JP2000128717A - Antifouling agent for underwater noxious attached organism - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain the subject antifouling agent having attachment preventing effects on underwater attached organisms by including at least one kind of specific guanidine-based compound as an active ingredient. SOLUTION: This antifouling agent is obtained by including at least one kind of guanidine-based compound represented by the formula [X is H, a halogen, a 1-4C alkyl, a 1-4C alkoxy or nitro; (n) is 1-5] as an active ingredient. 1,3-Dicyclohexyl-2-(3-chlorophenyl)guanidine, 1,3-dicyclohexyl-2-(4-chlorophenyl) guanidine, 1,3-dicyclohexyl-2-(3-bromophenyl)guanidine, 1,3-dicyclohexyl-2-(4- nitrophenyl)guanidine, etc., are preferably used as the guanidine-based compound represented by the formula. The guanidine-based compound represented by the formula is produced by adding anilines to dicyclohexylcarbodiimide.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to underwater facilities such as the bottom of ships and fishing nets, buoys, and other underwater facilities, underwater structures such as those for harbors and dams, condenser cooling water for thermal power plants, and the petrochemical industry. Barnacles,
The present invention relates to an antifouling agent for harmful aquatic organisms, which prevents underwater organisms such as mussels and laver from attaching and propagating to cause harm.

[0002]

2. Description of the Related Art Conventionally, in order to prevent the adhesion and propagation of seawater and freshwater pests, an antifouling agent that adheres to water and contains an organotin compound as an active ingredient has been used. Social problems have arisen, such as the possibility that the environment will be polluted or that humans will be harmed using fish as a medium. Therefore, the use and production of the organotin compound are subject to legal restrictions, and it has been desired to develop a similar antifouling agent that adheres to water using an organic compound instead of the organotin compound.

[0003] In recent years, an antifouling agent for biofouling in water using tetrachloroisophthalonitrile (TPN) as an active ingredient has been proposed and disclosed under such a background. However, there is still a need for a biofouling agent that adheres to water with improved effectiveness.

[0004]

SUMMARY OF THE INVENTION An object of the present invention is to provide an antifouling agent for harmful organisms attached to water, which has an excellent anti-adhesion effect on organisms attached to water.

[0005]

Means for Solving the Problems As a result of intensive studies conducted by the present inventors to solve the above-mentioned problems, the present inventors have found that certain guanidine compounds exhibit an excellent antifouling effect on living organisms attached to water. Was completed.

That is, the present invention has solved the above-mentioned problems by providing the following inventions (1), (2) and (3).

(1) General formula (I)

[0008]

Embedded image (Wherein, X represents a hydrogen atom, a halogen atom, a lower alkyl group having 1 to 4 carbon atoms, an alkoxy group or a nitro group having 1 to 4 carbon atoms, n represents an integer of 1 to 5, and n represents 2 or more. Wherein X may be the same or different.) An antifouling biofouling agent in water, which comprises one or more guanidine compounds represented by the formula:

(2) The antifouling agent for harmful organisms in water according to (1), wherein the guanidine compound is any of the following compounds.
1,3-dicyclohexyl-2- (3-chlorophenyl) guanidine, 1,3-dicyclohexyl-2- (4
-Chlorophenyl) guanidine, 1,3 dicyclohexyl-2- (3-bromophenyl) guanidine, 1,3-
Dicyclohexyl-2- (4-nitrophenyl) guanidine, 1,3-dicyclohexyl-2- (2,4-dichlorophenyl) guanidine, 1,3-dicyclohexyl-2- (2,5-dichlorophenyl) guanidine and 1,3- Dicyclohexyl-2- (2,5-dibromophenyl) guanidine

