JPH03255008A - Hydrogen peroxide formulation for using in water and its use - Google Patents

Abstract

PURPOSE:To obtain the subject formulation efficiently and readily controllable and exterminable parasite, etc., living in red tide or cultured fish by mixing aqueous hydrogen peroxide, flocculant formable of floc in water and inorganic particles sedimenting in water having a specific particle diameter. CONSTITUTION:(A) Aqueous hydrogen peroxide is mixed with (B) flocculant formable of floc in water, preferably carboxymethyl cellulose, methyl cellulose, polyacrylamide, alginate or fly ash and (C) water-granulated slag made of inorganic particles sedimenting in water having about 1-1000mum, preferably about 10-600mum particle diameter and contained in the objective hydrogen peroxide formulation for using in water as essential ingredients. Mixing weight ratio of the components are preferably: B:C=(0.01:30)-(99.99:70) and A/(B+C)=5-100 wt.%. Said hydrogen peroxide formulation is able to sediment in sea water with perfectly keeping and releasing the component A in a wrapped state in the floc by actions of the components B and C.

Description

DETAILED DESCRIPTION OF THE INVENTION (a) Field of Industrial Application This invention relates to a hydrogen peroxide preparation for use in water. More specifically, this invention is intended to control, for example, so-called red tide caused by the abnormal proliferation of plankton in seawater or freshwater, or to prevent parasites and pathogenic bacteria that are parasitic to fish cultivated in seawater or freshwater. Prevention of skin diseases etc. based on
Regarding extermination, this article relates to filtered hydrogen oxide preparations that are easily used for treatment and their uses.

(b) Conventional technology Plankton, which is the cause of red tide, can be used as feed for fish and shellfish, but when they multiply in large quantities, they reduce dissolved enzymes in the water, leading to reduced feeding, poor growth, or death of farmed fish. This has had a huge impact on the fishing industry. As a countermeasure, it was reported that hydrogen peroxide at a concentration of 15 pPmI or higher has the effect of rupturing the cells of Chattonella marina, which is a typical plankton cause of red tide, and is promising as a red tide control agent (1. Academic journal-55(6) 198
9) has been made, and furthermore, Japanese Patent Publication No. 15-1411
Publication No. 42 also reports that in addition to hydrogen peroxide, calcium peroxide and sodium percarbonate are effective in preventing red tide.

However, when such hydrogen peroxides are directly sprayed in areas where red tide occurs, they settle and disperse within the area in a short period of time, and as a result, red tide control cannot be carried out efficiently. .

Therefore, silicate colloids were used in combination with the above hydrogen peroxide,
It has been proposed that red tide plankton be prevented from escaping by forming flocs of silicate colloid, while trapping red tide plankton and preventing them from settling (Patent Publication No. 1-22.54).
Publication No. 30).

On the other hand, Benedenia 5eriolae, which is a surface parasite of seawater cultured fish such as yellowtail and yellowtail, and fish tl.
fffl parasite HeLeraxine hete
When parasites such as P. rocerca infest, their growth is inhibited and the fish die or the fish body discolors and its commercial value decreases.

For this reason, as a preventive measure, old-fashioned methods such as the freshwater bathing method and the agricultural salt water method are known, but since these treatment methods do not only inhibit the growth of fish but are also dangerous, improved methods include sodium percarbonate and sodium percarbonate pyrophosphate. The so-called medicinal bath method is being considered by Shizuoka Fisheries Experiment Station, etc.
Research report on fish disease control in 1966 (Research on Benedenia 5eriolae), etc.).

(c) Means for solving the problem However, in the red tide control method using the above-mentioned floc-forming agent, the ability of the flocs generated by spraying to capture plankton is insufficient, and the flocs remain near the sea surface for a long time. It floats quickly and is difficult to settle down. In particular, red tide plankton swims not only near the sea surface, but also in a certain extent in the depth direction, for example, up to about 15 meters below. However, even if it is possible to prevent plankton in the sea, it is inconvenient that it is not possible to quickly eliminate plankton, and this poses a major problem in terms of control efficiency.

