JPH0240309A - Controlling agent against algae, method for cleaning water using the same agent and preventing fish and shellfish from smelling - Google Patents

Abstract

PURPOSE:To effectively inhibit growth and propagation of aquatic algae without impairing safety for human bodies, fishes and shellfishes and purify industrial or drinking water and prevent fishes and shellfishes from smelling by using a controlling agent against algae containing protamines as an active ingredient. CONSTITUTION:A controlling agent against algae, containing protamine, a salt or derivative thereof as an active ingredient, capable of effectively controlling algae, etc., with simultaneous high safety for human bodies, fishes and shellfishes, etc. Furthermore, the above-mentioned active ingredient is sprayed on habitat environmental water of fishes and shellfishes to effectively inhibit growth and propagation of aquatic algae generating mold, mud smell, etc., without adversely affecting human bodies, fishes, shellfishes, etc., simultaneously improve various disorders occurring in handling industrial or drinking water or sanitary problems due to development of strange taste and offensive smell and simultaneously prevent smelling of the fishes and shellfishes. Thereby, taste is prevented from deteriorating.

Description

DETAILED DESCRIPTION OF THE INVENTION (Field of Industrial Application) The present invention relates to an algae control agent containing protamine as an active ingredient, and also to a method for purifying drinking water, etc., and for preventing odor from fish and shellfish using the control agent. Regarding the law.

(Prior art and its problems) Conventionally, algae growing in various cooling towers, industrial cooling water system towers, and drinking water tanks attached to buildings, etc. have caused a decrease in heat exchange efficiency, corrosion damage, and slime damage. This causes sanitary problems such as scale failure and the transfer of Type 1 off-taste and odor to drinking water.

Furthermore, if this algae occurs in the habitat of seafood,
The off-flavor and off-odor components of algae migrate and accumulate in the bodies of fish and shellfish, significantly impairing their taste and making them unfit for consumption, resulting in the problem of causing great damage to the aquaculture industry.

To solve this problem, various algae control agents including copper compounds, chlorine compounds, quaternary ammonium salts, etc. have been proposed, but all of these control agents are highly toxic and pose a risk to humans and fish. It has the disadvantage of having a negative impact on the class.

Therefore, an object of the present invention is to provide an algae control agent that can effectively control algae and the like and is highly safe for the human body, fish and shellfish, and the like.

Another object of the present invention is to prevent the growth and proliferation of aquatic algae without compromising safety for animals, thereby eliminating the aforementioned various problems that occur when handling industrial water, drinking water, etc. to provide purification methods.

Still another object of the present invention is to provide a method for preventing odor on fish and shellfish, which can prevent the transfer of off-taste and odor to fish and shellfish by preventing the growth and proliferation of algae in the habitat of the fish and shellfish. It is in.

(Means for Solving the Problems) According to the present invention, there is provided an algae control agent characterized by containing protamine, a salt thereof, or a derivative thereof as an active ingredient.

The present invention also provides a method for purifying industrial water or drinking water, which comprises spraying protamine, a salt thereof, or a derivative thereof into a water source or waterway to inhibit the growth and proliferation of aquatic algae.

The present invention further provides a method for preventing odor in fish and shellfish, which comprises spraying protamine, a salt thereof, or a derivative thereof into water in a fish habitat to inhibit the growth and proliferation of algae.

(Function) According to the present invention, protamine, its derivatives, or their salts can be used alone or in combination with other substances that increase the algae control effect to form an algae control agent, thereby achieving extremely high safety. The growth and proliferation of algae can be suppressed while maintaining the properties of the algae, and dead algae can also be easily removed.

Protamine used in the present invention is generally found in the testis of fish and is bound to deoxyribonucleic acid. Typical protamines listed in fish include salmin (in the sperm nucleus of salmon), scombrin (in the sperm nucleus of mackerel), sibulinin (in the sperm nucleus of carp), and sturin (in the sperm nucleus of sturgeon). (in the sperm nucleus of bonito), bonito brotamine (in the nucleus of bonito sperm), etc. Fish such as those mentioned above are commonly consumed in the human diet, and protamine that can be extracted from their testes is of course extremely safe and non-toxic and harmless.

