances attached to the calcium carbonate-containing substance of the animal may remain in the disinfectant, and as a result, the disinfectant may not exhibit excellent disinfecting ability. . Further, the heating element of the heat treatment apparatus may be damaged in a short period of time. That is, for example, at least one selected from the group consisting of shells, eggshells such as birds and buffaloes, shells such as crabs, vertebrate bones, corals, and pearls is washed with high-pressure jet water. This washing removes meat pieces, organic matter, bacteria, and the like attached to them. In the cleaning step S5, ultrasonic cleaning may be performed.

 In the case of shells that have been removed for more than two years since the living body of the shell is removed, organic substances and the like adhering to the surface of the shell undergo efflorescence and deliquescence, and are spontaneously removed. In addition, the scallop and the like remaining during the removal of the living body part of the shellfish rot and fall off. Therefore, when such shells are used as raw materials, there is no need to perform a washing step. That is, a bactericide can be produced more efficiently. Further, no malodor is generated in the heat treatment step S20. Next, in a heat treatment step S20, a calcium component-containing substance such as the calcium carbonate-containing substance described above is heat-treated. By performing the heat treatment, the calcium-containing substance has a sterilizing ability.

 In the heat treatment step S20, the temperature is set to be equal to or higher than 650 and lower than the melting point, and the heat treatment time is set to be equal to or longer than 2 hours. If the temperature is lower than 650 or the heat treatment time is shorter than 2 hours, sufficient sterilization ability will not be exhibited. A preferred heat treatment temperature is from 700 to 120, and a preferred heat treatment time is from 3 to 13 hours. If the temperature is higher than 1200: it is uneconomical, and if the heat treatment is performed for more than 13 hours, the production efficiency of the disinfectant decreases.

 Finally, in the pulverizing step S30, the heat-treated calcium-containing substance is pulverized to obtain a bactericide. This pulverization is performed until the average particle diameter of the calcium-containing substance becomes 10 zm or less, preferably 5 m or less. As described above, when the calcium-containing material is pulverized, the total surface area of the fungicide necessarily increases. That is, when immersed in water, the contact area between the bactericide and the bacteria in the water increases. For this reason, a better bactericidal effect can be obtained.

 If the grinding step S30 is performed before the heat treatment step S20, handling becomes difficult, for example, the finely pulverized calcium component-containing substance adheres to the inner wall of the heat treatment apparatus. . Also, when performing the heat treatment step S20, some of the particles are sintered, so that the average particle size cannot be reduced to 1 O ^ m or less.

Thus, according to the production method of the present embodiment, the calcium component-containing substance is The disinfectant as a raw material can be produced in a significantly shorter time than the production method according to the prior art. That is, it can be manufactured efficiently.

 When the fungicide thus produced is immersed in water, calcium contained in the calcium component-containing substance and calcium ions derived from the calcium compound elute into the water. This calcium ion provides a bactericidal action.

 Comparing the bactericidal ability of a bactericide using a calcium component-containing substance such as a commercially available calcium phosphate reagent as a raw material with the bactericidal ability of a bactericide using a calcium carbonate-containing substance such as a shell or a bone as a raw material, the latter is better. Are better. Moreover, when a fungicide is manufactured using shells as a raw material, a fungicide using an oyster shell as a raw material has superior sterilizing ability as compared to a fungicide using other shells as a raw material.

 Figure 2 shows the component analysis table for each of the oyster shells, pokeweed shells and ikiki shells. From Fig. 2, it can be seen that the shells contain, though trace amounts, magnesium, stonium, sodium, potassium, lithium, copper, zinc, iron, manganese, phosphorus, etc., in addition to calcium carbonate. Although not shown, such components are also contained in bones, eggshells, shells of crabs and the like, and pearls.

 When a disinfectant made of a calcium carbonate-containing substance as a raw material of an animal is immersed in water, cations derived from each of the above elements are also eluted into the water in addition to calcium ions. Compared to the bactericide using calcium carbonate reagent as a raw material, the bactericidal ability of a bactericide containing a calcium carbonate-containing compound in animals is superior to that of a bactericide because these cations are also eluted in water. It is presumed that there is. That is, it is considered that not only calcium ions perform the bactericidal action, but also the ions of the above elements also perform the bactericidal action.

