JPH06100405A - Underwater antifouling agent - Google Patents

Abstract

(57) [Summary] [Structure] (1) [Chemical 1] In-water antifouling agent containing (2) compound (I) and 2- (thiocyanomethylthio) benzothiazole, tetrachloroisophthalonitrile, tetraethylthiuram disulfide, 4,5-dichloro-2-n-octyl -3-isothiazolone, zinc dithiocarbamate, zinc pyrithione (ZPT), 2,2'-dithiobis (pyridine-N-
Oxide) and one or more compounds selected from the group consisting of (3) ditertiary nonylpentasulfide, polybutene (HV-35), liquid paraffin, and white petrolatum, and one or more compounds selected from The underwater antifouling agent as described in (1) or (2) above, which contains the above. [Effect] The underwater antifouling agent containing the compound of the present invention has a low pollution property and shows an excellent antifouling effect for aquatic fouling organisms over a long period of time.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention prevents aquatic fouling organisms from adhering to fishing nets for aquaculture or stationary and materials used for them such as floats and ropes, as well as ship bottoms and underwater structures. The present invention relates to an underwater antifouling agent containing a maleimide compound, which is useful as an antifouling component of a low-pollution underwater antifouling composition containing no heavy metal.

[0002]

2. Description of the Related Art Since fishnets for fishing or stationary, ship bottoms, underwater structures, etc. are retained in the sea for a long period of time, adhesion of marine fouling organisms such as seaweeds, barnacles, serpra, bryozoans, molluscs, etc. However, the current situation is that the economic operation of these resources is hindered, and the maintenance of them is laborious and expensive.

Various studies and proposals have been made as measures against this, but it is known that a series of organic tin compounds and cuprous oxide are practically effective. However, these organotin compounds are generally highly toxic, and careless handling of products containing them may cause troubles to the handler, and are disadvantageous in terms of environmental measures. Since cuprous oxide is eluted in seawater and remains as copper ions or copper compounds, it may have an unfavorable effect on the environment. Further, since it does not dissolve in a solvent, it has a drawback that it is difficult to prepare a formulation that is practical as a fishing net antifouling agent and has good workability.

For these reasons, the advent of a low-pollution underwater antifouling agent containing no heavy metals is desired.

For example, Japanese Patent Publication No. 51-10849 discloses an underwater antifouling coating composition containing a benzothiazole compound as an active ingredient, and Japanese Patent Publication Nos. 60-38306 and 63-63.
No. 284275 and Japanese Patent Publication No. 1-11606 disclose various anti-fouling agents for fishing nets, which are combinations of a tetraalkyl thiuram disulfide compound and other underwater antifouling compounds,
Antifouling paint composition and fishing net antifouling solution are disclosed in JP-B-61-50.
Japanese Patent Publication No. 984 discloses a pollution inhibitor for marine structures containing a 3-isothiazolone compound as an active ingredient.
No. 10, JP-A No. 54-15939 discloses an antibacterial agent containing a pyrithione metal salt as an active ingredient and an underwater antifouling paint.
JP-B-54-3889, JP-A-54-78733.
The publications disclose underwater antifouling paints containing 2,2'-dithiobis (pyridine-1-oxide) as an antifouling active ingredient.

[0006] However, none of these underwater antifouling agents have a sufficient effect of preventing adhesion to aquatic fouling organisms, and are strong against a wide variety of fouling organisms and exhibit a wide range of antifouling effects. Development of antifouling agents is desired.

On the other hand, Japanese Patent Application Laid-Open No. 53-9320 discloses that
It is disclosed that N-aryl maleimides are used as aquatic biorepellants. In addition, Japanese Patent Publication 2-24
No. 242 discloses that a 2,3-dichloro-N- (2,6-dialkylphenyl) maleimide compound exhibits an excellent anti-adhesion effect against a wide variety of water-adhering organisms. It is not effective against adherent organisms such as Hydrozoa. Furthermore, Japanese Patent Fairness 1-20
Although Japanese Patent No. 665 discloses 2,3-dichloro-N-cyclohexylmaleimide as an underwater antifouling agent, these compounds do not always have a sufficient antifouling effect, and further, a good preparation. It cannot be said that it has characteristics.

