JPH08295829A - Underwater antifouling coating material - Google Patents

Abstract

PURPOSE: To obtain a new underwater antifouling coating material containing a specific complex compound as an antifouling active ingredient, exhibiting low toxicity to mammals, safely usable and capable of expecting excellent antifouling effect over a long period and useful for ships and boats, etc. CONSTITUTION: This coating material contains a complex compound [e.g. tris(4- methylphenyl)borane nicotinamide complex] of formula I [R<1> is a lower alkyl, a lower alkoxy or a halogen; (n) is 1-3; A is a heterocyclic compound containing N or S or their both as ring atoms or ammonia or an amine compound expressed by the formula R<2> R<3> NH (R<2> and R<3> are each H, an alkyl or a cyclohexyl). Furthermore, the compound is preferably obtained by reacting an (un)substituted triphenylborane of formula II with a heterocyclic compound corresponding to the component A or ammonia or an amine compound in an equimolar ratio in the presence of an inert gas such as nitrogen at 0-50 deg.C in ethers such as ethyl ether.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an underwater antifouling paint having low toxicity and long-lasting antifouling effect, and particularly to ships, aquaculture nets, stationary nets, excavators for offshore oilfields, and seabed bases. It is used to paint structures such as buoys, buoys in power plants, bridges, etc., and is suitable for preventing adhesion of aquatic organisms that grow on the surface of the underwater part of these structures. A low toxicity underwater antifouling paint. Therefore, the present invention can be widely used in the fields of chemical industry, shipbuilding industry, fishnet manufacturing industry, and the like.

[0002]

2. Description of the Related Art Conventionally, various underwater antifouling paints have been developed,
It is also in practical use. A complex compound of a substituted or unsubstituted triphenylborane used as an antifouling active ingredient in the underwater antifouling paint of the present invention with a heterocyclic compound or an amine compound (including ammonia), or a chemistry similar to such a complex compound. Examples of the compound having a structure include the following compounds.

US Pat. No. 3211679 discloses the following general formula as an antifouling compound. (Wherein R represents a hydrogen atom, a halogen atom, a lower alkyl group, an amide group or a heterocyclic group, etc.), and a complex compound of triphenylborane with a substituted or unsubstituted pyridine or an aliphatic amine is described. To be done.

Japanese Patent Application Laid-Open No. 62-277307 discloses insecticide,
The following general formula for acaricidal and nematicidal compounds [In the formula, X and Y are each independently a hydrogen atom, a halogen atom,
A lower alkyl group or a lower alkoxy group, Z is the formula R ¹
It represents a compound of R ² NH or a nitrogen-containing heterocyclic compound (which may be substituted with a lower alkyl group). However, R ¹ , R ²
Each independently represents a hydrogen atom, a lower alkyl group, a lower alkenyl group, a cycloalkyl group, a phenyl group (which may be substituted with a halogen atom or a methyl group), or a heterocyclic group] Complexes are described.

JP-B-39-28579 discloses triphenylborane (provided that the phenyl group may have a halo or lower alkoxy substituent in the para position) or tritriborane as a compound that inhibits microbial growth. A complex compound of ruborane or trinaphthylborane with an amine compound having a pk _b value of about 10 or less is described.

Japanese Patent Publication No. 54-1571 discloses the following general formula as an antifouling compound. (In the formula, X represents a potassium atom, an ammonium group or a quaternized organic nitrogen-containing group, and the organic nitrogen-containing group may form a heterocycle containing a nitrogen atom.) Described are tetraphenylboron compound complexes.

Japanese Patent Publication No. 62-25710 discloses the following general formula as an antifouling compound. (In the formula, R ¹ represents a hydrogen atom, a halogen atom or a lower alkyl group, R ² represents a halogen atom, a lower alkyl group or a lower alkenyl group, and R ³ represents a heterocyclic amine.) -Ammonium or heterocyclic compound complexes are described.

Japanese Examined Patent Publication No. 62-24022 discloses the following general formula as an antifouling compound of an underwater antifouling paint. A tetraphenylboron derivative represented by the formula (wherein R represents a lower alkyl group) is described.

On the other hand, aquatic organisms such as barnacles, squirts, serpras, mussels, mussels, hemlock worms, hornworts, and sea lions attach to the surface of underwater structures and grow to cause various damages. For example, when aquatic organisms adhere to the hull of a ship and grow, the speed of the ship decreases and fuel consumption increases. Further, when aquatic organisms adhere to water or an underwater structure such as a port facility fixed on the surface of water, individual functions of these devices cannot be sufficiently exerted. further,
It is also known that, when attached to fishing nets such as aquaculture nets and set nets, the nets may block the fish.