Inhibition of algae growth by protamine is based on inhibition of photosynthesis in algae and aggregation of algae.

For example, in addition to chlorophyll, cyanobacteria contain an aqueous blue photosynthesis auxiliary pigment, phycocyamine or phycoerythrin pigment, and carry out oxygen-evolving photosynthesis, but protamine combines with macromolecular phosphate compounds involved in the respiratory system. Therefore, as a result of inhibiting electron transport in the respiratory system, photosynthesis by chlorophyll in the algae is inhibited, causing the algae to discolor and die.

Since protamine binds to negatively charged sites on the cell surface as a polycation, many algal bodies aggregate with each other via protamine. For this reason, it becomes impossible to adjust the gas pressure in the gas vesicles involved in the floating and sinking of cells in water, and intracellular metabolism is inhibited.

Among algae, aquatic algae such as Anabaena subiloides produce diosmin or dimethyl isoborneol as a byproduct of pigment production.

It causes moldy and muddy odor in the water. Furthermore, when diosmin or dimethyl isoborneol migrates into the body of seafood, moldy and muddy odors are imparted to the fish, similar to water. Protamine inhibits the pigment production of such aquatic algae, and since diosmin or dimethyl isoborneol is not produced, water and seafood are not contaminated by these.

In this way, the inhibition of algae growth by protamine is different from the growth-inhibiting effect recognized for bacteria and fungi, that is, the leakage of cytoplasm due to destruction of the cell wall or surface structure, and irreversible changes in the cytoplasmic membrane. This is due to metabolic and photosynthetic inhibition, and its effects can be said to be lethal.

(Preferred Embodiment of the Invention) The protamine that can be used in the present invention is not only natural protamine extracted from the testis of fish, but also synthetic protamine, a salt thereof, or a derivative thereof.

Since protamine is a basic protein, it is easily prepared in the form of salts such as sulfate, hydrochloride, and phosphate, but it can also be used in the form of free base.

In the present invention, the effect can be obtained by using this protamine as it is, but it can also be administered or sprayed in water etc. in any dosage form in combination with known carriers or additives for formulations. It can be used for.

For example, the algae control agent of the present invention can be used in dosage forms such as powders, granules, capsules, tablets, semi-solid preparations, and liquid preparations.

As carriers or excipients for solid preparations, amorphous silica,
Inorganic carriers such as kaolin, bentonite, talc, magnesium silicate, calcium carbonate, magnesium carbonate, sodium bicarbonate, gypsum, calcined gypsum, magnesium oxide, and organic carriers such as starch, dextrin, crystalline cellulose, licorice powder, grape, etc., and lactose. A carrier is used. For use in solid preparations, in addition to the above, one or more of various binders, lubricants, disintegrants, coating agents, capsules, etc. known per se may be used as necessary. .

As a liquid preparation, in addition to an aqueous solution, additives for improving dispersibility or solubility, such as emulsifiers, suspending agents, and solubilizing agents, can be used. In the case of liquid preparations, since protamines are generally stable at neutral to alkaline pH, it is effective to incorporate a buffering agent or a pH adjuster to maintain the liquid at the above pH. As such a buffering agent or pH adjusting agent, for example, glycine, hydrochloric acid, Tris base, sodium acetate, acetic acid, sodium hydroxide, etc. are used.

The protamines used in the present invention are contained in the above formulation at a concentration of 0.00
1 to 10% by weight, especially 0. Preferably, it is present in an amount of 1 to 2% by weight.

