JPS63230607A - Marine organism adhesion prevention agent - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

[Detailed Description of the Invention] (Industrial Application Field) This invention relates to an agent for preventing the adhesion of marine organisms, particularly to fishing nets,
By applying it to underwater structures such as ship bottoms, seawater intake channel walls, etc., or adding it to seawater, it provides a compound that is effective in preventing fouling caused by marine organisms such as Fujitbo and mussels. be.

(Prior Art) In factories such as thermal power plants and steel mills that use seawater, marine organisms such as mussels, fujibos, hydrobugs, and bryozoans adhere to their cooling water systems, reducing their functionality. Among them, the mussels adhere to each other and grow at a fast rate, so the mussels attached to the lowest layer cannot take in sufficient nutrients and dissolved oxygen and die. As the mussels die, the byssus threads attached to the wall become weak and fall off due to water pressure and water flow, clogging the cooling channels and preventing the passage of seawater, reducing their functionality.

In addition, aquaculture fishing for yellowtail and other fish has become popular in recent years, and because aquaculture nets, ropes, and fixed nets are placed in the sea for long periods of time, marine organisms such as mussels, bryozoans, and sea squirts attach to them. are suffering from disability. Among them, when large amounts of mussels, sea squirts, and bryozoans adhere to aquaculture nets, the passage of seawater is obstructed, leading to a lack of dissolved oxygen to the aquaculture fish, or causing the cables to sink or break, resulting in damage such as the death of the aquaculture fish. arise. In addition, the attachment of organisms such as Fujitbo and mussels to underwater structures causes a decrease in the speed of ships and a decrease in the amount of water flowing through seawater intake channels. deposits must be removed.

In order to prevent such problems, organic tin compounds, heavy metals, organic sulfur compounds, quaternary ammonium salts, and the like have conventionally been used.

(Problems to be Solved by the Invention) However, the above-mentioned organic tin compounds and heavy metals are highly toxic to humans, livestock and fish, and their use is being regulated, and the other drugs mentioned above have a problem in that their effects are not sufficient. have.

The inventors of this invention have conducted intensive research into marine organism adhesion prevention agents that are low in toxicity to humans, livestock and fish, cause little environmental pollution, and do not contain heavy metals. As a result, a specific isophthalonitrile derivative has met the above conditions and is extremely superior. It has been found that this compound exhibits an antifouling effect on marine organisms, and when used in combination with other specific marine organism antifouling agents, it develops an excellent synergistic effect and is effective at lower concentrations.

(Means for Solving the Problems) That is, according to the present invention, one or more isophthalonitrile derivatives represented by the general formula (I); M (where X represents a fluorine atom or a lower alkoxy group); Provided is a marine organism antifouling agent containing as an active ingredient.

Furthermore, one or more compounds represented by the general formula (I) and the general formula (■); is a hydrogen atom or a methyl group;
R3 is a hydrogen atom, a methyl group, or -(CH*)s
a group represented by NHx (provided that when R8 is a methyl group, R3 means a methyl group)] or a salt thereof and/or the general formula (■); and R1 are the same or independently a hydrogen atom or a halogen atom, and R3 is a hydrogen atom or an alkyl group containing 1 to 18 carbon atoms. A marine organism adhesion prevention agent is provided which is formed by blending one or more of the following.

The compound according to the present invention can be added in small amounts to a seawater cooling water system during the attachment growth of mussels, or a fishing net can be immersed in a solution containing this compound and used as aquaculture net during the attachment period of mussels, or a coating film can be added to the compound. The purpose is achieved by applying the forming material to the object.

Specific examples of the compound of general formula (1) which is the active ingredient of the marine organism adhesion prevention agent of this invention include, for example, 5-chloro-
2,4,6-Dolifluoroisophthalonitrile, 5-chloro-2,4-difluoro-6-medoxyisophthalonitrile, 5-chloro-2,4-difluoro-6-nitoxyisophthalonitrile, 5- Chloro-2,4-difluoro-6=imbutoxyisophthalonitrile is mentioned.

A general method for producing the compound of general formula (1) will be explained in relation to the following formula.

(A) (B) (In the formula, X represents a lower alkoxy group) By mixing the raw materials (A) and (B) in a solvent or without a solvent, the desired isophthalonitrile derivative (I) can be obtained. The resulting reaction temperature ranges from -20°C to the reflux temperature of the solvent.

