WO2001067866A1

WO2001067866A1 - Antibacterial agent comprising shell, method for purifying water by using the antibacterial agent and method for washing farm product by using the antibacterial agent

Info

Publication number: WO2001067866A1
Application number: PCT/JP2000/001495
Authority: WO
Inventors: Manabu Sasaki
Original assignee: Surfcera Co., Ltd.
Priority date: 2000-03-13
Filing date: 2000-03-13
Publication date: 2001-09-20
Also published as: AU2943100A; KR20020011412A; CN1269406C; CN1376034A

Abstract

An antibacterial agent having a high antibacterial effect which can be economically produced in a large amount from a natural material causing no problem when taken into the human body. This antibacterial agent is produced by starting with a surf clam (Spisula sachalinensis) shell powder and baking this shell powder in an inert gas atmosphere to attain a final temperature of 700 to 2500°C.

Description

Description Antibacterial agent comprising shells, water purification method using antibacterial agent, and agricultural crop cleaning method using antibacterial agent.

Technical field

The present invention uses an antibacterial agent that prevents food contamination by bacteria in the processed food manufacturing industry, the restaurant industry, and the home, and is suitable for sterilization, disinfection, and disinfection in the medical industry and the medical welfare industry. The present invention relates to purification of seawater and river water, and a cleaning method using water purified by the antibacterial agent. Background art

Chlorine compounds that have been used as general antibacterial agents sometimes cause trihalomethane during wastewater treatment and dioxin during incineration treatment. Examples of antibacterial agents that have been used as food additives include synthetic antibacterial agents such as sulfamidine and canolebadox as veterinary drugs used in livestock and marine products. It was necessary to strictly adhere to the residual standard value.

Therefore, the demand for antibacterial agents made from natural materials, not antibacterial agents composed of the above-mentioned chemically synthesized products, has become active, particularly in the field of those that may be orally ingested. For example, in 1995, a group of Professor Tadakatsu Shimamura of the Showa University School of Medicine announced the effect of green tea on 0-157, which attracted the attention of consumers. With this announcement, tea catechins, which have been used in traditional food additives, have become more popular.

The above-mentioned tea catechin, which has attracted attention as an antibacterial agent using natural materials as a raw material, is not suitable for mass production because it must be extracted from green tea, which is a raw material. Therefore, it can be produced in large quantities at low cost from natural materials that have no problem in ingestion into the human body, and high antibacterial effects, new antibacterial agents, antibacterial agents are required. RU

In particular, antibacterial agents made of natural materials that have no problem in ingestion into the human body are considered effective for water purification. The following are some examples that are currently in question. The first is desalination of seawater. In other words, in the Middle East countries, reverse osmosis Fresh water is obtained from seawater by distillation, refrigeration or electrodialysis. In this way, removing salt from seawater makes it easier for bacteria to proliferate. Therefore, Cr-based or C1-based disinfectants are added to prevent the propagation of sterilization. Cr and C1 are extremely harmful to the human body, and the risk of carcinogenesis cannot be ruled out.

Second is the purification of rivers. In other words, in rivers into which domestic wastewater (organic matter) flows, the BOD value increases, which also causes odor.

Third is the cleaning of crops. In other words, insecticides may be attached to crops after harvesting. Therefore, crops are washed with synthetic detergents to wash away pesticides, etc., and then rinsed with general water (tap water or river water). However, general water itself has poor antibacterial activity, and there is a risk that bacteria will grow on the surface of crops before reaching general consumers. Disclosure of the invention

In order to solve the above-mentioned problems, claim 1 specifies an antibacterial agent composed of shells. That is, the antibacterial agent according to the present invention can be obtained by heating the shell in an inert gas atmosphere, raising the temperature, and baking at a final temperature of 700 to 2500 ° C.

The shell is most preferably a sea scallop, which also has a bactericidal activity against general bacteria, but may be oysters, scallops, anemones, sazae, or oysters as long as it is baked. By baking, the shell itself becomes porous, which increases the contact area and greatly improves the antibacterial activity.

In particular, shellfish powder of sea mussels exerts strong and continuous antibacterial properties against pathogenic Escherichia coli 0_157 and other bacteria even when added in a small amount, by being baked in an inert gas atmosphere. In addition, it is a natural material that is mainly composed of calcium and is safe for the human body. And even if waste treatment is necessary, it will not pollute the air, wastewater, and soil. In addition, there is also an effective use and use of shells that have been left over as waste.