On the other hand, drugs that have been recognized as having medicinal efficacy in the method for exterminating parasites of seawater cultured fish (medicinal bathing method) are either poorly soluble in seawater or exhibit alkalinity in seawater, changing the properties of seawater. Because of its variable nature, there were difficulties in its usage.

This invention was made under such circumstances, and is particularly useful for controlling red tide or exterminating parasites that infect cultured fish.It is extremely easy to use as a practical technology and is easy to operate compared to conventional methods. The purpose is to provide an underwater hydrogen peroxide preparation that can efficiently achieve the purpose of pest control and extermination. In particular, the inventors of the present invention have taken into account that the dynamic movement or swimming of red tide or cultured fish in water has six different depths and spreads, and it has been found that such red tide can effectively come into contact with cultured fish in water. At the same time, as a result of intensive studies, we have arrived at this invention in order to provide a formulation and its uses that can exert the medicinal effects of hydrogen peroxide, which is a pest control and extermination agent.

(d) Means for Solving the Problems According to the present invention, (a) hydrogen peroxide solution, (
There is provided an underwater hydrogen peroxide preparation prepared by blending b) a flocculant capable of forming flocs in water, and (c) inorganic particles that settle in water and having a particle size of about 1 to 1000 μm.

In the formulation of this invention, hydrogen peroxide is the main medicinal ingredient for the use and purpose of this invention, but in general, when hydrogen peroxide alone is added to water, it quickly settles in the water and is unable to exert its medicinal effect. Therefore, in the present invention, a preparation consisting of the flocculant (b) and the inorganic particles (c) that settle in water is used in the form of an aqueous solution.

A flocculant capable of forming flocs in water (
As b), for example, carboxymethyl cellulose (hereinafter referred to as CMC) having an average molecular weight of 20,000 to 200,000, also has an average molecular weight! 20,000 to 200,000 sodium alginate,
Natural polymer compounds such as gum arabic, roasted pea gum, caseinate, guar gum, animal and vegetable gluten, or starch, 5 6 Methylcelluloses such as hydroquine methylcellulose, etquine methylcellulose, and methylcellulose with an average molecular weight of 20,000 to 200,000, average Cationic, anionic or nonionic synthetic polymer compounds such as polyacrylamide with a molecular weight of 20,000 to 200,000, polyethyleneimine with a molecular weight of tens of thousands to several million, polyethyleneamine with a molecular weight of several hundreds of thousands to several million, and even , flocculants which are inorganic compounds such as fly ash and polyaluminum chloride.

Such a flocculant has the effect of flocculating the hydrogen peroxide solution (a) and the sedimentary inorganic particles (c) in water to form a floc, and it is easy to prepare the preparation and the flocculation and flocculation. Among the flocculants mentioned above, CMC, methylcelluloses, polyacrylamide, sodium alginate, and fly ash are particularly preferred from the viewpoint of flocculating ability.

In general, red tide occurs when swimming and
Movement, and cultured fish are placed between 1m and 5-6m below the water surface in the cage.
Depending on its use, the formulation of the present invention can be settled and dispersed at a desired depth of water to allow sufficient contact with flowing or swimming red tide or cultured fish. should be adapted.

For this reason, the water-sedimentable inorganic particles used in the formulation of this invention have a specific gravity (usually a true specific gravity of 2 to 5) that exhibits sedimentation properties in freshwater and seawater. Porous or non-porous inorganic particles of a type are selected such that the formulation allows the flocs formed to settle at depths of water suitable for the intended use.

From this point of view, the water-sedimentable inorganic particles used in the formulation of the present invention include natural inorganic minerals known as so-called seabed quality improvers, such as clay, lime, oyster shells, and gravel, with a particle size of 1 to 1000 μm, and water. Artificial inorganic materials such as crushed slag are suitable.

Sedimentable inorganic particles with a particle size in the range of 1 to 1000 μm mix well with flocculants and are uniformly dispersed in water to form a mixed floc with sedimentation properties, but particles with a particle size of 1 μF
If the particle size is less than 1,000 μm, the flocs formed will tend to smudge the surface of the water when spraying the preparation from a comb, and if the particle size exceeds 1000 μm, they will settle quickly in deep water. Therefore, it tends to be difficult to disperse and hold the target water area for a certain period of time, which is undesirable.