As a reaction solvent, (B) itself is used as a solvent, or
or acetonitrile, chloroform, dichloromethane, benzene, toluene, dioxane, ethyl ether,
An appropriate aprotic solvent such as tetrahydrofuran and ethyl acetate is used. Furthermore, in the above reaction, the reaction may be allowed to proceed by using a catalytic amount or a base in an amount of from 1 to 10 times the mole of (A).

The base is appropriately selected from caustic alkali, triethylamine, pyridine, alkali carbonate, potassium fluoride and the like.

The above-mentioned raw material (A), which is also the active ingredient of the drug of the present invention, can be prepared using known methods such as tetrachloroisophthalonitrile.
It can be obtained from Chemical Industry Magazine Yu 447 (1970).

Next, as specific examples of the compound of general formula (n), for example,
Primary amines such as dodecylamine, tetradecylamine, hexadecylamine, octadecylamine, oleylamine, tallow alkylamine and coconut alkylamine; dodecylmethylamine, hexadecylmethylamine, octadecylmethylamine, tallow alkylmethylamine,
Secondary amines such as hardened tallow methylamine, coconut alkylmethylamine, didodecylamine, dioctadecylamine; dodecyl dimethylamine, hexadecyl dimethylamine, octadecyl dimethylamine, coconut alkyl dimethylamine, beef tallow alkyl dimethylamine, hardened beef tallow alkyl Tertiary amines such as dimethylamine; dodecyltrimethylenediamine, hexadecyltrimethylenediamine, octadecyltrimethylenediamine, oleyltrimethylenediamine, coconut alkyltrimethylenediamine, tallow alkyltrimethylenediamine, hardened tallow alkyltrimethylenediamine, etc. Examples include N-monosubstituted trimethylene diamines such as N-monosubstituted trimethylenediamine.

Among these amines, “coconut alkyl”
"U-Amine", "Beef tallow alkyl...
-Amine "Hardened beef tallow alkyl...
amine” means that the amine is coconut oil or coconut fat,
A mixture (mixture) of amines in which R1 in the above formula is a saturated or unsaturated linear aliphatic carbon group having 12 to 18 carbon atoms, produced by known means from beef tallow, etc. alkylamines).

In addition, examples of the salts of the compound of the general formula (n) that can be used in this invention include addition salts of the compound of the general formula (former formula) and inorganic or organic acids. Compounds and hydrochloric acid, nitric acid, nitrite, sulfuric acid, phosphoric acid, formic acid, acetic acid, a
Examples include addition salts with monoacid, oleic acid, t-phthenic acid, adipic acid, lactic acid, or citric acid.

Specific examples of the compound of general formula (III) include 4
-Inthiazolin-3-one, zinc chloride, 5-chloro-
2-Methyl-4-isothiazolin-3-one/magnesium chloride, 5-chloro-2-methyl-4-isothiazolin-3-one/calcium chloride, 2-methyl-4-isothiazolin-3-one/calcium chloride, 4 .5-dichloro-2-methyl-4-inthiazolin-3-one, calcium chloride, 2-n-butyl-4-isothiazoline-
3-one zinc chloride, 5-chloro-2-(2-ethylhexyl)-4-inthiazolin-3-one calcium chloride, 2-n-octyl-4-isothiazolin-3-one iron chloride, 4. 5-dichloro-2-(2-ethylhexyl)-4-isothiazolin-3-one/calcium chloride, 2-n-decyl-4-isothiazolin-3-one/
Examples include zinc chloride. Free isothiazolone forms of these compounds may also be used.

These compounds represented by general formula (U) and general formula (II) are disclosed in Japanese Patent Publication No. 60-23641 and Japanese Patent Publication No. 59, respectively.
-20641, Special Publication No. 56-3842 Special Publication No. 1983-
52725 and Japanese Patent Publication No. 60-37081, it is known as a marine organism adhesion prevention agent.

Isophthalonitrile derivatives represented by general formula (1) and amines represented by general formula (n) and/or general formula (
The ratio of combined use with 3-isothiazolones represented by I [ .

The amount of the compound of this invention to be added to the seawater cooling water system is generally 0.001 to O.L PPM per day for 1 to 24 hours per seawater flow rate, and the amount to be added depends on the type of compound. There will be some increase or decrease due to the strength or weakness of physiological activity against mussels, etc. It is also desirable to increase the amount if the number of mussels, etc., is particularly large.