(3) 1,3-dicyclohexyl-2-
(3-chlorophenyl) guanidine, 1,3 dicyclohexyl-2- (2-bromophenyl) guanidine,
3-dicyclohexyl-2- (3-bromophenyl) guanidine, 1,3-dicyclohexyl-2- (4-bromophenyl) guanidine, 1,3-dicyclohexyl-2-
(4-fluorophenyl) guanidine, 1,3 dicyclohexyl-2- (4-iodophenyl) guanidine,
1,3 dicyclohexyl-2- (3-methylphenyl)
Guanidine, 1,3 dicyclohexyl-2- (4-ethylphenyl) guanidine, 1,3 dicyclohexyl-2
-(3-isopropylphenyl) guanidine, 1,3 dicyclohexyl-2- (4-isopropylphenyl) guanidine, 1,3-dicyclohexyl-2- (4-nitrophenyl) guanidine, 1,3 dicyclohexyl-2
-(3-methoxyphenyl) guanidine, 1,3 dicyclohexyl-2- (4-ethoxyphenyl) guanidine, 1,3-dicyclohexyl-2- (2,4-dichlorophenyl) guanidine, 1,3 dicyclohexyl-2
-(2,6-dichlorophenyl) guanidine, 1,3 dicyclohexyl-2- (3,5-dichlorophenyl) guanidine, 1,3 dicyclohexyl-2- (2,5-dibromophenyl) guanidine, 1,3-dicyclohexyl-2 -(2,4-dibromophenyl) guanidine,
1,3 dicyclohexyl-2- (2,4-difluorophenyl) guanidine and 1,3 dicyclohexyl-2-
(2,4,6-trichlorophenyl) guanidine

[0011]

DETAILED DESCRIPTION OF THE INVENTION For example, a guanidine compound (hereinafter sometimes simply referred to as "the present compound") which can be used as an active ingredient of the antifouling biofouling agent compound in water of the present invention is the general compound described above. Any compound represented by the formula (I) may be used. Among the substituents represented by X in the formula, examples of the halogen atom include fluorine, chlorine, bromine, and iodine atoms. Examples of the alkyl group having 1 to 4 carbon atoms include a methyl group, an ethyl group, n-propyl group, i-propyl group, n
-Butyl group, i-butyl group, t-butyl group, sec-butyl group and the like. Examples of the alkoxy group having 1 to 4 carbon atoms include a methoxy group, an ethoxy group, an n-propoxy group and an i-propoxy group. , N-butoxy group, i-butoxy group, t-butoxy group, sec-butoxy group and the like. Further, X in the formula also represents a hydrogen atom and a nitro group.
When two or more substituents X are bonded, each substituent X may be the same or different.

Specific examples of the compound of the present invention having such a substituent X include the following compounds.
The present compound is not limited to these exemplified compounds. In the following description, the present compound may be abbreviated by the following compound number. Further, among the following exemplified compounds, (Compound 3), (Compound 5), (Compound 9),
(Compound 12), (Compound 15) and (Compound 18)-
(Compound 32) is a novel compound not described in the literature.

(Compound 1): 1,3-Dicyclohexyl-2-phenylguanidine (Compound 2); 1,3-Dicyclohexyl-2- (2-chlorophenyl) guanidine (Compound 3); 1,3-Dicyclohexyl-2- (3-chlorophenyl) guanidine (compound 4); 1,3-dicyclohexyl-2- (4-chlorophenyl) guanidine (compound 5); 1,3-dicyclohexyl-2- (3-bromophenyl)
1,3-dicyclohexyl-2- (2-methylphenyl) guanidine (compound 7); 1,3-dicyclohexyl-2- (4-methylphenyl) guanidine (compound 8); 1,3- Dicyclohexyl-2- (4-t-butylphenyl) guanidine (compound 9); 1,3-dicyclohexyl-2- (4-nitrophenyl) guanidine (compound 10); 1,3-dicyclohexyl-2- (2-methoxy) 1,3-dicyclohexyl-2- (4-methoxyphenyl) guanidine (compound 12); 1,3-dicyclohexyl-2- (2,4-dichlorophenyl) guanidine (compound 13); 1 , 3-Dicyclohexyl-2- (2,5-dichlorophenyl) guanidine (compound 4); 1,3-dicyclohexyl-2- (3,4-dichlorophenyl) guanidine (compound 15); 1,3-dicyclohexyl-2- (2,5-dibromophenyl) guanidine (compound 16); 1,3- Dicyclohexyl-2- (3-chloro-4-methylphenyl) guanidine (Compound 17); 1,3-Dicyclohexyl-2- (2,6-dimethylphenyl) guanidine (Compound 18); 1,3 Dicyclohexyl-2- ( 2-bromophenyl)
Guanidine (compound 19); 1,3 dicyclohexyl-2- (4-bromophenyl)
Guanidine (compound 20); 1,3 dicyclohexyl-2- (4-fluorophenyl) guanidine (compound 21); 1,3 dicyclohexyl-2- (4-iodophenyl)
Guanidine (compound 22); 1,3 dicyclohexyl-2- (3-methylphenyl)
Guanidine (compound 23); 1,3-dicyclohexyl-2- (4-ethylphenyl)
1,3-dicyclohexyl-2- (3-isopropylphenyl) guanidine (compound 25); 1,3-dicyclohexyl-2- (4-isopropylphenyl) guanidine (compound 26); 1,3-dicyclohexyl-2 -(3-methoxyphenyl) guanidine (compound 27); 1,3-dicyclohexyl-2- (4-ethoxyphenyl) guanidine (compound 28); 1,3-dicyclohexyl-2- (2,6-dichlorophenyl) guanidine (compound 29 1,3 dicyclohexyl-2- (3,5-dichlorophenyl) guanidine (compound 30); 1,3-dicyclohexyl-2- (2,4-dibromophenyl) guanidine (compound 31); 1,3 dicyclohexyl-2 -(2,4-difluorophenyl) gua Nidine (compound 32); 1,3-dicyclohexyl-2- (2,4,6-trichlorophenyl) guanidine