Conventionally, in order to prevent aquatic organisms from adhering to and growing on an underwater structure, an organic tin compound has been frequently used as an antifouling active ingredient in an underwater antifouling paint. But,
This organotin compound pollutes the environment and is prohibited.

[0011]

From the above, the development of a new underwater antifouling paint that shows low toxicity to mammals, can be used safely, and can maintain an excellent antifouling effect for a long period of time has been developed. Is desired.

[0012]

Means for Solving the Problems The inventors of the present invention have conducted extensive studies to develop an underwater antifouling coating composition that meets the above-mentioned needs. In connection with the research, a wide range of various compounds were tested in various tests, and the physiological activities of these compounds were examined.
As a result, they have found that the triphenylborane derivative represented by the general formula (I) described later in the present invention has excellent antifouling activity and low toxicity. Moreover, the paint prepared by blending the triphenylborane derivative of the general formula (I) with the paint base for the underwater antifouling paint not only has an excellent antifouling effect, but also has a long lasting antifouling effect. I found out that

Accordingly, the gist of the present invention lies in the following general formula [In the formula, R ¹ is one or more of a lower alkyl group, a lower alkoxy group or a halogen atom, n is an integer of 1, 2 or 3, and A is a nitrogen atom or a sulfur atom or both of them. Represents a heterocyclic compound containing as a ring atom, and the heterocyclic compound may be substituted with at least one substituent selected from a lower alkyl group, a carboxyl group, an aminocarbonyl group, a lower alkoxycarbonyl group, a hydroxyl group and a halogen atom. Well, or A is of the formula R ² R ³ N
H (provided that R ² and R ³ are each independently the same or different hydrogen atom, alkyl group or cyclohexyl group) or an amine compound] is used as an antifouling active ingredient. It is an underwater antifouling paint characterized by containing.

In the definition of R ¹ and A of the complex compound of the general formula (I) used as the antifouling active ingredient in the coating material of the present invention, the alkyl portion of the lower alkyl group, the lower alkoxy group or the lower alkoxycarbonyl group is direct. It may be chained or branched. The term "lower" as used herein refers to one containing an alkyl group having 1 to 6 carbon atoms or an alkyl moiety. Examples of such lower alkyl groups include methyl group, ethyl group, n
-Propyl group, isopropyl group, n-butyl group, t-butyl group, isobutyl group, sec-butyl group, n-pentyl group, isoamyl group, n-hexyl group and the like. Examples of the lower alkoxy group include methoxy group, ethoxy group, n-propoxy group, isopropoxy group, n-butoxy group, sec-butoxy group, t-butoxy group, isobutoxy group, n-pentyloxy group, iso- Examples thereof include a pentyloxy group, an n-hexyloxy group and an isohexyloxy group. Examples of the halogen atom include chlorine atom, fluorine atom, iodine atom and bromine atom.

In the complex compound of the general formula (I), when A represents a heterocyclic compound, the heterocyclic compound contains 1 to 3 nitrogen atoms or 1 to 2 sulfur atoms as a ring hetero atom, or It is preferably a 5- or 6-membered heterocyclic compound containing 1 to 3 nitrogen atoms and 1 to 2 sulfur atoms. It may also be a condensation type with a benzene ring. Suitable examples of the heterocyclic compound include pyridine, imidazole, pyrazole, triazole, thiazole, pyrazine, benzimidazole and benztriazole.

When A is an amine compound of the formula R ² R ³ NH, R ² and R ³ can be alkyl groups, which alkyl groups can be straight-chain or branched.
It has 1 to 8 carbon atoms.

Examples of the alkyl group in the above amine compound include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, t-butyl group, isobutyl group, sec-butyl group, n-pentyl group. Group, isoamyl group, n-hexyl group, heptyl group, octyl group and the like.

The production of the complex compound of the general formula (I) is carried out by the following formula The substituted or unsubstituted triphenylborane of the formula [wherein R ¹ and n have the above-mentioned meaning] and the heterocyclic compound corresponding to A or the ammonia or amine compound in an equimolar ratio such as nitrogen. It is carried out by reacting in ethers such as ethyl ether, aromatic hydrocarbons such as benzene and toluene, or halogenated hydrocarbons such as dichloromethane at a temperature of 0 to 50 ° C. under a stream of a reactive gas. . This reaction can be carried out according to the method described in JP-A-62-277307.