[0008]

DISCLOSURE OF THE INVENTION The present invention provides a practical underwater antifouling agent which does not contain heavy metals and has a low pollution property and an excellent antifouling effect against a wide variety of underwater adherent organisms. With the goal.

[0009]

Means for Solving the Problems Except for the above-mentioned drawbacks of conventional underwater antifouling agents, the present inventors do not contain heavy metals with low toxicity and less risk of environmental pollution, and have high safety and workability. As a result of earnest research on an underwater antifouling agent having good water resistance, N-phenethyldichloromaleimide has an excellent antifouling effect against aquatic fouling organisms, and the antifouling effect further enhanced by using it in combination with a certain compound. Therefore, the present invention has been completed.

That is, the present invention provides (1)

[0011]

[Chemical 9]

2,3-dichloro-N- represented by
(1-phenylethyl) maleimide (also referred to as N-phenethyldichloromaleimide in the present specification), an underwater antifouling agent, (2) N-phenethyldichloromaleimide of compound (I), (i) 2
-(Thiocyanomethylthio) benzothiazole, (ii) tetrachloroisophthalonitrile, (iii) general formula

[0013]

[Chemical 10]

(Wherein R represents alkyl having 1 to 4 carbon atoms), one or more compounds represented by the formula (iv)

[0015]

[Chemical 11]

[Wherein, X ¹ and X ² are the same or different and each represents hydrogen, halogen or alkyl having 1 to 4 carbon atoms (provided that at least one of X ¹ and X ² is halogen, and ^{When one of 1} and X ² is other than halogen, the solubility of the compound measured by UV method is 0.
5 to 500 ppm), Y is (a) carbon number 1 to 18
Unsubstituted alkyl, (b) at least one hydrogen is halogen, hydroxy, cyano, alkylamino, dialkylamino, phenylamino, halophenylamino, carboxy, alkoxycarbonyl, alkoxy, aryloxy, morpholino, piperidino, Substituted alkyl substituted by pyrrolidonyl, carbamoyloxy or isothiazolonyl (however, the total number of carbon atoms in the substituted alkyl does not exceed 18), (c) carbon number 2-18
Unsubstituted halo or halo substituted alkenyl,
(D) an unsubstituted alkynyl or halo-substituted alkynyl having 2 to 18 carbon atoms, (e) a hydrocarbon ring having 3 to 6 ring-constituting carbon atoms, and an unsubstituted cycloalkyl having a total carbon number of 12 or Alkyl-substituted cycloalkyl, (f) an unsubstituted aralkyl having a total number of carbons not exceeding 10 or an aralkyl substituted with halogen, lower alkyl or lower alkoxy, or (g) having a total of 10 carbons in an aryl group. It does not exceed unsubstituted aryl or aryl substituted with halogen, phenoxy, hydroxy, trihalomethyl, nitro, lower alkyl, lower alkoxy or lower alkoxycarbonyl. ] One or more isothiazolone compounds represented by

[0017]

[Chemical 12]

[0018]

[Chemical 13]

[0019]

[Chemical 14]

(In the formula, R ¹ , R ² , and R ³ have 1 to 4 carbon atoms.
Alkyl, M ¹ is a metal forming a water-insoluble metal salt of zinc, manganese, copper, iron or nickel, n is 2 or 3 and M ² is a water-insoluble metal salt of zinc, manganese, copper or nickel. Shows the metal forming the. ) One or more types of water-insoluble dithiocarbamic acid metal salts represented by

[0021]

[Chemical 15]

(Wherein each symbol has the same meaning as defined above), one or more water-insoluble pyrithione metal salts represented by the formula (v
ii) 2,2'-dithiobis (pyridine-N-oxide)
Underwater antifouling agent characterized by containing as an active ingredient one or more compounds of the (i) from (vii) to selected from and (3) (i) the general formula _{^{R 4 - (S) m -R}} 4 (VIII) (In the formula, R ⁴ represents alkyl having 1 to 20 carbon atoms, m
Represents an integer of 2 to 10. 1) of the compounds represented by
Or more, (ii) one or more of polybutene having an average molecular weight of 200 to 1,000, (iii) one or more of paraffins, and (iv) one or more of compounds (i) to (iv) selected from petrolatum. And an underwater antifouling agent as described in (1) or (2) above, which comprises:

The N-phenethyldichloromaleimide of the present invention comprises dichloromaleic anhydride and 1-phenylethylamine in the absence or presence of a dehydration catalyst in the presence or absence of a dehydration catalyst from room temperature to 120 ° C, preferably 90 to 110 ° C.
Then, it can be synthesized by reacting for 1 to 5 hours.