The preferred compound of the present invention as an active ingredient of the antifouling compound in water is 1,3-
Dicyclohexyl-2- (3-chlorophenyl) guanidine, 1,3-dicyclohexyl-2- (4-chlorophenyl) guanidine, 1,3 dicyclohexyl-2-
(3-bromophenyl) guanidine, 1,3-dicyclohexyl-2- (4-nitrophenyl) guanidine,
1,3-dicyclohexyl-2- (2,4-dichlorophenyl) guanidine, 1,3-dicyclohexyl-2-
(2,5-dichlorophenyl) guanidine and 1,3-
Dicyclohexyl-2- (2,5-dibromophenyl)
Guanidine can be mentioned.

The compound of the present invention can be produced, for example, by adding an aniline corresponding to the structure of the present compound to dicyclohexylcarbodiimide as shown in the following reaction formula (Formula 3).

[0016]

Embedded image

(Wherein X represents a hydrogen atom, a halogen atom, an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms or a nitro group. N represents an integer of 1 to 5; 2
In the above case, X may be the same or different. )

Specifically, dicyclohexylcarbodiimide, an aniline corresponding to the structure of the present compound and a solvent are charged, and after blowing hydrogen chloride gas, 80 to 150
C., preferably in the temperature range of 80 to 110 C.
It can be obtained by reacting for about an hour.

The anilines corresponding to the structure of the present compound include, for example, aniline, 2-chloroaniline, 3-chloroaniline, 4-chloroaniline, 3-bromoaniline, 2-methylaniline, 4-methylaniline (p -Toluidine), 4-t-butylaniline, 2,6-dimethylaniline, 4-nitroaniline, 2-methoxyaniline, 4-methoxyaniline (p-anisidine), 2,4
-Dichloroaniline, 2,5-dichloroaniline, 3,
4-dichloroaniline, 2,4-dibromoaniline,
2,5-dibromoaniline, 3-chloro-4-methylaniline, 2-bromoaniline, 4-bromoaniline,
-Fluoroaniline, 4-iodoaniline, 3-methylaniline, 4-ethylaniline, 3-isopropylaniline, 4-isopropylaniline, 3-methoxyaniline, 4-ethoxyaniline, 2,6-dichloroaniline, 3,5- Examples thereof include, but are not limited to, dichloroaniline, 2,4-difluoroaniline, and 2,4,6-trichloroaniline. The amount of the aniline corresponding to the structure of the present compound may be in the range of usually 1 to 5 mol, preferably 1 to 1.5 mol, per 1 mol of dicyclohexylcarbodiimide.