Further, if the above antibacterial agent is pulverized so that the maximum particle diameter is 100 μm or less and the average particle diameter is 1 to 50 μm, it is easily dissolved in water (hot water), and the antibacterial effect is further improved.

In addition, baked seashells made from natural materials are listed in the list of existing additives (announced on April 16, 1996), which is stipulated in the Food Sanitation Law and the Partial Amendment to the Nutrition Improvement Law. Sintered calcium (based mainly on calcium compounds obtained by baking shells etc.) And is certified to be safe for the human body.

Therefore, the use of the antibacterial agent of the present invention is suitable for prevention of food contamination by bacteria in the processed food manufacturing industry, the restaurant industry, and the home, and sterilization, disinfection, and bacteria elimination in the medical industry and the medical welfare industry.

Further, the present invention, which is applied to desalination of seawater, desalinates seawater using any one of a reverse osmosis membrane method, a distillation method, a cold freezing method, and an electrodialysis method, and the desalinated seawater is subjected to the antibacterial method. The agent was brought into contact.

By adopting such a configuration, it becomes possible to eliminate the addition of the Cr-based or C1-based bactericide, which has been conventionally added after desalination, or to significantly reduce the amount thereof.

In the present invention for application to purification of river water, the antibacterial agent is filled in a net (including a case through which river water can pass), and the net is laid in the river J11.

The baked shell, in addition to its own antibacterial action, becomes porous, and bacteria that decompose organic matter proliferate on the surface and promote the purification of river water. Then, when the acidity of the river water further increases, the baked shells dissolve and maintain the pH of the river water within the optimal range.

Further, according to the present invention, which is applied to the cleaning of agricultural products, agricultural products such as vegetables and fruits are washed with a synthetic detergent and then rinsed with water contacted with the antibacterial agent.

With this configuration, it is possible to suppress the growth of bacteria on the surface of agricultural products for a long period of time. BRIEF DESCRIPTION OF THE FIGURES

Figure 1 is a block diagram showing the seawater desalination process. Figure 2 (A) is a diagram illustrating the method of purifying river water, and Figure 2 (B) is a perspective view of a net installed on the riverbed. FIG. 3 (A) is a diagram showing a cleaning state of the crop, and FIG. 3 (B) is a diagram showing a rinsing state after the cleaning. BEST MODE FOR CARRYING OUT THE INVENTION

The sea mussel, which is a raw material of the antibacterial agent of the present invention, is an edible bivalve, also called a mussel, which is distributed in central Honshu and the northern Japan Sea. These crabs are used for canning, freezing, and eating raw foods, but at present, shellfish shells are not used effectively, so procurement costs are low.

In order to produce the antifungal agent of the present invention, crustacean shells are first crushed. As for the method of pulverization, after the shells are dried, they are roughly pulverized with a grind mill, for example, so that the maximum particle size is 5 mm or less. Next, the crushed shell is placed in an autoclave with a stirrer and heated while stirring in an inert gas atmosphere. Nitrogen gas is preferred as the inert gas. There is no limitation on the heating method, but the final temperature is 700 to 2500 ° C, preferably 900 ° C ± 50 ° C, and this temperature is maintained for 3 minutes or more.

If the final temperature is less than 700 ° C, the antibacterial activity is difficult to develop. If the temperature exceeds 1000 ° C, the active site of the particles will be destroyed and the antibacterial activity will also decrease. If the baking time is less than 3 minutes, it is difficult to exhibit antibacterial activity. The firing time may be long, but the cost is preferably about 3 to 5 minutes.

The calcined shell particles are allowed to cool in an inert atmosphere, and then finely pulverized and classified to obtain a powder having a maximum particle size of 100 zm or less and an average particle size of 1 to 50 m, preferably 2 to 5 m.

If the maximum particle size exceeds 100 Zm or the average particle size exceeds 50 μπι, it will not dissolve even when added to drinking water, for example, due to antibacterial treatment, and will precipitate and not function properly. ,. If the average particle size is less than 1 im, it becomes difficult to handle such as solidifying by absorbing moisture. However, depending on the mode of use, the baked shell can be used as it is without grinding. In other words, when miniaturized, the effect is large because it dissolves in water, but the effect disappears in a short period of time. If long-term effects are expected, it is preferable to use the baked shell as it is, or to knead the finely divided powder with a binder and then bake it into a predetermined shape.

The antimicrobial agent produced from the crab shellfish produced as described above is effective against food poisoning bacteria such as E. coli 157, Staphylococcus aureus, Pseudomonas aeruginosa, fungi, Salmonella, Vibrio parahaemolyticus, and even viruses. there were.