By selecting inorganic particles having a particle size [~1000 mark and a true specific gravity within the range of 2 to 5, it is possible to generate a controlled sedimentary floc according to the purpose of the present invention. Considering the ocean currents in the actual ocean area, the particle size is 10~600μ.
Preferably, m inorganic particles are used.

According to the inventor, it has been found that the control effect of hydrogen peroxide by the preparation of the present invention is superior to the already known effect of controlling red tide plankton by hydrogen peroxide itself. . Although the reason for this is not clear, divalent metal components (e.g., iron, calcium, magnesium, etc.) contained in the precipitable inorganic particles used in this invention are leached and released in water, and It is speculated that this is due to the activation of the medicinal effect of hydrogen oxide. Therefore, as the inorganic particles that can settle in water, granulated slag containing a particularly large amount of such divalent metals is most preferable.

The hydrogen peroxide preparation of the present invention can be prepared by mixing hydrogen peroxide solution (a), flocculant (b), and precipitable inorganic particles (c) in a suitable container. At this time, by increasing or decreasing the amount of hydrogen peroxide solution and the amount of water, the preparation of the present invention in the form of a solid, fluid gel, or liquid can be obtained. For example, solid preparations can be crushed and used as appropriate, but from the viewpoint of ease of preparation and work when spraying the preparation into water, it is preferable to use a liquid form with appropriate liquid viscosity. Preferably.

The hydrogen peroxide concentration in such preparations varies depending on the purpose of use, but usually in liquid preparations the final concentration is 0.01 to 0.01.
A suitable content is 10% by weight. The specific preparation method including such concentration adjustment is not particularly limited, but
In order to improve formulation stability, especially to prevent decomposition of hydrogen peroxide, the flocculant, precipitable inorganic particles and water are first mixed uniformly, and then 1-10% by weight, preferably 5-6% by weight of hydrogen peroxide is added. It is preferable to add 9 10 water. If the storage period of the prepared preparation is expected to be long, it is recommended to add hydrogen peroxide immediately before use to prevent the hydrogen peroxide from decomposing and reducing its efficacy. Ru.

As mentioned before, when the formulation of this invention is sprayed on the water surface, the flocs formed do not remain suspended on the water surface, but contain hydrogen peroxide in the flocs and slowly settle in the water. During this time, plankton is captured and hydrogen peroxide is gradually released.In order to retain the functions of floc generation, submergence in water, and release of hydrogen peroxide, the proportions of each component of the formulation are as follows: First, the ratio of flocculant to sedimentary inorganic particles is about 0.01 to 30.70 to
99.99 is suitable, and in order to have a liquid viscosity that is easy to handle when spraying the preparation into water, the water content is preferably 98 to 85% by weight, preferably 95 to 9%, based on the total solid content.
Suitably, the content is 0% by weight.

The formulation of this invention can be used in waters where red tide occurs to prevent damage to fish.

More specifically, when the red tide moves in the ocean or approaches the aquaculture cage, the preparation of the present invention is uniformly applied to the entire surface or outer edge of the red tide using a watering pump or the like from the air or a ship. Spray on. The sprayed preparation forms flocs near the water surface, but according to experiments conducted by the inventors, it has been confirmed that the flocs also adsorb red tide, enveloping it, and sinking in the water. During this period, the red tide plankton is effectively contacted from the upper layer where the swimming concentration is high to the deep water area of the swimming area, and during this time, the plankton is prevented by stopping swimming, and causing the plankton to become round and even burst.

The amount of spraying of the preparation added for the prevention of red tide is determined by calculating the amount to be 5 to 1100 pp, preferably 10 to 5099 m, which is the previously confirmed effective concentration of hydrogen peroxide for red tide prevention. Should.

Furthermore, the formulation of the present invention is effective in preventing and exterminating parasites that infect cultured fish (yellowtail, yellowtail, Japanese horse mackerel, Japanese yellowtail, yellowtail, sea bream, flounder, etc.) in seawater.

To be more specific, I use korai anyu.