When adding the compound of this invention to a seawater cooling water system, it should be dissolved in an appropriate solvent (water or an organic solvent such as alcohol, acetone, xylene, dimethylformamide, methyl cellosolve, etc.) or emulsified so that it is uniformly dispersed in seawater. It is preferable to use a preparation with an appropriate concentration by adding a surfactant to the cloud, if necessary.Surfactants in this case include higher fatty acid salts, polyoxyethylene alkyl ethers, polyoxyethylene alkyl esters, and sorbitan. Examples include alkyl esters, polyoxyethylene polyoxypropylenes, alkyltrimethylammonium salts, alkylbetaines, and the like.

In addition, when dipping treatment is performed for fishing nets, the compound of the present invention is added to a natural resin, oil-based synthetic resin vehicle, or synthetic rubber vehicle, and a plasticizer or solvent, or a coloring pigment is added and used by dissolving and dispersing it. The natural resin, oil-based synthetic resin, or synthetic rubber vehicle mentioned here includes rosin, boiled oil, asphalt, coal tar, coumaron fat, vinyl chloride resin, vinyl acetate resin, polyollein resin such as polybutene, polystyrene, and acrylic resin. Examples include resins, polyurethane resins, amino fats, epoxy resins, phenolic resins, alkyd resins, and unsaturated polyester resins.

In addition, when applying the compound of this invention to an object, the coating film-forming materials include a natural resin, synthetic resin, or rubber derivative vehicle as the main component for forming the coating, and a paint in addition to a small amount of the above-mentioned main components. Drying agents, curing agents, plasticizers, surfactants for emulsification or dispersion, etc. are used as coating film forming subelements to improve the dispersion, drying and curing of coating films, and various physical properties.
Furthermore, in order to make the paint easier to apply, a solvent or diluent is used as a coating film-forming auxiliary element. In addition to these components, pigment components such as coloring pigments, extender pigments, and special pigments (rust-preventing pigments, luminescent pigments, etc.) are usually added as a component of the film forming agent.

The natural resin-based, synthetic resin-based or rubber derivative-based vehicles used as the main element for forming the coating film include those mentioned above.

Plasticizers used as coating film-forming subelements include tributyl phosphate, trioctyl phosphate, tricresyl phosphate, dibutyl fucurate, dioctyl phthalate,
Examples include dibutyl malate.

In addition, the surfactants used as coating film forming subelements include polyoxyethylene alkyl ethers, polyoxyethylene alkyl esters, bodioxyethylene polyoxypropylenes, sorbitan alkyl esters,
Examples include alkyltrimethylammonium salts and alkylbetaines.

Examples of the solvent or diluent as a coating film-forming auxiliary element include water, alcohol, xylene, kerosene, methyl isobutyl ketone, butyl acetate, dimethylformamide, methyl cellosolve, butyl cellosolve, and the like.

Examples of pigment components include talc, titanium white, yellow lead, navy blue, red iron, phthalocyanine blue, and various other inorganic or organic pigments.

When using each component as the above film forming agent, 1 of each
More than one species is selected and blended.

The formulation of the antifouling paint formulation of this invention takes into account the type of object to be painted, the coating method (brushing, spraying, dipping, etc.), storage period, storage method, etc., and the physical properties of the paint and the physical properties of the paint film depending on the application. It is determined that Usually, the amount of coating film forming agent is 95 to 40 parts by weight of one or more active ingredients of this invention.
~60! It is blended so that it becomes the quantity part. More specifically, for 10 to 30 parts by weight of one or more active ingredients, as a film forming material: 10 to 40 parts by weight of the main film forming element, 5 to 65 parts by weight of the film forming side element, and a film forming aid. 0-65 parts by weight of elements and 0-40 parts of pigment components! parts are added.

This invention will be illustrated below with reference to Examples and Comparative Examples.

(Margin below, continued on next page) (Example) Synthesis Example 5-Chloro-2,4-difluoro-6-medoxyisophthalonitrile 5-chloro-2,4,6-trifluoroisophthalonitrile t, ogg A solution of 0.28 g of potassium hydroxide in 10 m of methanol was added dropwise to the methanol solution under stirring. The reaction solution was stirred for 1 hour, and methanol was distilled off under reduced pressure. The residue was poured into water, extracted with chloroform, the extract was dried over magnesium sulfate, and the solvent was distilled off under reduced pressure to obtain 1.02 g (yield 90%) of the title compound.