Examples of the solvent include nonpolar solvents such as toluene, xylene and benzene, polar solvents such as dimethylformamide and dimethylsulfoxide, organic acids such as acetic acid, formic acid and propionic acid, and sulfuric acid and hydrochloric acid as dehydration catalysts. , Acetic acid, glacial acetic acid, p-toluenesulfonic acid and the like.

The amount of N-phenethyldichloromaleimide of the present invention can be arbitrarily changed depending on the application target of the underwater antifouling agent and the application environment, and is not particularly limited.
Usually, it is 3 to 30% by weight, preferably 5 to 20% by weight.

The compound represented by the general formula (II) is
For example, tetramethyl thiuram disulfide, tetraethyl thiuram disulfide, tetraisopropyl thiuram disulfide, and tetra-n-butyl thiuram disulfide can be mentioned, but not limited thereto.

The compound represented by the general formula (III) is
For example, 4,5-dichloro-2-n-octyl-3-
Isothiazolone, 5-chloro-2-n-decyl-3-isothiazolone, 4,5-dichloro-2- (4-chlorobenzyl) -3-isothiazolone, 4,5-dichloro-2
-(4-chlorophenyl) -3-isothiazolone, 4,
5-dichloro-2-n-hexyl-3-isothiazolone, 4,5-dichloro-2- (2-methoxy-3-chlorophenyl) -3-isothiazolone, 4,5-dibromo-2- (4-chlorobenzyl) -3-isothiazolone,
4-methyl-5-chloro-2- (4-hydroxyphenyl) -3-isothiazolone, 5-chloro-2- (3,4
-Dichlorophenyl) -3-isothiazolone, but not limited thereto.

The compound represented by the general formula (IV) is, for example, bis (dimethyldithiocarbamate) zinc, tris (dimethyldithiocarbamate) iron, bis (dimethyldithiocarbamate) copper, bis (dimethyldithiocarbamate) nickel, bis. Examples thereof include (diethyldithiocarbamate) zinc and bis (dibutyldithiocarbamate) zinc, but are not particularly limited thereto.

Examples of the compound represented by the general formula (V) include zinc ethylenebisdithiocarbamate and manganese ethylenebisdithiocarbamate, but are not particularly limited thereto.

Examples of the compound represented by the general formula (VI) include zinc bis (dimethyldithiocarbamoyl) ethylenebisdithiocarbamate and manganese bis (dimethyldithiocarbamoyl) ethylenebisdithiocarbamate, but are not particularly limited thereto. Not something.

The compound represented by the general formula (VII) is, for example, pyrithione zinc (zinc pyrithione, ZP
T), copper pyrithione, manganese pyrithione, iron pyrithione, nickel pyrithione, but are not particularly limited thereto.

The N-phenethyldichloromaleimide of the present invention, 2- (thiocyanomethylthio) benzothiazole, tetrachloroisophthalonitrile, one or more compounds (II), one or more compounds (III), and a compound (IV ), Compound (V), one or more compounds (VI), one or more compounds (VII) and 2,2′-dithiobis (pyridine-N—
In an underwater antifouling agent containing at least one compound selected from the group consisting of oxides) 3 to 30% by weight, preferably 5 to 2
It is 0% by weight. The mixing ratio of the respective active ingredients can be arbitrarily changed depending on the conditions of the antifouling performance and the usage environment required. Furthermore, known effective and safe active ingredients may be added, and a more balanced effect can be expected against various fouling organisms.