Examples of the solvent which can be used in the production of the present compound include aromatic hydrocarbon solvents such as toluene and xylene; and halogenated hydrocarbon solvents such as chloroform, methylene chloride and carbon tetrachloride. it can. The amount of the solvent used may be in the range of 500 ml to 5000 ml, preferably 1000 ml to 2000 ml per 1 mol of dicyclohexylcarbodiimide.

Hydrogen chloride gas is used in an amount of 1.0 to 1.5 mol, preferably about 1.0 to 1.2 mol, per 1 mol of aniline corresponding to the structure of the present compound used, for about 1 hour. And blow.

Hereinafter, the antifouling agent for harmful underwater organisms of the present invention will be described.

As the biofouling agent for harmful adherent organisms in water of the present invention, the present compound itself can be used as it is, but depending on the purpose and object, for example, a suitable agent such as a paint, a solution, an emulsion, a pellet, or a flake. By formulating this compound in a mold, for example, underwater structures such as the bottom of ships, fishing nets, buoys, etc., submerged structures such as dam attachments, condenser cooling water for thermal power plants, and petrochemical industry It can be used for a wide range of objects requiring antifouling organisms attached to water, such as a water intake channel for heat exchanger cooling water. Equipment placed underwater such as the bottom of a ship and fishing nets, buoys, etc.
When used in parts that are in constant contact with seawater, such as underwater structures such as auxiliary equipment for dams, and condenser cooling water for thermal power plants or heat exchanger cooling water for the petrochemical industry, this compound is usually used. It is used by being formulated into a paint, but if desired, may be added into the water intake channel in the form of an emulsifying dispersant using an organic solvent and a surfactant. Alternatively, the present compound may be formed into pellets by a method such as hot melt molding or mixed compression molding with a hydrophilic resin, a surfactant or the like, and then placed in a cooling water system using seawater.

When the present compound is formulated as a paint,
The compound of the present invention is mixed with a film-forming agent and, if necessary, a plasticizer, a coloring pigment, an extender pigment, and other components commonly used in the preparation of a coating material, and then coated with a stirrer or a conventional disperser such as a three-roll mill or a sand mill. I just want to make it. That is, for example, the present compound and an aromatic solvent such as toluene, xylene, cumene, and naphtha; an alcohol solvent such as propanol;
Alternatively, a solvent such as a ketone solvent such as methyl isobutyl ketone, a synthetic resin such as an oil varnish, an acrylic resin, a synthetic rubber, a film forming agent such as a rosin, a dye, a dioctyl phthalate (DOP), and a chlorinated paraffin if necessary. It can be formulated into a paint by appropriately mixing a plasticizer, a coloring pigment such as a red stem, or an extender such as barium sulfate or talc. The compound of the present invention can be formulated into an emulsion by mixing water, for example, a water-immiscible solvent such as the above-mentioned aromatic solvent, and a known surfactant such as anionic, nonionic and cationic. . Further, for example, a hydrophilic resin such as polyethylene glycol which is solid at ordinary temperature is used as a base, and the present compound and, if necessary, a plasticizer, a surfactant and the like are blended as constituent components, and pelletized by a method such as melt molding or compression molding. And flakes. The compounding amount of the present compound in the case of formulation is appropriately selected depending on the purpose, dosage form, method of use, etc., and the compounding amount is not limited as long as the present compound does not interfere with the formulation. For example, when it is made into a paint, a solution, an emulsion or the like, it may be usually added at a ratio of 1 to 40% by weight, preferably 3 to 20% by weight, and when it is made into a pellet or the like, it is usually 30 to 95% by weight. , Preferably 50 to 90% by weight. The other components may be those commonly used in each preparation, and the type, combination, blending amount, and the like are not limited to the examples in this specification, and may be appropriately adjusted in a wide range according to desired formulation properties and the like. Can be changed.