Melting point = 18°C Boiling point: 128~b'' Fnmr (CCl2&, external standard trifluoroacetic acid) IL7ppI11, 22.7ppm (d, JFr
= 3.4Hz, each IP)'Hnmr (CC124, internal standard tetramethylsilane) 4.5ppm (S) IR (neat) + 2950cm-', 2240c
m-' Example 1 In order to find out the effect of the marine organism adhesion prevention agent of the present invention, a test was conducted using mussel larvae, which are representative of fouling organisms. That is, a formulation prepared according to the formulation example shown in Table 1 was dissolved or suspended in water, and diluted with seawater to prepare a test solution. Next, 20 to 30 mussel larvae collected from seawater with a plankton net were placed in a thick-walled glass tube with a diameter of 60 mm and a height of 100 mm, and each concentration of each compound was tested. The larvae were immersed in the liquid for 8 hours and reared for 48 hours in a running seawater tank, and then the number of surviving larvae and the number of dead larvae were counted under a microscope. The results of determining the 50% lethal concentration of each compound are shown in Table 2.

(See the margins below) (Test results in Table 2) Example 2 An antifouling agent for fishing nets was prepared using a ball mill according to the formulation examples (ratios are weight percentages) shown in Table 3. Then, polyethylene nets (60 pieces, 4 knots, no knots) were soaked in these antifouling agents for fishing nets, air-dried, and then immersed in the sea at a depth of 1 m for 6 months, including the period when mussels were attached, and then washed every month. Table 4 shows the results of investigating the state of adhesion of fouling organisms.

(Margin below, continued on next page) (Table 4 Test results) Note) The meaning of each symbol in the table is as follows.

- No adhesion of two fouling organisms.

+: There is no practical problem even if there is a slight amount of fouling organisms attached.

++: Fouling organisms have adhered to the product and it is no longer usable.

++: Fouling organisms are significantly attached.

Implementation PI 3 Next, after thoroughly kneading the mixture shown in Table 5 in a ball mill, a 15 cm
It was applied twice to a 3Gcm soft rope with a coating weight of 1.5 to 2.0Kg/s, and immersed in the sea at a depth of 1.5m.
The adhesion status of fouling organisms was investigated every month. The results are shown in Table 6.

(Left below) (Table 6 Test results) Note: The numbers in the table indicate the percentage of area covered by fouling organisms.

(Effects of the Invention) As shown from the above examples, the marine organism adhesion preventing agent of the present invention is found to be highly effective in preventing marine organism adhesion compared to heavy metals and the like.

In addition, blending the isophthalonitrile derivative of the general formula (I) with the compound of the general formula (I[) or its salt and the compound of the general formula (III) or a metal salt complex thereof has a synergistic effect on the marine organism adhesion prevention effect. It was found that it has a positive effect.

Furthermore, since the present invention has low toxicity to humans, livestock, and fish, it has the effect of more safely preventing the adhesion of marine organisms.

Claims (1)

[Claims] 1. General formula (I); ▲There are mathematical formulas, chemical formulas, tables, etc.▼……………………‥(
I) A marine organism adhesion prevention agent containing as an active ingredient one or more isophthalonitrile derivatives represented by (wherein, X represents a fluorine atom or a lower alkoxy group). 2. One or more compounds represented by general formula (I) and general formula (II); ▲There are mathematical formulas, chemical formulas, tables, etc.▼……………………‥(
II) [In the formula, R^1 is a saturated or unsaturated linear aliphatic hydrocarbon group having 12 to 18 carbon atoms; R^2 is a hydrogen atom or a methyl group; R^3 is a hydrogen atom, a methyl group, or - (CH_
2) One or more compounds or salts thereof and/or the general formula (III); ▲There are mathematical formulas, chemical formulas, tables, etc.▼……………………‥(
III) (In the formula, R^1 and R^2 are the same or different and are a hydrogen atom or a halogen atom, R^3 is a hydrogen atom or a carbon number of 1 to
means an alkyl group containing 18. ) indicated by 3
- The marine organism adhesion prevention agent according to claim 1, which is blended with one or more of isothiazolone derivatives or metal salt complexes thereof. 3. The marine organism adhesion prevention agent according to claim 1 or 2, wherein the marine organisms are organisms mainly composed of mussels.