The known effective and safe active ingredients are copper compounds such as cuprous thiocyanate, copper naphthenate, copper oleate, copper abietic acid and copper 8-oxyquinoline; 2- (4-thiazolyl). Benzimidazole, 2
-Benzoimidazole compounds such as thiocyanomethylthiobenzimidazole and 2- (methoxycarbonylamino) benzimidazole; nitrile compounds such as 5-chloro-2,4-difluoro-6-methoxyisophthalonitrile and tetrafluoroisophthalonitrile ; 2
3,5,6-tetrachloro-4- (methylsulfonyl)
Pyridine compounds such as pyridine, 2,3,6-trichloro-4-propylsulfonylpyridine, 2,6-dichloro-3,5-dicyano-4-phenylpyridine; 2,
4-dichloro-6- (o-chloroanilino) -s-triazine, 2-chloro-4-methylamino-6-isopropylamino-s-triazine, 2-chloro-4,6-bis (ethylamino) -s- Triazine, 2-methylthio-4,6-bis (ethylamino) -s-triazine, 2
-Methylthio-4-ethylamino-6-isopropylamino-s-triazine and other triazine compounds; 3-
(3,4-Dichlorophenyl) -1,1-dimethylurea, 3- (3,4-dichlorophenyl) -1-methoxy-1-methylurea, 1- (2-methylcyclohexyl)
Urea compounds such as 3-phenylurea; 2-amino-3
-Chloro-1,4-naphthoquinone, 2,3-dichloro-
Quinone compounds such as 1,4-naphthoquinone and 2,3-dicyano-1,4-dithia-1,4-dihydroanthraquinone; N-trichloromethylthiotetrahydrophthalimide, N-trichloromethylthiophthalimide, N-
Phthalimide compounds such as fluorodichloromethylthiophthalimide; methylenebisthiocyanate, ethylenebisthiocyanate, phenylisothiocyanate,
Examples thereof include (iso) thiocyanate compounds such as benzyl isothiocyanate, allyl isothiocyanate, and 3,4-dichlorophenyl isothiocyanate, but are not limited thereto.

Further, the compound represented by the general formula (VIII) used as an elution regulator is, for example, diethyl pentasulfide, dipropyl tetrasulfide,
Ditertiary butyl disulfide, ditertiary butyltetrasulfide, ditertiary amyltetrasulfide, ditertiary nonylpentasulfide, ditertiary dodecylpentasulfide, Examples thereof include, but are not limited to, dinonadecyl tetrasulfide.
It may also be a mixture thereof.

Polybutene having an average molecular weight of 200 to 1000 used as an elution regulator is, for example, a product of Nippon Oil Co., Ltd. and has trade names LV-5 and LV.
-10, LV-25, LV-50, LV-100, HV
-15, HV-35, HV-50, and HV-100 can be mentioned, but the invention is not particularly limited to these products, and a mixture thereof may be used.

Examples of paraffins used as the dissolution modifier include liquid paraffin, paraffin wax, and chlorinated paraffin, but are not particularly limited to these, and a mixture thereof may be used. Good.

Further, petroleum jelly used as the elution regulator includes white petrolatum and yellow petrolatum.

Compounds used as dissolution modifiers (VII
In the underwater antifouling agent containing one or more compounds selected from I), polybutene, paraffins and petrolatum, it is 3 to 20% by weight, preferably 5 to 10% by weight. The mixing ratio of each elution regulator can be arbitrarily set depending on the use conditions of each active ingredient.

The underwater antifouling agent of the present invention is generally used in the form of paint or solution, and can be easily produced by a usual method. For example, antifouling agents for fishing nets include N-phenethyldichloromaleimide of compound (I) alone or N-phenethyldichloromaleimide of compound (I), 2- (thiocyanomethylthio) benzothiazole, tetrachloroisophthalonitrile, compound One or more of (II), one or more of compound (III), one of compound (IV), one of compound (V) and one of compound (VI)
At least one compound, at least one compound (VII) and at least one compound selected from 2,2′-dithiobis (pyridine-N-oxide), as a dissolution modifier, from compound (VIII), polybutene, paraffins and petrolatum. The resin may be added to one or more selected and dissolved or dispersed in a solvent.
The resin used here includes, for example, rosin resin, acrylic resin, polybutene resin, chlorinated rubber resin, vinyl chloride resin, alkyd resin, coumarone resin, polybutadiene resin, ethylene-vinyl acetate resin, and one of them or You may use together more. Further, as a solvent or a viscosity modifier, xylene, solvent naphtha,
Pseudocumene, butanol, isopropyl alcohol, methyl isobutyl ketone, methyl ethyl ketone, acetone, butyl acetate, diethylbenzene, triethylbenzene, mesitylene, toluene, alkyl cellosolve (methyl cellosolve, ethyl cellosolve, etc.) and the like can be mentioned. When applied to the bottom of a ship, cuprous oxide,
It can be used in the form of paint by adding rouge, talc, barium sulfate, tricresyl phosphate and the like.

