JP2003286111A - Antifouling agent for harmful organisms in water - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an antifouling agent for controlling marine pollution by marine harmful organisms, which is considered to be highly safe for fish and shellfish and human beings, and which is easily obtained from naturally occurring substances. Provide antifouling agent at a price. SOLUTION: The following chemical formula 1 As an active ingredient.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to an antifouling agent for pests for controlling marine fouling by marine pests.

[0002]

2. Description of the Related Art Marine adhering organisms such as barnacles, mussels, hydroids, bryozoans, which are known as fouling substances, are used in ship bottoms, aquaculture fish nets, set nets, buoys, undersea structures such as offshore oilfield rigs, and thermal power. The water is attached to seawater intake facilities such as cooling water intake channels of waterfront plants such as power plants, heat exchanger cooling water piping systems, aquariums, and fisheries and fisheries centers, resulting in great damage.

Conventionally, tribu has been used for controlling these organisms.
Antifouling agents containing organotin compounds such as tyltin oxide (TBTO) and heavy metals such as copper zincate and copper sulfate have been mainly used. Organic tin-based antifouling paints have been widely used as ship bottom paints because they have excellent antifouling effect, but as the amount used increases, they cause sterilization of snails and affect other marine products. Has been found to affect. Therefore, manufacturing and use are banned in Japan, and discussions are in progress to ban use worldwide. Copper zincate has been reported to be accumulated on the seabed in places such as yacht harbors, where it is used in large amounts, and to concentrations that cause concern that it may affect marine life. Such conventional antifouling agents utilize the toxicity of heavy metals, and have a problem that they have an antifouling effect but have an adverse effect on the environment. Also, in recent years, silicon-based paints have come to be used in cooling water channel systems at power plants, but the antifouling performance is not perfect due to the drawback that the antifouling performance deteriorates in places where the water flow is weak, and the cost is also low. There is a problem that is high.

Under these circumstances, it is urgently necessary to develop an economical and pollution-free countermeasure against adherent organisms, and among them, natural biological substances (ecology affecting other individuals such as pheromones and allelochemicals). A method of controlling adhesion by using a substance is being considered ((Fund) Central Research Institute of Electric Power, "Report of Central Electric Power Research Institute," December 1999). In such a movement, the use of an adhesion repellent substance as a new antifouling agent is drawing attention. For example, Japanese Patent No. 2902579 proposes a new substance, but it is not completely toxic, and the elution concentration during use is controlled within a narrow range in order to increase the adhesion inhibition rate and maintain safety. There is the difficulty of having to. For example, in the case of 10-formamide-4-cadinene, which is an example of the patent, 3 μ
Barnacle larvae begin to die at concentrations above g / ml, 1
100% mortality occurs at a concentration of 0 μg / ml. Moreover,
The cost is high because a compound is newly synthesized.

In addition, as an adhesion repellent substance with little toxicity,
Many substances have already been reported, but only one example has been studied for practical use, and in many cases, there is a problem that obtaining a large amount of the adhesion repellent substance requires a great deal of cost. Further, even in the case of a compound obtained in a large amount, the antifouling effect is lost when an immersion test is actually carried out, and thus it is the current situation that it has not been put into practical use.

As described above, an inexpensive and highly safe antifouling agent having an excellent antifouling effect has not yet been obtained.

[0007]

DISCLOSURE OF THE INVENTION The present invention is different from the conventionally used antifouling agents using heavy metals such as organotin compounds, and is highly safe against fish and shellfish or human beings against harmful adhering organisms in water. The purpose is to provide an antifouling agent. Another object of the present invention is to provide a low-cost antifouling agent against harmful adhering organisms in water.

[0008]

In order to achieve the above object, the antifouling agent for aquatic harmful adhering organisms of the present invention is represented by the following chemical formula 2.

[Chemical 2] The casinos represented by are included as active ingredients.

A paint prepared by mixing the antifouling agent with a film forming agent, wherein the antifouling agent is 0.1 to 50% in terms of casino based on the weight of the paint. Which is a solution prepared by mixing the antifouling agent with a film forming agent and dissolving it in a solvent, wherein the antifouling agent is 0.1 to 100% in terms of casino based on the weight of the solution. And an emulsion prepared by dissolving the antifouling agent in a solvent and further adding a surfactant, wherein the antifouling agent is 0.1 wt.
It provides an emulsion formulated in a proportion of -80% by weight.