The biological antifouling agent that adheres to water in the water of the present invention can be used by appropriately selecting a commonly used technique such as application, impregnation, addition in water, and installation in water, depending on the place of use, purpose, and dosage form. That is, when the underwater biofouling agent of the present invention is formulated, for example, as a paint, the bottom of a ship, a fishing net, an underwater structure,
It can be used by a method such as application to an intake channel or the like. When the target is a fishing net, the fishing net is immersed in the paint or the underwater biofouling agent of the present invention formulated as a solution, coated and / or impregnated. This can also be exemplified as an effective usage.
When the target is an intake channel, a method prepared by adding a solution or an emulsion prepared in water, or a method prepared as pellets or flakes, for example, by suspending or attaching, is appropriately selected depending on the actual use situation. A known method of installation can also be used. Further, for example, the compound of the present invention is incorporated at the production stage of a rope or a fiber material used for fishing nets or the like, and the rope or the fiber material itself is used in a dosage form and a method other than the above examples, such as imparting a water-controlling property to organisms attached to water. You can also.

The compound of the present invention, which is an active ingredient of the antifouling agent for harmful organisms in water of the present invention, can be used in combination with other organic agents in order to further improve the antifouling effect and the antifouling period. . Organic agents that can be used for these purposes include, for example, 2,4,6-trichlorophenylmaleimide, 3
-(3,4-dichlorophenyl) -1,1-dimethylurea (DCMU), 2-methylthio-4-t-butylamino-6-cyclopropylamino-S-triazine, tetrachloroisophthalonitrile, 4,5- Dichloro-2
-N-octyl-3 (2H) isothiazolone, zinc dimethyldithiocarbamate and the like. One or more of these organic agents may be used. In the antifouling agent for harmful adherent organisms in water of the present invention, for example, a copper compound such as cuprous oxide may be used in combination, and in this case, the formulation is performed using the above-described components and the like in the above-described manner. It may be used as a coating material, and may be used in combination with silicone resin, silicone oil or the like.

[0027]

According to the present invention, there is provided an antifouling agent for water-adhering organisms, which has an improved effect of preventing the adhesion of organisms adhering to water, as compared with those using a conventionally known antifouling compound.

[0028]

EXAMPLES Hereinafter, the underwater biofouling agent of the present invention will be described more specifically with reference to synthesis examples and test examples for evaluation. However, the scope of the present invention is not limited to these synthetic examples and test examples.

(Synthesis Example 1) [Synthesis of 1,3-dicyclohexyl-2- (3-chlorophenyl) guanidine (compound 3)] Toluene 200m
l, 41.3 g of dicyclohexylcarbodiimide (0.
2 mol), 28.05 g of 3-chloroaniline (0.22
Mol) in a reaction flask, heated to 100 ° C., and stirred at the same temperature, 8.0 g (0.22 mol) of hydrogen chloride gas.
For 1 hour. After the completion of the hydrogen chloride gas injection, stirring was continued for another 5 hours at the same temperature to complete the reaction. After completion of the reaction, the reaction solution was cooled to room temperature, the reaction system was neutralized with 29.3 g (0.22 mol) of a 30% aqueous sodium hydroxide solution, and the precipitated crystals were collected by filtration and washed with water to obtain a crude product. Was.
The obtained crude product was recrystallized from ethanol to give 28.7 g of the desired product as a white powder.

Melting point: 141 to 142 ° C. Instrumental analysis data: ¹ H-NMR (CDCl ₃ , δ value): 1.03 to 2.01
(M, 20H), 3.41 (m, 2H), 3.64
(M, 2H), 6.72-7.17 (m, 4H)

(Synthesis Example 2) [Synthesis of 1,3 dicyclohexyl-2- (3-bromophenyl) guanidine (compound 5)] Instead of 28.05 g of 3-chloroaniline, 37.8 of 3-bromoaniline was used.
In the same manner as in Synthesis Example 1 except that g (0.22 mol) was used, 42.1 g of the target product was obtained as a white powder.

Melting point: 125-127 ° C. Instrumental analysis data ¹ H-NMR (CDCl ₃ , δ value): 1.03-2.01
(M, 20H), 3.39 to 3.42 (m, 2H),
3.63 to 3.66 (m, 2H), 6.75 to 7.12
(M, 4H)

(Synthesis Example 3) [Synthesis of 1,3-dicyclohexyl-2- (4-nitrophenyl) guanidine (compound 9)] Instead of 28.05 g of 3-chloroaniline, 30.4-nitroaniline was used.
In the same manner as in Synthesis Example 1 except that g (0.22 mol) was used, 53.7 g of the target product was obtained as a yellow-orange powder.