Specific examples of the compound of the general formula (I) used in the coating composition of the present invention are shown in Table 1 below. The compound Nos. Of these specific examples are also referred to in Examples and Test Examples described below.

[0020]

[0021]

[0022]

[0023]

[0024]

[0025]

[0026]

[0027]

[0028]

In order to demonstrate that the complex compound of the general formula (I), which can be incorporated as an antifouling active ingredient in the antifouling paint of the present invention, has low toxicity to mammals, typical examples of the complex compound are shown. As such, the complex compounds shown in Table 2 below (see Table 1 for compound No.) were orally administered to mice, and their acute toxicity was tested. Also, for comparison, US Pat.
The following formula described in the specification of No. 679 as an antifouling compound The triphenylborane pyridine complex represented by (hereinafter,
“Comparative compound A”) The triphenylborane pyridine complex represented by (hereinafter,
"Comparative compound B") The triphenylborane pyridine complex represented by (hereinafter,
"Comparative compound C"), and Japanese Patent Publication No. 62-24022 disclose the following formula as an underwater antifouling agent. The tetraphenylboron compound represented by (hereinafter, referred to as “comparative compound D”) was similarly tested for acute toxicity of these comparative compounds.

The test method for acute toxicity by oral administration to mice as described above is as follows. ICR of 6 animals per group
To a mouse (male, 5 weeks old, body weight range; 25.0 to 26.5 g), the test substance of the compound No. shown in Table 2 was suspended in 0.5% carboxymethylcellulose sodium salt aqueous solution,
It was forcibly administered once in a volume of ml / 10 g (body weight). afterwards,
Intoxication symptoms and life or death of the mice were observed daily until 14 days after the administration of the test substance. The LD ₅₀ value was calculated from the number of dead cases using the method of Weil. In addition, the body weight of the mouse immediately before administration of the test substance,
The measurement was performed 7 days and 14 days after administration.

The test results are summarized in Table 2.

[0032]

As is clear from Table 2 above, the complex compound of the above-mentioned general formula (I) is more acute than the triphenylborane-pyridine complex of Comparative Compounds A to C or Comparative Compound D when administered orally to mice. High toxicity LD ₅₀ values indicate low toxicity to mammals. Therefore, it is recognized that the complex compound of the general formula (I) is highly safe for mammals even if it is incorporated into an underwater antifouling paint. In particular, the complex of nicotinic acid or its amide or alkyl ester with tris (substituted phenyl) borane corresponding to the compounds No. 20, 21 and 22 according to the present invention is highly safe.

Further, the underwater antifouling paint of the present invention will be described in detail. To prepare the antifouling coating composition of the present invention, at least one of the complex compounds of general formula (I) used as the antifouling active ingredient is added to the coating composition to be rendered antifouling by conventional means. Is appropriate. As means for blending such an active ingredient compound, the active ingredient compound is dissolved in an organic solvent which dissolves it, or, in the absence of a suitable organic solvent, the active ingredient compound is mixed and ground as a powder, for example, It is mechanically uniformly pulverized and mixed by an atomizer or the like. An organic solvent for the paint, a surfactant, a paint resin, a plasticizer, a pigment and other necessary auxiliary components for paint are added to the solution of the active ingredient compound thus obtained or the powder of the active ingredient compound. It is possible to formulate the antifouling paint by mixing the ingredients uniformly.

The paint resin which can be used in the underwater antifouling paint of the present invention is a film-forming resin for forming a coating film on the surface of a substrate, which is usually used in conventional underwater antifouling paints. The same resin as the existing resin can be used. For example, as the resin, vinyl chloride-vinyl acetate copolymer, vinyl chloride-
Vinyl isobutyl ether copolymer, styrene-butadiene copolymer, chlorinated rubber resin, chlorinated polypropylene resin, petroleum resin, alkyd resin, acrylic resin, phenol resin, synthetic rubber, epoxy resin, silicone Examples thereof include rubber, silicone resin, Teflon resin, and rosin resin.

In the underwater antifouling paint of the present invention, the compounding amount of the complex compound of the general formula (I) is in the range of 0.1 to 350 parts by weight, preferably about 1 to 100 parts by weight of the coating resin.
A range of 150 parts by weight is suitable. Further, it is desirable that the above-mentioned plasticizer is blended in an amount of 20 parts by weight or less per 100 parts by weight of the resin for coating.