[0040]

The N-phenethyldichloromaleimide-containing underwater antifouling agent of the present invention has low toxicity, high safety, and exhibits a long-lasting antifouling effect. In addition, N-phenethyldichloromaleimide of the present invention, one or more of 2- (thiocyanomethylthio) benzothiazole, tetrachloroisophthalonitrile, compound (II), compound (III)
One or more of compound (IV), compound (V), compound (V
One or more of I), one or more of compound (VII) and 2,
An underwater antifouling agent containing one or more compounds selected from 2'-dithiobis (pyridine-N-oxide) exhibits a further enhanced antifouling effect as compared with a single agent.

[0041]

EXAMPLES Hereinafter, production examples and examples will be shown, but the present invention is not limited thereto. In addition, the compounding in an Example shows weight%.

Production Example 2,3-dichloromaleic anhydride 16 was placed in a four-necked flask equipped with a cooling tube equipped with a water separator, a thermometer and a stirrer.
7 g and 500 ml of toluene were charged, and 121 g of 1-phenylethylamine was added dropwise at room temperature in about 30 minutes. The liquid temperature was raised to 110 ° C., the produced water was removed by azeotropic distillation, and the mixture was washed 5 times with 1 L of warm water at room temperature, and then toluene was concentrated by distillation to obtain 240 g of crude crystals. Recrystallized from 90% isopropyl alcohol, 201 g of 2,3-dichloro-N- (1-phenylethyl) maleimide having a melting point of 56-57.5 ° C.
Was obtained as white needle crystals.

Example 1 According to the following formulation example, each component was mixed and dissolved or dispersed to prepare an antifouling agent for fishing nets.

Formulation Example 1 N-phenethyldichloromaleimide 15% Acrylic resin (50% xylene solution) 50% Xylene 35% Formulation example 2 N-phenethyldichloromaleimide 10% Acrylic resin (50% xylene solution) 40% Ditertiary grade Nonylpentasulfide 5% Liquid paraffin (reagent) 5% Xylene 40% Formulation example 3 N-phenethyldichloromaleimide 8% 2- (thiocyanomethylthio) benzothiazole 8% Liquid paraffin (reagent) 5% Polybutene (HV-35) ) 5% acrylic resin (50% xylene solution) 40% xylene 34% Formulation example 4 N-phenethyldichloromaleimide 8% Tetraethylthiuram disulfide 8% Ditertiary nonylpentasulfide 5% Vaseline 5% acrylic resin (50% xylene solution) 40% Ren 34% Formulation Example 5 N-phenethyldichloromaleimide 6% Tetrachloroisophthalonitrile 6% Polybutene (LV-50) 5% Vaseline 5% Acrylic resin (50% xylene solution) 22% Pseudocumene 20% Solvent K-73 34% Formulation Example 6 N-phenethyldichloromaleimide 5% 4,5-dichloro-2-n-octyl-3-isothiazolone 5% Tetraethylthiuram disulfide 5% Ditertiary nonylpentasulfide 5% Vaseline 5% Acrylic Resin (50% xylene solution) 40% Xylene 35% Formulation Example 7 N-phenethyldichloromaleimide 8% Bis (dimethyldithiocarbamoyl) ethylenebisdithiocarbamate zinc 8% Ditertiary nonylpentasulfide 5% Liquid paraffin 5 % Acrylic resin (5 % Xylene solution) 40% xylene 34% Formulation Example 8 N-phenethyl-dichloro maleimide 8% zinc pyrithione (ZPT) 8% polybutene (LV-50) 5% Vaseline 5% acrylic resin (50% xylene solution) 40% xylene 34%

Example 2 An antifouling paint for ship bottom was prepared by pulverizing and kneading with a ball mill according to the following prescription example.