Melting point: 154 to 160 ° C. Instrumental analysis data ¹ H-NMR (CDCl ₃ , δ value): 1.14 to 2.00
(M, 20H), 3.42 (m, 2H), 4.38 (b
rs, 2H), 6.96-6.99 (d, J = 8.1H)
z, 2H), 8.10 to 8.13 (d, J = 8.1H
z, 2H)

(Synthesis Example 4) [Synthesis of 1,3-dicyclohexyl-2- (2,4-dichlorophenyl) guanidine (compound 12)] Instead of 28.05 g of 3-chloroaniline, 2,4-dichloroaniline 35 was used. In the same manner as in Synthesis Example 1 except that 0.6 g (0.22 mol) was used, 41.0 g of the desired product was obtained as a white powder.

Melting point: 135-137 ° C. Instrumental analysis data ¹ H-NMR (CDCl ₃ , δ value): 1.09 to 2.01
(M, 20H), 3.42 (m, 2H), 4.38 (b
rs, 2H), 6.92-6.95 (d, J = 8.6H)
z, 1H), 7.12-7.16 (dd, J = 8.6,
2.4 Hz, 1 H), 7.36 to 7.37 (d, J =
2.2Hz, 1H)

Synthesis Example 5 Synthesis of 1,3-dicyclohexyl-2- (2,5-dichlorophenyl) guanidine (Compound 13) Instead of 28.05 g of 3-chloroaniline, 2,5-dichloroaniline 35 was used. In the same manner as in Synthesis Example 1 except that 6.6 g (0.22 mol) was used, 34.9 g of the desired product was obtained as a white powder.

Melting point: 119-120 ° C. Instrumental analysis data ¹ H-NMR (CDCl ₃ , δ value): 1.04 to 2.05
(M, 20H), 3.36-3.47 (m, 2H),
3.53 to 3.57 (m, 2H), 6.81 to 6.85
(Dd, J = 8.1-8.6, 2.7-3.2 Hz, 1
H), 6.92-6.93 (d, J = 2.4 Hz, 1
H), 7.23 to 7.26 (d, J = 8.4 Hz, 1
H)

Synthesis Example 6 Synthesis of 1,3-dicyclohexyl-2- (2,5-dibromophenyl) guanidine (compound 15) Instead of 28.05 g of 3-chloroaniline, 2,5-dibromoaniline was used. 73.1 g of the target product was obtained as a pale brown-white powder in the same manner as in Synthesis Example 1 except that 55.2 g (0.22 mol) was used.

Melting point: 118-119.5 ° C. Instrumental analysis data ¹ H-NMR (CDCl ₃ , δ value): 1.10 to 2.06
(M, 20H), 3.41 to 3.47 (m, 2H),
3.53 to 3.55 (m, 2H), 6.88 to 6.93
(Dd, J = 8.1-8.6, 2.7-3.2 Hz, 1
H), 7.06-7.07 (d, J = 2.4 Hz, 1
H), 7.35 to 7.39 (d, J = 8.6 Hz, 1
H)

(Test Example 1) [Adhesion Inhibition Test on Larvae of Barnacles in Indoor Laboratory Screening]
ppm was dissolved, and 0.1 ml of the solution was uniformly applied to a 4 cm-diameter circular dish. The methanol was dried, and 5 ml of filtered seawater and 30 cypris larvae, which were larvae of the attachment stage of barnacle barnacles, were placed at 30 ° C at 23 ° C. It was left in the dark. Twenty-four hours later, it was taken out and the number of barnacles that had been transformed to adhere to the bottom of the petri dish was examined to determine the adhesion inhibiting effect. In addition, a test was performed in which the adhesion of barnacle barnacles was observed using tetrachloroisophthalonitrile (TPN) and diphenylguanidine as comparative compounds. The test was repeated three times, the average was obtained, and the results are shown in (Table 1). In addition, the adhesion inhibition rate (%) was calculated assuming that the adhesion inhibition rate in the untreated section was 0%.