Specific examples of use of the antibacterial agent of the present invention include use as an additive in foods such as kamaboko, sterilization of drinking water and hand washing water, addition to dental materials such as dentures, and the form of an antibacterial powder pack. put in a home for the pot or, disaster can be the child and the force ^s used in the disinfection of emergency drinking water as. It can be added to sheets and used for wiping, or used as an antibacterial functional additive for paper, wallpaper, or building materials. As another method of use, it is possible to make this antibacterial agent itself a ceramic, or to make a sterilizer using the antibacterial function.

The antibacterial agent of the present invention exhibits higher antibacterial properties than antibacterial agents such as tea catechin and oyster shell. I Therefore, it is characterized by the ability to exert an antibacterial function in a very small amount and a long duration of the effect. For example, the addition amount of 0.025% by weight with respect to the weight of drinking water and other sterilized substances is sufficient. It has also been confirmed that the antimicrobial effect lasts for 48 hours or more.

(Example)

Production of antibacterial agent:

After drying the clamshell, 500 g of pre-ground to about 2 to 3 mm was put into a 2-liter autoclave with a stirrer filled with nitrogen gas, and the temperature was raised while gently stirring. This heating was continued until the temperature reached 900 ° C. After the temperature reached 900 ° C, the heating was stopped by heating for 5 minutes, and the autoclave was allowed to cool in a nitrogen gas flow until the inside of the autoclave returned to normal temperature.

After cooling, the calcined shell powder was taken out of the autoclave, further pulverized in a mortar, and only particles having a particle size of 50 zm or less were fractionated with a classifier to produce the antibacterial agent of the present invention.

The component concentrations of this antibacterial agent are shown below (Table 1) (analysis by soil nutrient analysis performed by Yamagata Prefectural Physical and Chemical Analysis Center, Yamase No. 778).

(table 1)

Separately, bamboo charcoal was pulverized and prepared into particles having a particle size of 50 μm or less in the same manner as described above, and mixed with the above-mentioned anti-bacterial agent for sea otters and shells at a weight ratio of 1: 1 to produce an anti-bacterial agent as a modified example. .

Further, oyster shell powder was produced by performing the same baking and crushing treatment using oyster shells in place of the above-mentioned crab.

Test strain:

Escherichia coli (Escherichia coil ATCC 8739), Staphylococcus aureus ATCC 6538) and Pseudomonas aeruginosa ATCC 9027) were used. The medium used was a DD checker for general bacteria, blood agar plates, and the culture conditions were ₃₇ to ₁₈ hours.

Test method:

Each of the produced antibacterial agents was dissolved in distilled water to adjust to a predetermined concentration, and each of the above-mentioned test bacteria was added to these antibacterial agent-dissolved distilled water so as to be about 106 π. After the addition of the bacteria, the mixture was stirred well, and then allowed to stand at room temperature. After a predetermined time, sampling was performed to measure the number of growing bacteria (Zml).

(Example 1)

Solution in distilled water Hotsuki shellfish shells made antibacterial agent prepared by the use of (1 wt%, 0.5 wt ^_0/0, 0.1 wt% and 0.05 wt%), Escherichia coli, the sterilization effect of Staphylococcus aureus and Pseudomonas aeruginosa Examined. Table 2 shows the results.

(Example 2)

The sterilization effect was examined in the same manner as in Example 1 except that a mixed antibacterial agent of bamboo charcoal and a seafood shell (weight ratio 1: 1) was used instead of the antibacterial agent made of the seashell. Table 2 shows the results. (Example 3)

The sterilization effect was examined in the same manner as in Example 1 except that an antibacterial agent made from oyster shells was used instead of an antibacterial agent made from crab shells. Table 2 shows the results.

(Table 2)

Example Antimicrobial agent Escherichia coli S. aureus Pseudomonas aeruginosa and comparative concentration 15 minutes 24 hours 15 minutes 48 hours 15 minutes 2 hours Example (w%)