In the present invention, halogenated phenols such as pentachlorophenol, 2.4.5-trichlorophenol, and 2.4.6-trichlorophenol, which have been conventionally used as industrial disinfectants, and their salts, cuprous oxide, etc. , copper agents such as copper oxide and copper naphthenate, thickening agents such as bitributyltin acetate and bitributyltin hydroxide,
Aminobenzoic acid esters such as p-aminobenzoic acid butyl ester, salicylic acid derivatives such as salicylic acid anilide and halogenated salicylanilide, chlorhexine, monoalkyl-bis(aminoethyl)glycine and its salts, 1,2-benzimidazole, p-chloro-m
-xylenol, 2,2-dihydroxy-5,5°-dichlorophenylmethane, dehydroacetic acid, formalin, nitrofurans, oxyquinoline, 0-phenylphenol, biphenyl, cresol soap, creosote, zinc dimethyl, dithiocarbamates, benzene Mixing with thiazoles, methylene bisthiocyanate, etc.
They can be used in combination as long as the safety of the present invention for humans and animals is not compromised.

According to the present invention, the above-mentioned control agent is applied to the water from which algae are to be removed as follows.

1. If protamine or its salts are added alone or in combination with other substances that increase the action to water where aquatic algae may grow, the growth of algae will be inhibited, resulting in colorless,
Produces tasteless and odorless water.

2. If protamine or its salt is added alone or in combination with other substances that increase its action to water where aquatic algae are growing, the algae will aggregate and settle, inhibiting their growth. Growth is inhibited in water.

3. When protamine or its salts are added alone or in combination with other substances that increase the effect to water in which aquatic algae that produce moldy or muddy odors are growing, the growth of the algae is inhibited; Since the components that give off moldy and muddy odors are not produced, the production of off-tastes and odors in the water is suppressed.

4. When fish and shellfish are raised in the treated water described in the previous section 3, the transfer and accumulation of off-taste and odor components such as musty and muddy smells does not take place within the fish and shellfish, so that the fish and shellfish maintain their delicious taste.

The effective amount of protamines to be administered into water varies depending on the type of algae and the degree of control, but in general,
．． 001 to 1% by weight, especially 0.001 to 1% by weight. Ol to 0.5% by weight
Among the above doses, administration at relatively high concentrations is effective when the purpose is to rapidly remove existing aquatic algae, and administration at relatively high concentrations is effective for the purpose of prevention. Administration of small targeted concentrations is sufficient.

Examples of algae that can be effectively controlled according to the present invention include the following.

・Diatoms Asterinel la Cyclotella Diatoma Fragj, laria Melosira Synedra Tabellaria ・Blue-green algae Anabaena Aphanizomenon ostoc Osci Latoria Polycystis ・Green Algae Actinastrum Chlamydomonas (1:Losterium Cosmariuw Dictyosphaerium Eudorina Pandorina Pediastru* Scene deswus Spirogyra Ulothrix olvox Yellow algae Dinobryon Mailomonas ynura Uroglenopsis Dinoflagellate Ceratiuo+ Glenodiniun+ Peridinium Instead of adding the protamine-based algae control agent of the present invention directly to the water in which algae proliferate, it can also be included at least on the surface of objects that come into contact with this water for the purpose of algae control. For example, In the present invention, protamine may be mixed with a synthetic resin such as nylon to create a synthetic resin thread, and an aquaculture net made of this synthetic resin thread may be created. In this case, protamine may be added to 0 per synthetic resin thread. It is preferable to incorporate the compound in an amount of .1 to 10% by weight in order to achieve the effects of the present invention.

Furthermore, in the present invention, protamine can also be used by blending it into a paint or the like. In this case, procumin is preferably blended in an amount of 0.1 to 5% by weight based on the paint.

(Effects of the Invention) According to the present invention, it is possible to effectively exterminate algae that occurs in single-layer cooling towers, industrial cooling water system towers, and drinking water tanks attached to buildings, etc., thereby reducing work efficiency and drinking water. Strange taste in water
The hygiene problem of strange odors has been resolved.

Furthermore, it is possible to effectively inhibit the growth of algae in the habitat of fish and shellfish without adversely affecting the fish and shellfish, and the off-flavor and odor components of the algae can migrate and accumulate in the fish and shellfish, significantly impairing the taste. It was also effectively prevented from becoming unfit for consumption.