[0042]

[Table 1]

Although the compounds of Comparative Examples 1 and 2 also exhibited some adhesion-inhibiting activity, the compound of the present invention exhibited an adhesion-inhibiting activity far exceeding these.

(Test Example 2) [Test for inhibiting growth of algal spores] 5 g of Hira anonori collected from the sea was pulverized in a mortar, diluted with 1 L of sea water, and filtered with gauze. When the filtered seawater was observed under a microscope, the movement of a large number of spores was observed. 19 ml of seawater containing this spore was transferred to a petri dish having a diameter of 9 cm to obtain a sample. On the other hand, each of the compounds to be studied was dissolved in a diluent composed of [cyclohexanone: Tween 80 (manufactured by Wako Pure Chemical Industries)] = (10: 1) to form an emulsion. Thereafter, the mixture was diluted to a predetermined concentration with seawater, and 1 ml of the diluted mixture was added to a petri dish containing the above-mentioned spores. Petri dish at 20 ℃
After 1 hour, the presence or absence of spore movement was examined under a microscope. This test was repeated three times to determine the minimum spore growth inhibitory concentration. The results are shown in (Table 2).

[0045]

[Table 2]

Although the compound of Comparative Example 1 also showed some activity, the compound of the present invention exhibited an activity even higher than this.

(Test Example 3) [Preparation of antifouling paint] Formulation examples in which the water-fouling biofouling agent of the present invention is formulated as a paint are shown in Table 3.

[0048]

[Table 3]

Each component containing the compound of the present invention was blended in the proportions shown in Table 3 and mixed with a small laboratory attritor.
It was dispersed to a micron to obtain an antifouling paint. Further, a coating material was similarly prepared using the compound of Comparative Example 2 (diphenylguanidine).

(Test Example 4) [Evaluation of antifouling performance in sea immersion test] The paint prepared in Test Example 3 was reinforced with a 10 × 30 cm reinforced plastic plate (FR).
P) and immersed in Shimizu Bay, Shizuoka Prefecture (March 1998)
Month). Thereafter, the presence or absence of attached organisms was periodically determined. The results are shown in (Table 4). In the evaluation, the area of the adhered substance occupying on the plate was expressed in%.

[0051]

[Table 4]

The compound of the present invention exhibited much better antifouling performance than the compound of Comparative Example 2, confirming its usefulness.

 ──────────────────────────────────────────────────続 き Continued on the front page (72) Inventor Hiroshi Shibuya 7-4 Nihonbashi Kobunacho, Chuo-ku, Tokyo Ouchi Shinko Chemical Industry Co., Ltd. (72) Inventor Shigemasa Ouchi 7 Nihonbashi Kobunacho, Chuo-ku, Tokyo No. 4 Ouchi Shinko Chemical Co., Ltd. (72) Inventor Masao Kuwahara 7-4 Nihonbashi Kobunacho, Chuo-ku, Tokyo Fuchi term in Ouchi Shinko Chemical Co., Ltd. 4H011 AD02 BA01 BB11 BC19 DA23 DC10 4J038 EA011 GA09 GA12 JB20 NA05

Claims (2)

[Claims] 1. A compound of the general formula (I) (Wherein, X represents a hydrogen atom, a halogen atom, an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms or a nitro group, n represents an integer of 1 to 5, and n represents 2 or more. When
X may be the same or different. ) A harmful biofouling agent for harmful adherents in water, comprising one or more of the guanidine compounds represented by the formula (1) as an active ingredient. 2. The antifouling agent according to claim 1, wherein the guanidine compound is one of the following compounds. 1,3
-Dicyclohexyl-2- (3-chlorophenyl) guanidine, 1,3-dicyclohexyl-2- (4-chlorophenyl) guanidine, 1,3 dicyclohexyl-2-
(3-bromophenyl) guanidine, 1,3-dicyclohexyl-2- (4-nitrophenyl) guanidine,
1,3-dicyclohexyl-2- (2,4-dichlorophenyl) guanidine, 1,3-dicyclohexyl-2-
(2,5-dichlorophenyl) guanidine and 1,3-
Dicyclohexyl-2- (2,5-dibromophenyl)
Guanidine