1% <20 20 <2 <2 <2 <2 Example 1 0.5% <20 <20

0.1% 20 <20 1.9X10 ² 60 <2 <2

0.05% <20 <20

1% 20 <20 2.0 X10 ² 80 <2 <2 Example 2 0.5% <20 20

0.1% <20 20 2.0 10 ⁴ 2.0X10 ² <2 <2

0.05% 4.0 X10 ³ <20

1% <20 <20 40 2 <20 2 Comparative Example 1 0.5% 6.4X10 ² <20

0.1% 2.5X10 ³ 2.5X10 ⁶ 4.0X10 ⁵ 5.2X10 ⁵ 2.2 X10 ² <1

0.05% 2.5X10 ⁵ 1.2X10 ⁵

Control Distilled water 6.0X10 ⁵ 4.0 10 ⁵ 4.0X10 ⁵ 3.6X10 ⁵ 8.0 10 ⁵ 4.0X10 ⁶ As is clear from the test results in Table 2, the antimicrobial agent of the shellfish shellfish achieved a sufficient sterilization effect even at a low concentration of 0.05%, and the effect was maintained after 24 hours and 48 hours. On the other hand, the antibacterial agent for oyster shell was effective at 1% concentration. Therefore, seafood is most effective

8 "Yes.

(Example 4)

The concentration of the distilled water solution of the antibacterial agent of the shellfish shell was further reduced (0.025 weight /. And 0.005 weight) as compared with Example 1, and the sterilizing effect of Escherichia coli and Pseudomonas aeruginosa was examined. Table 3 shows the results.

(Example 5)

The sterilization effect was examined in the same manner as in Example 4 except that a mixed antibacterial agent of bamboo charcoal and sea urchin (weight ratio: 1: 1) was used instead of the antibacterial agent made of the seashell. Table 3 shows the results. (Table 3)

From the test results shown in Table 3, it was found that the antimicrobial agent made of the sea oyster shell has a sufficient antimicrobial effect even at a low concentration of 0.025% by weight.

Next, a further sterilization test was conducted on the antibacterial agent (surf clam calcium powder), calcium bicarbonate, scallop, sea cucumber, scallop, oysters, and oysters according to the present invention. It was done in. The results are shown in the following (Table 4) to (Table 16). (Table 4) Specimen: Surf crumb calcium powder (the present invention)

Number of general bacteria (/ ml) Number of coliforms (ml) Standard agar medium Desoxycholate medium Test solution

(Specimen containing 0.1¾W / V 12.0.

Hot spring miscellaneous water collected 10 minutes later)

Control solution 11000.410.

(Hot spring miscellaneous drainage)

(Table 5) Sample: Calcium bicarbonate (calcined at 1000 ° C)

Number of general bacteria (/ ml) Number of coliforms (ml) Standard agar medium method Desoxycholate medium method Test solution

(Sample 0.1XW / V-containing river water 56.0.

10 minutes later)

Control solution 17000.57.

(River water)

(Table 6) Specimen: calcium bicarbonate (unfired)

Number of general bacteria (ml) Number of coliforms (ml) Standard agar medium method Desoxycholate medium test solution

(Sample river water containing 0.1% W / V 18000.26.

10 minutes later)

Control solution 17000.57.

(River water) (Table 7) Specimen: dried scallops

Number of general bacteria (ml) Number of coliforms (ml) Standard agar medium method Desoxycholate medium method Test solution

(Sample river water containing 0.1% W / V 720.0.

10 minutes later)

Control solution

3100.56.

(River water)

(Table 8) Specimen: unbaked scallop

Number of general bacteria (Zml) Number of coliforms (Zm1) Standard agar medium method Desoxycholate medium test solution

(Sample river water containing 0.1% W / V 4100.62.

10 minutes later)

Control solution 3100.56.

(River water)

(Table 9) Sample: Dried clams

Number of general bacteria (/ ml) Number of coliforms (Zm1) Standard agar medium method Desoxycholate medium method Test solution

(Sample river water containing 0.1% W / V 630.0.

10 minutes later)

Control solution 3100.56.

(River water) (Table 10) Specimen: Unbaked clams

(Table 11) Sample: Dried product

(Table 12) Specimen: Unbaked product Sazae

(Sample 0.1WV / V containing river water 3700.54.

10 minutes later)

Control solution 3100.56.

(River water) (Table 13) Specimen: dried oyster

(Sample river water containing 0.1% W / V 650.0.

10 minutes later)

Control solution

3100.56.

(River water)

(Table 14) Specimen: Unbaked product persimmon

Number of general bacteria (ml) Number of coliforms (Zm1) Standard agar medium method Desoxycholate medium test solution

(Sample river water containing 0.1% W / V 3600.

10 minutes later)

Control solution 3100.56.

(River water)

(Table 15) Sample: Dried oyster

Number of general bacteria (ml) Number of coliforms (/ ml) Standard agar medium method Desoxycholate medium method Test solution

(Sample river water containing 0.1 WV / V 620.0.