In the underwater antifouling paint of the present invention, if necessary, a coloring pigment or a coloring agent such as titanium white, red iron oxide, carbon, cyan blue, cyanine green or the like, or an extender pigment such as talc, barita or zinc white. Etc. can be blended. Further, water or an organic solvent can be added in order to adjust the viscosity of the paint. The type of organic solvent used is not particularly limited as long as it can dissolve or disperse the above-mentioned coating resin and other components to be blended.

Examples of the organic solvent include alcohols (methyl alcohol, ethyl alcohol, n-propyl alcohol, isopropyl alcohol, n-butyl alcohol, ethylene glycol, benzyl alcohol, etc.), aromatic hydrocarbons (benzene, toluene,
Xylene, ethylbenzene, chlorobenzene, cumene,
Methylnaphthalene etc.), halogenated hydrocarbons (chloroform, carbon tetrachloride, dichloromethane, chloroethylene, trichlorofluoromethane, dichlorodifluoromethane etc.), ethers (ethyl ether, ethylene oxide, dioxane, tetrahydrofuran etc.), ketones (acetone) , Methyl ethyl ketone, cyclohexanone, methyl isobutyl ketone, etc.), esters (ethyl acetate, butyl acetate, ethylene glycol acetate,
Amyl acetate, etc.), Nitriles (acetonitrile, propionitrile, acrylonitrile, etc.), Sulfoxides (dimethyl sulfoxide, etc.), Glycol ethers (ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, etc.), Amines (ethylamine, dimethylamine) , Triethylamine, isobutylamine, etc.), aliphatic or alicyclic hydrocarbons (n
-Hexane, cyclohexane, etc., industrial gasoline (petroleum ether, solvent naphtha, etc.) and petroleum fractions (paraffins, kerosene, light oil, etc.) and the like.

In the underwater antifouling coating composition of the present invention, a surfactant can be added for the purpose of emulsification, dispersion, wetting, foaming and spreading during formulation. As such a surfactant,
Examples thereof are given below, but the present invention is not limited to these examples.

(A) Nonionic surfactants such as polyoxyethylene alkyl ether, polyoxyethylene alkyl ester, polyoxyethylene sorbitan alkyl ester, sorbitan alkyl ester, etc. (b) Anionic surfactant such as alkylbenzene Sulfonates, alkyl sulphosuccinates, alkyl sulphates, polyoxyethylene alkyl sulphates,
(C) cationic surfactants, such as laurylamine as alkylamines, stearyltrimethylammonium chloride, alkyldimethylbenzylammonium chloride, and (d) amphoteric surfactants, such as betaine-type compounds. Sulfate ester etc.

In addition to the above-mentioned ingredients, various auxiliary agents such as polyvinyl alcohol (PVA), carboxymethyl cellulose (CMC), arabic rubber, polyvinyl acetate, gelatin, casein, sodium alginate are added to the antifouling paint of the present invention. it can.

The underwater antifouling paint of the present invention exhibits sufficient antifouling effect only by blending one or more complex compounds of the general formula (I) as an antifouling active ingredient. Accordingly, conventionally known antifouling and antifungal algae agents such as zinc dimethyldithiocarbamate, 2-methylthio-4-t-butylamino-6-cyclopropylamino-s-triazine, 2,4,5,6. -Tetrachloroisophthalonitrile, zinc ethylene bisdithiocarbamate, 4,5-dichloro-2-n-octyl-3 (2H)
Isothiazoline, N- (fluorodichloromethylthio)
Phthalimide, N, N'-dimethyl-N'-phenyl-
(N-fluorodichloromethylthio) sulfamide, 2
-Pyridinethiol-1-oxide zinc salt, tetramethylthiuram disulfide, 2,3,5,6-tetrachloro-4- (methylsulfonyl) pyridine, 2,4,6
-Trichlorophenylmaleimide, 3-iodo-2-propynylbutyl carbamate, diiodomethyl paratolyl sulfone, bisdimethyldithiocarbamoyl zinc,
Addition of one or two kinds of ethylene bisdithiocarbamate, 2-methyl-4-isothiazolin-3-one, 2-methylthio-4-tetrabutyl-6-cyclopropylamino-s-triazine and salts and esters thereof. You may mix it.

Hereinafter, the present invention will be described more specifically with reference to examples. All parts in these examples are parts by weight.

