JPH06305908A - Aquatic antifouling agent - Google Patents

Abstract

PURPOSE:To obtain an aquatic antifouling agent exhibiting excellent antifouling effect on aquatic fouling organisms over a long period and having low polluting property by using a specific maleimide compound singly or in combination with other aquatic antifouling agent. CONSTITUTION:The aquatic antifouling agent contains (A) an N- benzyldichloromaleimide compound of formula I (R<1> and R<2> are H, halogen or alkyl) singly or in combination with (B) compounds selected from (i) 2-(thiocyanomethylthio)benzothiazole, (ii) tetrachloroisophthalonitrile, (iii) isothiazolone compound of formula II (X<1> and X<2> are H, halogen or alkyl; Y is alkyl, alkenyl, cycloalkyl, aralkyl, aryl, etc.), (iv) compound of formula III (R<3> is alkyl; (p) is 1 or 2), (v) water-insoluble dithiocarbamic acid salt of formula IV (R<4> is alkyl; M<1> is Zn, Mn, Cu, etc.; (n) is 2 or 3), (vi) water-insoluble dithiocarbamic acid salt of formula V (M<2> is Zn, Mn, etc.), (vii) compound of formula VI (R<5> and R<6> are alkyl), (viii) water-insoluble pyrithione metal salt of formula VII and (ix) 2,2'-dithiobis(pyridine-N-oxide).

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 fishing nets for fishing or stationary, ship bottoms, underwater structures, etc. are retained in the sea for a long period of time, marine fouling organisms such as seaweeds, barnacles, serpras, bryozoans, molluscs, etc. will not adhere to them. It is severely hindering the economical operation of these, and it is the current situation that a lot of labor and cost are required for their maintenance. Various studies and proposals have been made as measures against this, but it is known that a series of organotin 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 appearance of a low-pollution underwater antifouling agent that does not contain heavy metals is desired. For example, JP-B-51-10849 discloses an underwater antifouling paint containing a benzothiazole compound as an active ingredient.
No. 306, JP-A No. 63-284275 and Japanese Patent Publication No. 1-11606 disclose various anti-fouling agents for fishing nets and anti-fouling agents that combine a tetraalkyl thiuram disulfide compound with other underwater antifouling compounds. A coating composition and a fishing net antifouling solution are disclosed in JP-B-61-50984, and an anti-contamination agent for marine structures containing a 3-isothiazolone compound as an active ingredient is disclosed in JP-B-54-14610 and JP-A-54-410.
No. 15939 discloses an antibacterial agent and an underwater antifouling coating containing a pyrithione metal salt as an active ingredient, and JP-B No. 54-3889 and JP-A No. 54-78733 disclose 2,2′-dithiobis (pyridine-1). -Oxide) is disclosed as an antifouling active ingredient. However, all of these underwater antifouling agents have a weak effect of preventing adhesion to underwater fouling organisms, and therefore are strong against a wide variety of fouling organisms, and are practical practical underwater antifouling agents exhibiting a wide range of antifouling effects. Development is desired. On the other hand, JP-A-52-9376
Japanese Patent Publication No. 5 discloses that a 2,3-dichloro-N-benzylmaleimide compound is used as a fungicide for agriculture and horticulture. Further, JP-A-53-9320 discloses that N-arylmaleimide is used as an aquatic organism repellent.
It has been disclosed that -dichloro-N- (2,6-dialkylphenyl) maleimide compounds show an excellent anti-adhesion effect against a wide variety of adhering organisms in water. Is not effective against. Furthermore, Japanese Patent Publication No. 1-20665 discloses a few
-Dichloro-N-cyclohexylmaleimide and the like are disclosed as antifouling agents in water, but these compounds do not necessarily have sufficient antifouling effect, and further, they are said to have good formulation characteristics. I can not say.

[0004]

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.

[0005]

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 studies on a good antifouling agent in water, it was found that the N-benzyldichloromaleimide compound exhibits an excellent antifouling effect against aquatic fouling organisms, and further exhibits excellent formulation characteristics, and completes the present invention. Came to.

That is, the present invention provides (1) the general formula

[Chemical 9] (Wherein R ¹ and R ² are the same or different and each represents hydrogen, halogen, or an alkyl having 1 to 4 carbon atoms), and the underwater protection is characterized by containing an N-benzyldichloromaleimide compound. Fouling agent, (2) N of general formula [Chemical Formula 6]
-Benzyldichloromaleimide compound, (i) 2- (thiocyanomethylthio) benzothiazole, (ii) tetrachloroisophthalonitrile, (iii) general formula

[Chemical 10] 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) C2-C18 unsubstituted alkenyl or halo-substituted alkenyl, (d) C2-C18 unsubstituted alkynyl 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 aralkyl substituted with lower alkoxy, or (g) substituted with unsubstituted aryl or halogen, phenoxy, hydroxy, trihalomethyl, nitro, lower alkyl, lower alkoxy or lower alkoxycarbonyl whose total number of carbons in aryl does not exceed 10. The aryl is shown. ] One or more isothiazolone compounds represented by

[Chemical 11] (In the formula, R ³ represents alkyl having 1 to 4 carbon atoms, and p represents 1 or 2.)
(v) General formula