 Figure 2 also shows that the oyster shells have a significantly higher phosphorus content than other shells, and that the calcium carbonate in the oyster shells has a calcite structure over almost all layers. Is done. The reason that bactericides made from oyster shells are superior to bactericides made from other shells as raw materials is based on such differences in component content and structure. It is presumed that there is.

Next, the bactericidal ability of the bactericide produced by the production method according to the present embodiment against Escherichia coli will be described. First, the relationship between the heat treatment time and the heat treatment temperature in the heat treatment step S20 and the disinfecting ability of the disinfectant was examined. That is, a bactericide was produced by pulverizing oyster shells or shells of oyster shells to 10 mm, heat-treating them at various temperatures and times, and then pulverizing them to an average particle size of 10 / m. 0.25 g of each of these germicides was put into 500 ml of distilled water and stirred, and E. coli K-12 was added and stirred, and the mixture was allowed to stand. After a lapse of a predetermined time, the number of bacteria of K-12 per 1 ml of water was measured by a roller counting method, and the change with time was examined. The results are shown in Figure 3. In FIG. 3, “0 min” indicates the number of bacteria immediately after K-12. The same applies to each figure described later.

 For comparison, when no fungicide was added, no heat treatment was applied (unheated) When oysters or shells of oyster shells were added, the sterilization method manufactured by the above-described conventional manufacturing method was used. The change over time in the number of K-12 cells when the agent was added was examined. Figures 4 to 6 show the results.

 From Fig. 3 and Fig. 5, almost no bactericidal activity is exhibited in unheated shells (see Fig. 5) and oyster shells heat-treated in 600 (see 600 column in Fig. 3). You can see that they did not. Also, comparing the bactericidal ability of the bactericide using oyster shells as a raw material with the bactericidal ability of a bactericide using husk shells as a raw material, as shown in Fig. 5, for example, when heat treatment is performed at 700 for 3 hours The results and the results of the heat treatment at 900 for 13 hours indicate that the former is a more rapid-acting fungicide. Also, from Figure 4, it is clear that the bacterial count does not decrease spontaneously.

 Furthermore, comparing FIG. 3 with FIG. 6, it is clear that the fungicide produced by the production method according to the present embodiment has a faster effect than the fungicide produced by the production method according to the prior art. Is understood. That is, according to the production method of the present embodiment, it is possible to obtain a germicide having a bactericidal ability better than the bactericide produced by the production method according to the related art. In addition, while the conventional manufacturing method requires firing again for 48 hours at 845 t after firing once, the time required for heat treatment in the manufacturing method of the present embodiment is as follows: If it is 850, about 2 to 13 hours is enough.

After all, according to the production method of the present embodiment, a bactericide having excellent bactericidal ability can be produced with high efficiency. Next, oyster shells, bird bones, eggshells, crab shells, limestone, cold water powder (crystalline limestone), a calcium agent consisting of calcium lactate, calcium phosphate and calcium hydroxide

Heat treatment was performed at 85 ° C. for 13 hours. Except for the calcium agent, it was preliminarily pulverized before the heat treatment, and the average particle size was set to 10 mm. In addition, bird bones, eggshells and crab shells were washed before pre-milling.

 3.5 g of the fungicide thus produced was added to 50 liters of tap water (from which tap water was freed of chlorine) and stirred, and then K-12 was added. After stirring, the mixture was allowed to stand. Then, the time-dependent change in the number of K-12 cells was examined. Figure 7 shows the results. From FIG. 7, it can be seen that the sterilizing agent manufactured by the manufacturing method according to the present embodiment can obtain a sufficient sterilizing effect even with a mere 3.5 g of water having a volume of 50 liters. I understand.

 Also, from Fig. 7, it can be seen that all the fungicides made from oyster shells are killed in 5 minutes, despite the fact that a larger number of K-12 are used than other fungicides. I understand. From this, it is understood that this bactericide has the best bactericidal ability and the fastest effect.

 Figure 7 further shows that the fungicide based on calcium is the slowest-acting. This supports that the bactericidal action is performed not only by calcium ions but also by other ions such as phosphorus, magnesium and potassium, as described above. That is, the cation eluted from the calcium agent is only calcium ion.