(Example) Hereinafter, the method of the present invention will be explained in detail with reference to Examples.

Example 1 The growth inhibition effect of Algae P. and Tesprotamine on algae was tested. This efficacy test included Chlorella vulgaris (Chlorella vulgaris)
lla vulgaris), Anabaena 5piroidas, Achnanthes m.
Three species of algae (Fnutissima) were used.

Pour 100ml of algae culture solution into a 300ml Erlenmeyer flask, and add 0.5% protamine (sulfuric acid) to it.

A certain amount of the above pure cultured algae liquid was added to the water at a concentration of 0.1% and 0.01%, and the temperature was raised to 25%.
The cells were cultured (stationary) for 7 days at a temperature of 3,000 lux (12 hours light, 12 hours dark). Growth was observed for 7 days according to the following evaluation criteria.

Excellent growth = 4 Good growth = 3 Poor growth = 2 Very poor growth = No growth 20 The results obtained are shown in Table 1.

Example 2 One culture of algae, Chlorella vulgaris (Ch.
lorella vulgaris) and Anabaena 5piroidas (approximately 10' cells/ml).
), to which protamine sulfate was added to give a concentration of 0.05%. This was cultured with shaking at 25° C. and approximately 3000 lux for 5 days. The growth inhibition rate was 660 for each treated area and untreated area.
The absorbance at nm was measured and calculated using the following method.

Growth inhibition rate = The results are shown in Table 2.

Table 2: Effect of protamine on reproductive removal Results: The product containing 0.05% of 6M acid protamine,
It suppressed the growth of algae, and growth inhibition was observed.

Example 3 Protamine sulfate was added to a culture solution of Anabaena 5piroidas, an alga that is said to produce an odor, to a concentration of 0.05%.
The cells were cultured for 7 days at approximately 3000 lux at °C. A sensory test was conducted to compare the odor with no additives. The results are shown in Table 3.

Table 3: Results of the odor suppression effect of protamine on Anabaena Results: The number of people who felt that the odor was stronger when 0.05% protamine sulfate was added was clearly lower than when no additive was added, and the odor generation was suppressed.

Representative examples of prescriptions are shown below.

Example 4 2 parts of protamine and 98 parts of water are mixed to form a solution.

The product of the present invention was added once a day to an elevated water tank for drinking water at a concentration of 0.1-0.5%.

Even after one month, there was no algae growth in the elevated tank.

The drinking water did not have any strange odor such as mold odor.

Example 5 40 parts of protamine sulfate, 45 parts of starch, 3 parts of sodium bicarbonate, and 2 parts of talc are mixed, and granules are made using 5% starch paste as a binder and compressed into tablets. This tablet was placed in a fish tank and the protamine concentration was adjusted to 0.05%. 1 fish tank (sunlight shines through glass)
Observations were made after 1 week, 2 weeks, 3 weeks, and 4 weeks, but no algae (blue-green algae) was observed.

Example 6 A water-resistant oil-based paint containing 1% protamine as an algae control agent was applied to an iron plate and immersed in the water of a pond with a lot of algae for one week, but the algae did not adhere to the surface of the treated iron plate. There were hardly any.

Example 7 One part of protamine was kneaded into 100 parts of nylon, and a fishing net was made from the nylon thread. In order to use this fishing net as a fishing net, it was immersed in water containing algae for one month. The algae that were initially entangled in the fishing net stopped clinging to it after a week.

Claims (3)

[Claims] (1) An algae control agent characterized by containing protamine, a salt thereof, or a derivative thereof as an active ingredient. (2) A method for purifying industrial water or drinking water, which comprises spraying protamine, a salt thereof, or a derivative thereof into a water source or waterway to inhibit the growth and proliferation of aquatic algae. (3) A method for preventing odor in fish and shellfish, which comprises spraying protamine, its salt, or its derivative into fish habitat water to inhibit the growth and proliferation of algae.