10 minutes later)

Control solution 3100.56.

(River water) (Table 16) Sample: Unbaked product oyster

(Sample o.i w / v-containing river water 3700.62.

10 minutes later)

Control solution 3100.56.

(River water)

From Tables 4 to 16, it can be seen that the shellfish powder of sea mussels baked in an inert gas atmosphere has lower sterilizing power than calcium bicarbonate, but has higher sterilizing power than other shell powders. You can see Also, it can be seen that there is a marked difference in sterilization power between the baked products including other shell powders and those not baked.

Next, specific examples of desalination of seawater, purification of river water, and washing of crops using the above-described fired shells will be described with reference to FIGS.

Figure 1 is a block diagram of seawater desalination. To desalinate seawater, first pump seawater into a storage tank using a pump.

A separation tank is provided below the storage tank. The separation tank is separated into a primary chamber and a secondary chamber by a reverse osmosis membrane, and the seawater in the storage tank is sent to the primary chamber via a pipe.

Headwater pressure acts on seawater in the primary chamber, and freshwater from which NaCl etc. has been removed permeates the reverse osmosis membrane and is collected in the secondary chamber.

Then, the fresh water in the secondary chamber passes through a column filled with an antibacterial agent obtained by baking shells such as surf clam, and is sterilized during that time and supplied to a predetermined location.

Fig. 2 (A) is a diagram illustrating the method of purifying river water, and (B) is a perspective view of a net installed on the riverbed. In this embodiment, a shell such as a safari clam (butterfly clam) is used. The fired material is filled into a net, and this net is laid on the riverbed.

In the case of this embodiment, the fired shells should not be crushed finely. The fired shells become porous, and the baked shells grow as soon as patella, which has a large specific surface area and decomposes organic matter, breeds. It also has the effect of dissolving itself and keeping the pH of river water constant.

Fig. 3 (A) is a diagram showing the cleaning state of the crop, and (B) is a diagram showing the rinsing state after the cleaning. In this example, the crop was placed in a container した filled with a synthetic detergent. The basket is immersed, then the skewers are taken out, and the water in contact with the baked shells is showered and sprinkled on the crops to remove the detergent attached to the surface. Industrial applicability

As described above, the method for producing the antibacterial agent of the present invention and the method obtained by this method The antibacterial agent has high antibacterial properties by being manufactured by baking shell powder such as sea mussels in an inert gas atmosphere.

Specifically, it exhibits a bactericidal effect at a low concentration on food poisoning bacteria such as Escherichia coli such as O-157, Staphylococcus aureus, Pseudomonas aeruginosa, fungi, Salmonella, Vibrio parahaemolyticus, and even viruses, and retains antibacterial function. Time is long, too.

In addition, shell powder such as sea mussels is a natural material mainly composed of calcium, which is also used as a food additive, so it can provide a safe antibacterial agent to the human body. Does not pollute air, wastewater or soil.

Further, by utilizing the antibacterial agent of the present invention, shells such as sea otters, which have been conventionally left over as wastes, can be effectively used for desalination of seawater, purification of river water, or washing of agricultural products.

Claims

The scope of the claims

1. An antibacterial agent consisting of shells obtained by heating shells in an inert gas atmosphere, raising the temperature, and baking at a final temperature of 700 to 2500 ° C.

2. The antibacterial agent according to claim 1, wherein the shell is a scallop.

3. The antibacterial agent according to claim 1, wherein the shell is any of oyster, scallop, hamadari, sazae, and oyster shell.

4. The antibacterial agent according to claim 1, wherein the antibacterial agent is pulverized before or after baking, and is characterized by shell strength.

5. The antibacterial agent according to claim 4, wherein the maximum particle size of the crushed antibacterial agent is 100 / m or less, and the average particle size is 1 to 50m. .

6. The antibacterial agent according to claim 1, wherein the antibacterial agent includes powder obtained by pulverizing bamboo charcoal.

7. The seawater is desalinated using any of the reverse osmosis membrane method, distillation method, freezing method or electrodialysis method, and the desalinated seawater is described in claims 1 to 6. A method for purifying seawater, comprising contacting with an antibacterial agent.

8. A method for purifying river J11 water, comprising filling a net with the antibacterial agent according to claims 1 to 6 and laying the net in river J11. .

9. After cleaning agricultural products such as vegetables and fruits with a synthetic detergent, the agricultural products are characterized by being rinsed with water that has been brought into contact with the antibacterial agent described in claims 1 to 6 of the claims. Cleaning method.