[0010]

BEST MODE FOR CARRYING OUT THE INVENTION The casino oils used in the antifouling agent of the present invention are sesquiterpene alcohols contained in many essential oils including the essential oils of cypress family plants such as cypress and hiba, and are extracted from the essential oils. be able to. It can also be extracted from marine organisms such as sponges. It is easy to extract, a large amount is contained in the essential oil of the Cypressaceae plant, and the cost is low. Extraction may be performed by any method, and the substances from which casinos are extracted are not limited to these.

As the antifouling agent of the present invention, it is possible to use the plant essential oil containing casino oils as it is. In this case, there is no need for extraction, and it can be manufactured at low cost.

The inventors of the present invention have shown from the experiment that the following chemical formula 3

[Chemical 3] It was discovered that T-Casino and other casinos represented by the following formula have an effect of repelling adhesion to aquatic pests. Figure 1
Is a graph showing the relationship between the concentration of T-casino and the adhesion inhibition rate and mortality of barnacles. When the adhesion inhibition rate is 50%, the T-casinoal concentration is 0.5 μg / ml, and more At a concentration of 3 μg / ml or more, the adhesion inhibition rate is 100%. Therefore,
If the concentration when dissolved in seawater or the like is 0.5 to 3 μg / ml, the adhesion repellent effect can be obtained. However, it is very difficult to control the elution concentration in such a narrow range during actual use. In addition, considering the possibility that the concentration will decrease due to the speed of the flow of seawater, etc., it may be better to increase the concentration. The antifouling agent of the present invention has a mortality rate of 0 even at a concentration of T-casinoal of 30 μg / ml, and does not show toxicity even if the concentration is exceeded. Therefore, when the antifouling agent of the present invention is used, the T-casinol concentration when eluted in seawater or the like is 0.5 μm.
It can be controlled in a wide range of g / ml or more,
It is a very easy-to-use antifouling agent. The half-adhesion-repellent concentration is 0.
It is 5 μg / ml, and less than 0.5 μg / ml has no effect. Further, even if the concentration exceeds 30 μg / ml, the adhesion repellent activity does not change and there is no toxicity, but it is not preferable in terms of cost. Therefore, the preferred T-when using the antifouling agent of the present invention
The elution concentration of casino is 0.5 to 30 μg / ml, more preferably 1 to 10 μg / ml, particularly preferably 3 to
It is 10 μg / ml. Further, the antifouling agent of the present invention has a mortality rate of 0 even at a concentration 10 times the concentration when the inhibition rate is 100%, and is extremely safe for the environment.

The antifouling agent of the present invention may be casino oil alone, vegetable essential oil containing casino oil, or other known antifouling agent. The antifouling agent of the present invention is
Like conventional antifouling agents, they are prepared and used in the form of paints, solutions, emulsions, capsules and the like. These preparations can be carried out by adopting a commonly-used general recipe.

For example, when used as a paint, the antifouling agent of the present invention is mixed with a paint preparation agent to prepare an antifouling paint,
It can be applied to ship bottoms, underwater structures, cooling intakes, etc. Examples of the film forming agent used in this case include oil varnish, synthetic resin, artificial rubber and the like.
If desired, a solvent, an extender pigment or the like can be added to the antifouling paint. In this case, the amount of the antifouling agent of the present invention blended in the paint is adjusted so that the elution concentration of the casino is within the above-mentioned range at the time of use. For example, it is blended in a proportion of 0.1 to 50% in terms of casino based on the weight of the paint.

When the antifouling agent of the present invention is used as a solution, for example, it is mixed with a film-forming agent and dissolved in a solvent to prepare a solution, which is used for the purpose of preventing the aquatic organisms from adhering and propagating. It can be applied to fishing nets and the like. As the film forming agent, for example, natural resin, synthetic resin, artificial rubber, etc. are used, and as the solvent, toluene, xylene, cumene, ethyl acetate, methyl isobutyl ketone, methanol, etc. are used. If necessary, additives such as a plasticizer can be added to this solution. When used as a solution, the amount of the antifouling agent of the present invention blended in the solution is adjusted so that the elution concentration of the casino is within the above-mentioned range at the time of use. For example, it is blended at a rate of 0.1 to 100% in terms of casino based on the weight of the solution.

When used as an emulsion, the antifouling agent of the present invention is dissolved in a solvent, and a surfactant is further added to prepare an emulsion by a conventional method. Commonly used surfactants are generally used. When used as an emulsion, the amount of the antifouling agent of the present invention to be blended is adjusted so that the concentration of the casino is within the above range at the time of use. For example, it is blended in a proportion of 0.1 to 80% in terms of casino based on the weight of the emulsion.