Formulation Example 9 N-phenethyldichloromaleimide 15% Tetramethylthiuram disulfide 15% Rouge 15% Talc 3% Barium sulfate 5% Rosin resin 11% Chlorinated rubber resin 5% Ditertiary nonylpentasulfite Do 3% Liquid paraffin (reagent) 3% Xylene 25% Formulation example 10 N-phenethyldichloromaleimide 15% Tetrachloroisophthalonitrile 15% Cuprous oxide 15% Rouge 5% Talc 5% Barium sulfate 5% Rosin resin 11% Chlorinated rubber resin 5% Vaseline 3% Polybutene (LV-10) 3% Xylene 18% Formulation Example 11 N-phenethyldichloromaleimide 15% 4,5-Dichloro-2-n-octyl-3-isothiazolone 10% Tetraethylthiuramdisul Fid 10% Rouge 15% Talc 3% Sulfur Barium acid 5% Rosin resin 11% Chlorinated rubber resin 5% Ditertiary nonylpentasulfide 3% Vaseline 3% Xylene 20% Formulation example 12 N-phenethyldichloromaleimide 15% Bis (dimethyldithiocarbamoyl) ethylenebisdithiocarbamin Zinc acidate 15% Rouge 15% Talc 3% Barium sulfate 5% Rosin resin 11% Chlorinated rubber resin 5% Di-tertiary nonylpentasulfide 3% Vaseline 3% Xylene 25% Formulation example 13 N-phenethyldichloromaleimide 15 % Zinc pyrithione (ZPT) 15% Rouge 15% Talc 3% Barium sulfate 5% Rosin resin 11% Chlorinated rubber resin 5% Ditertiary nonylpentasulfide 3% Polybutene (LV-50) 3% Xylene 25%

[0047]

【The invention's effect】

Experiment 1 The antifouling agent for fishing nets of Example 1 of the present invention was applied to polyethylene knotless nets (6 sections, 400 denier / 60 pieces) by dipping and air-dried, and then from February 1991, Kitabe, Wakayama Prefecture. The sea was maintained at a depth of about 50 cm below the sea level in the bay and the state of adhesion of fouling organisms to the net was investigated. The results were evaluated according to the criteria shown in Table 1.

[0048]

[Table 1] Table 1 ──────────────────────────────────── Status with valuation ── ─────────────────────────────────── A: No deposit B: Some deposit is practical There is no hindrance to it. C There are many deposits that cannot be used as a net for aquaculture. D There is an extremely large amount of deposits ─────────────────────── ─────────────

The comparative formulation is as follows. Comparative Example 1 Tetraethyl thiuram disulfide 15% Acrylic resin (50% xylene solution) 50% Xylene 35% The results are shown in Table 2.

[0050]

[Table 2] Table 2 ──────────────────────────────────── 1 month later 2 months later After 3 months After 4 months ──────────────────────────────────── Prescription example 1 A A B B 2 A A A B 3 A A A B B 4 A A A B 5 A A A B 6 A A A A B B 7 A A A B 8 A A A A B ──────────────── ──────────────────── Comparative Example 1 A B B C ─────────────────────── ───────────── Untreated network CD ──────────────────────────────── ────

As shown in Table 2, N-phenethyldichloromaleimide of the present invention alone or N-phenethyldichloromaleimide and 2- (thiocyanomethylthio) benzothiazole, tetrachloroisophthalonitrile, compound (II), compound (III) ), Compound (VI) and compound (VI
A fishing net antifouling agent containing at least one of I) as an active ingredient exhibits a sustainable and practical effect, and can provide an antifouling agent with low toxicity, high safety, and good storage stability. There was found.

Experiment 2 The ship bottom antifouling paint of Example 2 of the present invention was evenly applied twice with a brush to a test steel plate previously coated with a rust preventive paint and air dried. The obtained test steel sheets were kept in the sea at a depth of 1.5 m in Kii Tanabe Bay, Wakayama Prefecture, for 1 year from August 1990, and the state of adhesion of fouling organisms was investigated for each test steel sheet every two months.

Comparative Example 2 Cuprous oxide 40% Rouge 8% Talc 5% Rosin resin 10% Chlorinated rubber resin 6% Tricresyl phosphate 3% Xylene 28% The results are shown in Table 3. The numbers in the table represent the fouling organism attached area percentage.