5iO232-35% as a sedimentary inorganic compound,
F e 20-0.6-0.9%, Ca0 41-44
Various types of water with particle sizes of 1 to 80 microns (Type A), 80 to 200 microns (Type B), and 40 (1 to 1.000 microns (Type C), respectively, with true specific gravity of 2.9 and containing % as the main component. Uses crushed slag.

A mixture containing the combinations and proportions shown in Table 10.
Filtered seawater and hydrogen peroxide at a concentration of 5.85% were added to 59 and the total amount was made into LO side Q, and the mixture was stirred and mixed to obtain various formulations of the present invention (viscosity: 5 to 700 cp).

Add various preparations to the test solution in the test tube, add filtered seawater to make the total volume 100i (!), then gently invert 10 times, let stand, and after 15 minutes, 30 minutes, and 60 minutes, the water surface Water was sampled from a depth of 2 cm (the main floating water depth where C.marina is active) and examined under a microscope.
The ecological condition of the ina and its enemies were measured to determine the extermination rate.

At the same time, tests were also conducted in which the formulation of the present invention was not added to the test liquid, and one and two components of a flocculant, an inorganic compound, or hydrogen peroxide were added, and the differences in control rates were compared.

The formula for the control rate in 1 is: Show test results Shown in 1.

(Left below) 1/7- -l? - Discussion As is clear from the test results, when hydrogen peroxide is used alone (trial numbers No. 2, No. 3), hydrogen peroxide easily settles, so the contact time with C, marina is short. It can be seen that C. marina cannot be sufficiently controlled.

In addition, in preparations consisting of granulated slag and hydrogen peroxide (test numbers No. 5. No. 7. No. 9), C,
It can be seen that although the control rate of marina increases slightly, it is not sufficient, and that granulated slag with a small particle size has poor sedimentation properties.

In addition, preparations using granulated slag or flocculant alone or in combination with both (Test No. No. 4. No. 6. No. 8. No.
.

10 No, I2. No, 14 No, 16. No
, +8. N.

20) It can be seen that the control effect of C. marina is insufficient and cannot withstand actual use.

In comparison with the above formulations, the formulation of the present invention (No. 11
No. +3 No, 15. No, 17. No, +
9. N.

In 21), the control rate of C. marins was significantly better than that of hydrogen peroxide alone or the formulation using granulated slag and hydrogen peroxide in combination. It can be seen that the properties are also good. Even when used in actual sea areas, it is believed that sufficient control effects will be exhibited because C and marina will be adsorbed to deep water areas, enveloping them, and sinking into the water.

(f) Effects of the Invention According to the hydrogen peroxide of this invention alone, hydrogen peroxide is ideally retained and released in the form of flocs due to the action of its flocculant component and inorganic particles that settle in water. It can be sunk into the ocean.

The red tide plankton is captured by flocs.

Therefore, the formulation of this invention can be used to control red tide plankton,
It is extremely useful as a chemical for pest control and extermination treatments that require the action of hydrogen peroxide not only on the sea surface but also within a certain area and for a certain period of time in the sea, such as the extermination of fish parasites.

I

Claims (1)

[Claims] 1. (a) hydrogen peroxide solution; (b) a flocculant capable of forming flocs in water; (c) inorganic particles that settle in water and have a particle size of about 1 to 1000 μm;
Hydrogen peroxide preparation for underwater use. 2. The formulation according to claim 1, wherein the flocculant (b) is carboxymethyl cellulose, methyl cellulose, polyacrylamide, alginate or fly ash. 3. The inorganic particles (c) that settle in water have a particle size of approximately 10 to 600μ
2. The formulation according to claim 1, which is a granulated slag prepared at m. 4. The preparation according to claim 1, wherein the flocculant (b) and the water-sedimentable inorganic particles (c) are blended in a weight ratio of 0.01:30 to 99.99:70. 5. The formulation according to claim 1, wherein the content of hydrogen peroxide is 0.05 to 1 part by weight per 1 part by weight of the total amount of the flocculant (b) and the water-sedimentable inorganic particles (c). 6. The formulation according to claim 1, which is used for controlling red tide. 7. A method for controlling red tide, which comprises spraying the underwater hydrogen peroxide preparation according to claim 1 in a sea area where red tide occurs.