Example 1 Compound No. 100 20 parts, rosin 12 parts, chlorinated isopropylene rubber 15 parts, zinc oxide 10 parts, red iron oxide 5 parts, colloidal silica 3 parts, talc 8 parts, xylene 10
Parts, 15 parts of methyl isobutyl ketone, and 2 parts of n-butyl alcohol for a total of 100 parts were subjected to a dispersion treatment by tumbling and mixing in a ball mill for 5 hours to obtain a uniform coating composition.

Examples 2 to 13 and Comparative Examples 1 to 4 Examples 2 to 13 were prepared in the same manner as in Example 1 except that the ingredients were mixed according to the composition of the coating composition shown in Table 3 below.
And the paints of Comparative Examples 1 to 4 containing the antifouling compound for comparison were prepared. The formulation of these prepared paints, including the paint of Example 1, is summarized in Table 3.

[0046]

[0047]

Test Examples 1 to 13 and Comparative Test Examples 1 to 4 An ordinary rust preventive paint was applied to a sandblasted steel sheet in advance, and the dried coating film was applied to Examples 1 to 13 and Comparative Examples 1 to 1. A test plate (100 mm x 3) in which the paint of No. 4 was brushed twice to make the dry paint film thickness of the antifouling paint about 100 μm.
I made 00 mm). The test plate thus obtained was immersed in a 1.5 m deep sea in Aburatsubo Bay, Miura City, Kanagawa Prefecture for 24 months, and the aquatic organism adhesion area was measured every month for the period shown in Table 4 below. . And the antifouling effect was shown by percentage (%) by the following formula. The test results are shown in Table 4.

[0049]

[Equation 1]

[0050]

As is clear from the results in Table 4, the test plates coated with the coating materials of Examples 1 to 13 containing various complex compounds (I) as the antifouling active ingredient according to the present invention were dipped 18 The antifouling rate remained in the 95-100% range even at the end of the month, and most of it remained in the 95-100% range at the 24th month. On the other hand, the comparative test plates coated with the paints of Comparative Examples 1 to 4 containing the antifouling compound not according to the present invention were dipped.
By the 12th month, the antifouling effect rate has already dropped to the 80-90% range.

Test Example 14 Compound Nos. 1, 2, 4, 6, 8 to 10, 12, 13, 15 to 18, 23 of Table 1 were used in place of the complex of Compound No. 100 used in Example 1.
Various coating compositions were prepared in the same manner as in Example 1 using the complexes of -42,44-52,54-73,75-99,101-106.
Test samples coated with samples of these coating compositions in the same manner as in Test Examples 1 to 13 were tested in the same manner as in Test Examples 1 to 13, and the value of the antifouling effect 18 months after immersion was 95 to 100%. It was recognized as a stand.

Further, most of the exemplified complex compounds shown in Table 1 above are known substances, but among the exemplified complex compounds, the complex compounds of Compound Nos. 20, 21 and 22 are novel compounds. is there. Moreover, as shown in Table 2 above, these complex compounds have extremely low toxicity to mammals.

Therefore, in another aspect of the present invention, as a novel substance, [Wherein R ^1a is a lower alkyl group, a lower alkoxy group or a halogen atom, especially a chlorine atom, and X is a hydroxyl group, an amino group or a lower alkoxy group], and tris (substituted phenyl) borane and nicotinic acid or A complex compound with the derivative is provided.

The complex compound represented by the general formula (I ') is
The following formula [Wherein R ^1a has the above-mentioned meaning] and tris (substituted phenyl) borane is represented by the following formula: It can be produced by reacting with nicotinic acid, nicotinic acid amide, or nicotinic acid alkyl ester represented by the formula [wherein X has the above-mentioned meaning].

This reaction is carried out by reacting the compound of formula (II ') with the compound of formula (II
The compound of I) is dissolved in an organic solvent such as ethyl ether, tetrahydrofuran, benzene, toluene, chloroform, dichloromethane in an equimolar ratio or substantially, and the reaction mixture is removed in the presence of an inert gas such as nitrogen by excluding air. Is preferably carried out at 0 to 50 ° C. with stirring for 1 hour to 2 days.

The production methods of the complex compounds of the above compound Nos. 20, 21, and 22 are shown below in Reference Production Examples 1 to 3 below.