[0054]

[Table 3] Table 3 ──────────────────────────────────── Days (Mon) 2 46 8 10 12 ──────────────────────────────────── Prescription example 9 0 0 0 0 0 5 5 10 0 0 0 0 5 5 10 11 0 0 0 0 0 5 5 12 0 0 0 0 0 5 5 10 13 0 0 0 0 0 0 5 5 ───────────────────────── ──────────── Comparative example 2 0 20 35 35 65 95 ───────────────────────────── ─────── Unpainted 80 100 ─────────────────────────────────────

As shown in Table 3, N-phenethyldichloromaleimide of the present invention alone or N-phenethyldichloromaleimide and tetrachloroisophthalonitrile, compound (II), compound (III), compound (VI) and compound (V)
It has been found that ship bottom antifouling paints containing one or more of II) as active ingredients have a long-lasting practical effect and can provide highly safe antifouling agents with low toxicity.

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁵ Identification code Internal reference number FI Technical display location A01N 43/80 102 8930-4H 47/14 8930-4H (72) Inventor Naoki Kumagai Chikujo-gun, Fukuoka Prefecture Yoshitomi-cho, Oita small holiday 955 Yoshitomi Pharmaceutical Co., Ltd. Yoshitomi factory

Claims (3)

[Claims] Claims: An underwater antifouling agent comprising N-phenethyldichloromaleimide represented by: 2. [Chemical formula 2] N-phenethyldichloromaleimide represented by
(i) 2- (thiocyanomethylthio) benzothiazole,
(ii) tetrachloroisophthalonitrile, (iii) general formula: (Wherein R represents alkyl having 1 to 4 carbon atoms), one or more compounds represented by the formula (iv) Wherein, X ¹ and X ² are the same or different and represent a hydrogen, halogen or having 1 to 4 carbon atoms alkyl (provided that at least one of X ¹ and X ² is a halogen, more X ¹ and X ^When one of ² is other than halogen, the solubility of the compound measured by UV method is 0.5 to 50.
Y is (a) unsubstituted alkyl having 1 to 18 carbon atoms, (b) at least one hydrogen is halogen,
Substituted alkyl substituted by but not limited to hydroxy, cyano, alkylamino, dialkylamino, phenylamino, halophenylamino, carboxy, alkoxycarbonyl, alkoxy, aryloxy, morpholino, piperidino, pyrrolidonyl, carbamoyloxy or isothiazolonyl. The total number of carbons in the alkyl does not exceed 18), (c) unsubstituted alkenyl having 2 to 18 carbons or halo-substituted alkenyl, (d) unsubstituted alkynyl having 2 to 18 carbons or halo-substituted alkynyl, (E) having a hydrocarbon ring having 3 to 6 ring-constituting carbon atoms and having a total carbon number of up to 12 unsubstituted cycloalkyl or alkyl-substituted cycloalkyl, (f) the total number of carbon atoms in aralkyl is 10 Unsubstituted aralkyl or halogen, lower alk Or an aralkyl substituted with a lower alkoxy or (g) an unsubstituted aryl having a total number of carbon atoms in the aryl does not exceed 10, or substituted with halogen, phenoxy, hydroxy, trihalomethyl, nitro, lower alkyl, lower alkoxy or lower alkoxycarbonyl. The aryl is shown. ] One or more isothiazolone compounds represented by the formula (v) [Chemical 6] [Chemical 7] (In the formula, R ¹ , R ² and R ³ are alkyl having 1 to 4 carbon atoms, M ¹ is a metal forming a water-insoluble metal salt of zinc, manganese, copper, iron or nickel, and n is 2 or 3, M ² represents a metal which forms a water-insoluble metal salt of zinc, manganese, copper or nickel), and (vi) a general formula: (Wherein each symbol has the same meaning as defined above), one or more water-insoluble pyrithione metal salts, (vii) 2,2 ′
-Dithiobis (pyridine-N-oxide)
An underwater antifouling agent comprising one or more of the compounds (i) to (vii) as an active ingredient. (I) General formula R ⁴ — (S) _m —R ⁴ (VIII) (wherein R ⁴ represents alkyl having 1 to 20 carbon atoms, m
Represents an integer of 2 to 10. 1) of the compounds represented by
Or more, (ii) one or more of polybutene having an average molecular weight of 200 to 1,000, (iii) one or more of paraffins, and (iv) one or more of compounds (i) to (iv) selected from petrolatum. The underwater antifouling agent according to claim 1, further comprising: as an elution regulator.