When used as a capsule, an antifouling agent of the mM order is included in the capsule, and the capsule is attached to a fishing net or the like so as to be gradually released and diffused. Also,
The antifouling agent of the present invention may be used by kneading it into a polymer resin of an underwater construction material such as an aquaculture fishing net and a stationary net.

[0018]

The present invention will be described in more detail below with reference to examples, but the present invention is not limited thereto.

[Extraction of T-Casino and 10-formamido-4-cadinene] Unidentified sponges of the genus Acantella (150 g (frozen wet weight)) collected in Izu were finely pulverized, and then 3 g with 300 ml of methanol.
Extracted twice. After concentrating the extract, it was partitioned into two layers with water and chloroform, and then with n-hexane and 90% methanol.
The layers were submitted for partitioning. The active n-hexane layer was fractionated by silica gel column flash chromatography using chloroform and methanol, and gel filtration was performed using Toyopearl HW40 (manufactured by Tosoh Corporation). After gel filtration, ODS column (Shiseido Co., Ltd. Capcell Pak UG120, φ20 mm × 2)
HPLC (high performance liquid chromatography) using 50 mm) was performed. 75% to 10 at a flow rate of 5 ml / min
Separation was carried out with a linear gradient of 0% methanol, and the measurement wavelength was detected at 210 nm to obtain two kinds of compounds exhibiting adhesion repellent activity. Each retention time is 4
It was 6.0 minutes and 56.2 minutes. Each of the two compounds was repurified by HPLC to give compound A (3.9 m
g) and compound B (0.7 mg) were obtained.

NMR measurement of compound A and compound A
The compound obtained by converting the formamide group of 1 to an isonitrile group was determined by NMR to be the known 10-isocyano-4-cadinene, and therefore the compound A was 10-
It was found to be formamide-4-cadinene. In addition, the compound B has the following chemical formula 4 as measured by NMR.

[Chemical 4] It was found to be T-Casino.

[Activity Test] The activity test method used in this example is the Rittscho method using a multi-well plate.
It was carried out based on the method devised by F et al. (Rittsc
hof et. al, J .; Exp. Mar. Bio. E
cl. , 82, 131-146 (1984)).

The repellent activity of the antifouling agent T-Cascinar of the present invention was tested using Cyprus larvae of Tadema barnacles, which were raised and fed with diatoms in an incubator at 25 ° C. For the repellent activity test, a 24-well polystyrene multi-well plate manufactured by Coaster was used, and a solution of this compound in methanol was added to each well at 20 μm.
After being poured and dried, 2 ml of filtered seawater was added. The size of the well is 15.5 mm in diameter and 17.6 mm in height,
The volume is 3.2 ml. The concentration of the compound tested is (μg
/ Ml) is 0.03, 0.1, 0.3, 1, 3, 10,
Thus, the concentration was adjusted to about 3 times. 1
Six barnacle larvae were housed in each well, and 4 wells were used as one concentration group. After 5 days, the number of adhered individuals and the number of dead individuals were counted under a stereoscopic microscope. The mortality was judged as an apparently disintegrated individual or an individual that did not react when contact stimulus was applied with an anatomical needle. After 5 days, the adhesion rate and mortality rate for each concentration were calculated.

In addition to this, 24 wells each containing 6 barnacle larvae were placed in a well containing only filtered seawater containing no compound.
The number of adhered individuals of barnacle larvae of 144 individuals in total was counted in the same manner, and the adhesion rate of the untreated plot was obtained. It was not used as test data when the adhesion rate of barnacle larvae in the untreated area was low. The adhesion inhibition rate of the treated section was calculated by the following formula when the adhesion inhibition rate of the untreated section was 100. Adhesion inhibition rate (%) = (100-Adhesion rate (%) of treated area /
Adhesion rate (%) of untreated section × 100 The test is repeated 3 to 5 times, the average value is obtained, and the compound concentration is plotted on the horizontal axis (logarithmic axis) and the adhesion inhibition rate is plotted on the vertical axis on a semilogarithmic graph. did. As a comparative example, the same experiment was conducted using 10-formamide-4-cadinene and copper sulfate.

The results are shown in the graphs of FIGS. As shown in FIG. 1, the antifouling agent of the present invention has an adhesion inhibitory activity, and the concentration showing 100% adhesion inhibition in barnacle larvae was 3 μg / ml, but even at a concentration of 30 μg / ml barnacle larvae. No mortality was observed. On the other hand, in the case of the copper sulfate of the comparative example, as shown in FIG. 3, the half-adhesion inhibition concentration was 0.27 μg / ml and 0.3 μg / ml.
The barnacle larvae begin to die when the amount exceeds ml, and half of the barnacle larvae die at 2.7 μg / ml, which is 10 times the half-adhesion inhibitory concentration. In addition, the mortality rate is as high as 70% at a concentration of 100% adhesion inhibition rate. Further, in the case of 10-formamide-4-cadinene of Comparative Example, as shown in FIG. 2, barnacle larvae began to die at a concentration of more than 3 μg / ml and 100% died at a concentration of 10 μg / ml. .
From these results, it was found that the antifouling agent of the present invention is obviously highly safe for marine organisms and is an extremely effective antifouling agent.