 Next, the pearl or coral was washed and preliminarily pulverized to an average particle diameter of 10 mm, and then heat-treated at 850: for 13 hours to produce a bactericide. 0.25 g of each of these disinfectants and the disinfectant containing the above-mentioned oyster shells as raw materials were put into 500 ml of distilled water and stirred, and further, K-12 was put and stirred. After that, it was left still. Then, the time-dependent change in the number of K-12 cells was examined. Fig. 8 shows the results.

 From FIG. 8, it can be seen that heat-treated pearls and corals also have a bactericidal activity, and that pearl ゃ coral repellents are also more effective with fungicides made from oyster shells.

Pearls contain more calcium carbonate than oyster shells. However, as mentioned above, bactericides made from oyster shells show better bactericidal activity. are doing. This is presumed to be due to the fact that pearls contain a hard protein (organic matter) called concholine. In other words, in pearls, during the heat treatment step S20, calcium ions and other cations are partially covered with concholine, and as a result, it is considered that these ions are less likely to elute into water. .

 It can be understood from FIGS. 3 to 8 that the bactericidal ability is exhibited by heat-treating and pulverizing calcium-containing substances such as calcium carbonate-containing substances, calcium carbonate-containing minerals, or calcium-containing reagents possessed by animals. You. It can also be seen that the use of oyster shells as the calcium-containing substance, which is a raw material, has excellent bactericidal activity and is still the fastest-acting bactericide.

 Further, comparing the bactericide produced by the production method according to the prior art with the bactericide according to the present embodiment, the latter has more excellent bactericidal ability. Moreover, the latter completes the entire process in a shorter time than the former. From this, it can be said that the production method according to the present embodiment can efficiently produce a germicide having excellent bactericidal ability. In the above-described embodiment, the preliminary pulverizing step S 10 was performed. However, the pre-pulverizing step S 10 was not performed. Heat treatment. Industrial applicability

 As described above, according to the method for producing a disinfectant according to the present invention, a disinfectant can be efficiently produced. Moreover, the bactericide produced by this production method has a better bactericidal activity against bacteria such as Escherichia coli than the bactericide produced by the production method according to the prior art. In other words, the method for producing a bactericide according to the present invention can provide a bactericide having excellent bactericidal activity with high efficiency. Therefore, it is possible to stably supply a large amount of a disinfectant required in accordance with an increase in the consumption and distribution of food.

 In addition, the fungicides produced in this way do not release substances that cause health hazards to animals and plants when used. Therefore, for example, water and food can be sterilized without using sodium hypochlorite.

Claims

The scope of the claims 1. a heat treatment step of heat-treating the calcium component-containing substance at a temperature of at least 65 and below the melting point for at least 2 hours;  A pulverizing step of pulverizing the heat-treated calcium component-containing substance to an average particle diameter of 10 m or less;  A method for producing a bactericide, comprising: 2. The method for producing a disinfectant according to claim 1,  A method for producing a disinfectant, comprising a preliminary pulverizing step of pulverizing the calcium component-containing substance to an average particle diameter of 100 / xm to 20 mm before the heat treatment step. 3. The method for producing a disinfectant according to claim 1 or 2,  A method for producing a bactericide, characterized in that at least one of a calcium carbonate-containing substance and a calcium carbonate-containing mineral of an animal is used as the calcium component-containing substance. 4. The method for producing a disinfectant according to any one of claims 1 to 3,  As the calcium carbonate-containing substance, at least one selected from the group consisting of shells, eggshells, shells of shellfish, bones, corals, and pearls is used, and limestone is used as the calcium carbonate-containing mineral. A method for producing a fungicide. 5. The method for producing a disinfectant according to claim 4,  A method for producing a disinfectant, comprising using a mussel as the shell. 6. The method for producing a bactericide according to claim 4 or 5, A method for producing a bactericide, characterized in that a shell obtained by removing two or more years from a living body of a shell is used as the shell. 7. The method for producing a germicide according to any one of claims 3 to 6,  When a calcium carbonate-containing substance possessed by an animal is used as the calcium component-containing substance, the method further comprises a washing step of washing the calcium carbonate component-containing substance possessed by the animal before the heat treatment step or the preliminary pulverization step. Manufacturing method of disinfectant.