Reference Production Example 1 Synthesis of tris (4-methylphenyl) borane / nicotinic acid amide complex (Compound No. 21) Tris (4-methylphenyl) was placed in a glove box in which nitrogen gas was passed to expel air and moisture. ) Borane 2.84g
(10 mmol) was dissolved in 50 ml of a mixed solvent of tetrahydrofuran and benzene (1: 1) and placed in a 100 ml separating funnel. Separately, 1.22 g (10 mmol) of nicotinic acid amide and 50 ml of the above mixed solvent were placed in a 200 ml four-necked flask equipped with a thermometer, an agitator, and a nitrogen inlet, and the mixture was stirred and melted. Nitrogen gas was flown through the nitrogen inlet to replace the inside of the flask with nitrogen gas. With stirring, the above tris (4-methylphenyl) borane solution was added dropwise from the above separating funnel over 10 minutes at room temperature, and the mixture was stirred at the same temperature for 5 hours for reaction. After completion of the reaction, the solvent was distilled off under reduced pressure to obtain a white solid. This white solid was mixed with dichloromethane and n-
The crystals were recrystallized from a mixed solvent of hexane (1: 2), filtered and dried to obtain 3.90 g (yield 96.1%) of the title complex compound as white crystals having a melting point of 155 to 158 ° C (decomposition).

Reference Production Example 2 Synthesis of tris (4-chlorophenyl) borane / nicotinic acid complex (Compound No. 20) Tris (4-chlorophenyl) borane (3.46 g, 10 mmol) and nicotinic acid (1.23 g, 10 mmol) were combined. The reaction was carried out by the same method as in Reference Production Example 1. The white solid obtained was recrystallized in the same manner as in Reference Production Example 1 to give 4.49 g (yield 95.8%) of the title complex compound as the melting point of 234 to 237 ° C.
Was obtained as white crystals.

Reference Production Example 3 Synthesis of tris (4-methylphenyl) borane / methyl nicotinate complex (Compound No. 22) Tris (4-methylphenyl) borane 2.84 g (10 mmol) and methyl nicotinate 1.37 g (10 Was reacted in the same manner as in Reference Production Example 1. The white solid obtained was recrystallized in the same manner as in Reference Production Example 1 to obtain 3.95 g of the title complex compound (yield 96.4%) at a melting point of 114-119 ° C.
Was obtained as white crystals.

[0061]

INDUSTRIAL APPLICABILITY The underwater antifouling paint of the present invention is applied to an underwater structure to adhere aquatic organisms such as barnacles, squirts, serpras, mussels, mussels, hemlock worms, aonori and aosa for a long period of time. It can be prevented for a long time and an excellent antifouling effect can be exhibited. And
The antifouling effect of the antifouling coating composition of the present invention and the duration of the antifouling coating composition are far superior to those in the case of using a coating composition containing an antifouling active ingredient compound which has been frequently used. Further, the complex compound of the general formula (I), which is an antifouling active ingredient mixed in the antifouling paint of the present invention, has low toxicity to human livestock and seafood, and thus the antifouling paint of the present invention can be safely used. .

 ─────────────────────────────────────────────────── ─── Continuation of front page (72) Inventor Masayuki Umeno 3 at 521 Chigasaki, Chigasaki City, Kanagawa Prefecture (72) Inventor Mitsuo Hamada 14 (72) Inventor, 2-28, East Asahina, Kanazawa-ku, Yokohama City, Kanagawa Prefecture Yuichiro Kawasaki 19-17 Ikedanaka-cho, Neyagawa-shi, Osaka Japan Paint Co., Ltd. (72) Inventor Emiko Yasuhara 19-17 Ikedanaka-cho, Neyagawa-shi, Osaka Japan Paint Co., Ltd.

Claims (1)

[Claims] 1. The following general formula [In the formula, R ¹ is one or more of a lower alkyl group, a lower alkoxy group or a halogen atom, n is an integer of 1, 2 or 3, and A is a nitrogen atom or a sulfur atom or both of them. Represents a heterocyclic compound containing as a ring atom, and the heterocyclic compound may be substituted with at least one substituent selected from a lower alkyl group, a carboxyl group, an aminocarbonyl group, a lower alkoxycarbonyl group, a hydroxyl group and a halogen atom. Well, or A is of the formula R ² R ³ N
H (provided that R ² and R ³ are each independently the same or different hydrogen atom, alkyl group or cyclohexyl group) or an amine compound] is used as an antifouling active ingredient. An underwater antifouling paint characterized by containing.