[0025]

INDUSTRIAL APPLICABILITY The antifouling agent of the present invention has an excellent repellent effect on marine attached organisms, does not use heavy metals, and is highly safe to marine organisms, and therefore has an extremely high value from the viewpoint of environmental protection. Have.

That is, the antifouling agent of the present invention has an action of inhibiting the adhesion of barnacles, which are main adherent organisms. Moreover, since the mortality rate of barnacle larvae is 0 even at a concentration 10 times higher than the concentration of 3 μg / ml which shows 100% adhesion inhibition of barnacle larvae, it is considered highly safe for marine organisms. Even when compared with copper sulfate, which had an equivalent adhesion inhibition concentration, in the case of copper sulfate, the mortality rate was as high as 70% at a concentration of adhesion inhibition rate of 100% (3 μg / ml). It turns out that it is excellent in safety.

Further, even when compared with the case of 10-formamido-4-cadinene disclosed in Japanese Patent No. 2902579, which is said to have relatively low toxicity, it shows excellent safety. That is, in the case of 10-formamido-4-cadinene, barnacles started to die at a concentration exceeding the adhesion-inhibiting concentration of 3 μg / ml, and at a concentration of 10 μg / ml, 10
Although it is 0% dead, T- which is an example of the embodiment of the present invention.
Casinol has a concentration 10 times higher than the adhesion inhibition concentration (30 μg
/ Ml), the mortality rate of barnacle larvae is 0, and thus it can be said that it shows excellent safety. Also, 10-
With formamide-4-cadinene, the concentration must be lower than 3 μg / ml to achieve a mortality rate of 0%, and the concentration range that can be used is extremely narrow in order to increase the adhesion inhibitory effect. At the time of use, it is very difficult to control the concentration of the antifouling agent to be eluted in seawater or the like within a narrow range and around 3 μg / ml, but the casinos of the present invention have high safety as described above. The concentration when eluted is 0.5
Since it can be controlled in a wide range of μg / ml or more, it is an easy-to-use antifouling agent from this point as well.

Further, the active ingredients casinools can be provided at low cost because they can be easily extracted from naturally-occurring substances. That is, the antifouling agent casino of the present invention is contained in a large amount in the essential oil of cypress or hiba, and can be easily obtained and extracted at low cost.

[Brief description of drawings]

1] Concentration (μg / m) of T-casino
It is a graph which shows the relationship between 1) and an adhesion inhibition rate (%) and a mortality rate (%).

FIG. 2 is a graph showing the relationship between the concentration (μg / ml) of 10-formamide-4-cadinene and the adhesion inhibition rate (%) and mortality rate (%).

FIG. 3 is a graph showing the relationship between the concentration (μg / ml) of copper sulfate and the adhesion inhibition rate (%) and mortality rate (%).

Continued front page    (72) Inventor Kyoji Niijima             1646 Abiko, Abiko City, Chiba Prefecture Foundation             Central Research Institute of Electric Power Industry, Abiko Research Center F term (reference) 4H011 AD01 BB03 BB22 DA05 DA13                       DA16 DD01                 4J038 JA19 KA02 MA07 MA09 MA10                       NA05

Claims (5)

[Claims] 1. The following chemical formula 1 An antifouling agent against aquatic fouling organisms containing as an active ingredient casinools represented by. 2. An antifouling agent against aquatic fouling organisms, which comprises a plant essential oil containing the casino of claim 1. 3. A paint prepared by blending the antifouling agent according to claim 1 or 2 with a film forming agent, wherein the antifouling agent is based on the weight of the paint and is 0.1. 1-5
A paint compounded at a ratio of 0%. 4. A solution in which the antifouling agent according to claim 1 or 2 is mixed with a film-forming agent and dissolved in a solvent, wherein the antifouling agent is based on the weight of the solution. 1 to
A solution formulated at 100%. 5. An emulsion prepared by dissolving the antifouling agent according to claim 1 or 2 in a solvent and further adding a surfactant, wherein the antifouling agent is based on the weight of the emulsion. Emulsion blended at a ratio of 0.1 to 80% in terms of type.