[Chemical 12] (In the formula, R ⁴ is an 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.) One or more water-insoluble dithiocarbamate represented by (vi)
General formula

[Chemical 13] (Wherein M ² represents a metal forming a water-insoluble metal salt of zinc, manganese, copper or nickel.) One or more water-insoluble dithiocarbamate salts represented by the formula (vii)

[Chemical 14] (In the formula, R ⁵ and R ⁶ are alkyl having 1 to 4 carbons,
² represents a metal forming a water-insoluble metal salt of zinc, manganese, copper or nickel. ) One or more water-insoluble dithiocarbamate salts represented by the formula (viii)

[Chemical 15] (Wherein M ¹ and n have the same meanings as defined above), and at least one water-insoluble pyrithione metal salt represented by the formula (ix) 2,2 ′.
-Dithiobis (pyridine-N-oxide) from (i) to (i
underwater antifouling agent characterized by containing as an active ingredient one or more compounds of the x) and (3) (a) the general formula ^{R 7 - (S) m-} R 7 ( wherein, R ⁷ carbon Represents a number 1 to 20 alkyl, m
Represents an integer of 2 to 10. 1) of the compounds represented by
1 or more, (b) 1 or more of polybutene having an average molecular weight of 200 to 1000, (c) 1 or more of paraffins, and (d) 1 of (a) to (d) selected from petrolatum.
The underwater antifouling agent as described in (1) or (2) above, which contains at least one species as an elution regulator.

The N-benzyldichloromaleimide compound of the present invention contains dichloromaleic anhydride and the corresponding benzylamine 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 non-polar 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 as a dehydration catalyst.
Examples thereof include hydrochloric acid, acetic acid, glacial acetic acid, p-toluenesulfonic acid and the like. The N-benzyldichloromaleimide compound of [Chemical Formula 9] of the present invention obtained by the above method is, for example, 2,3-dichloro-N-benzylmaleimide, 2,3-
Dichloro-N- (2-chlorobenzyl) maleimide,
2,3-dichloro-N- (4-chlorobenzyl) maleimide, 2,3-dichloro-N- (2-methylbenzyl)
Maleimide, 2,3-dichloro-N- (4-methylbenzyl) maleimide, 2,3-dichloro-N- (2,4-
Dimethylbenzyl) maleimide, 2,3-dichloro-N
-(3,4-Dimethylbenzyl) maleimide, 2,3-
Examples thereof include dichloro-N- (2,4-dichlorobenzyl) maleimide and 2,3-dichloro-N- (2,4,6-trimethylbenzyl) maleimide, but are not particularly limited thereto. The blending amount of the N-benzyldichloromaleimide compound of the present invention can be arbitrarily changed depending on the application subject of the underwater antifouling agent and the application environment and is not particularly limited, but is usually 3 to 30% by weight, preferably It is 5 to 20% by weight.

The compound represented by the chemical formula 10 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)
Examples thereof include -3-isothiazolone and 5-chloro-2- (3,4-dichlorophenyl) -3-isothiazolone, but are not particularly limited thereto. [Chemical 1
Examples of the compound represented by 1] include, but are not limited to, tetramethylthiuram disulfide, tetraethylthiuram disulfide, tetraisopropylthiuram disulfide, and tetra-n-butylthiuram disulfide.

The compound represented by [Chemical Formula 12] is, for example, bis (dimethyldithiocarbamate) zinc, tris (dimethyldithiocarbamate) iron, bis (dimethyldithiocarbamate) copper, bis (dimethyldithiocarbamate) nickel, bis ( Examples thereof include zinc diethyldithiocarbamate and zinc bis (dibutyldithiocarbamate), but are not particularly limited thereto.

Examples of the compound represented by [Chemical Formula 13] include zinc ethylenebisdithiocarbamate and manganese ethylenebisdithiocarbamate.
It is not particularly limited to these.

Examples of the compound represented by [Chemical Formula 14] include zinc bis (dimethyldithiocarbamoyl) ethylenebisdithiocarbamate, manganese bis (dimethyldithiocarbamoyl) ethylenebisdithiocarbamate, and the like. Not something.

The compound represented by [Chemical Formula 15] is, for example, pyrithione zinc (zinc pyrithione, ZPT),
Examples thereof include copper pyrithione, manganese pyrithione, iron pyrithione, and nickel pyrithione, but are not particularly limited thereto.

The N-benzyldichloromaleimide of [Chemical Formula 9] of the present invention, 2- (thiocyanomethylthio) benzothiazole, tetrachloroisophthalonitrile, [Chemical Formula 1]
0], one or more compounds of [Chemical formula 11], one or more compounds of [Chemical formula 12], [Chemical formula 13], or [Chemical formula 14]
One or more, one or more compounds of [Chemical Formula 15] and 2,2 ′
-The amount of one or more active ingredients of compounds selected from dithiobis (pyridine-N-oxide) used is 3 to 30% by weight, preferably 5 to 20% by weight, based on the total amount of the antifouling agent in water.
Is. 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 include 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-methylphenyl) -3-
Urea compounds such as phenylurea; 2-amino-3-chloro-1,4-naphthoquinone, 2,3-dichloro-1,4
-Quinone compounds such as naphthoquinone and 2,3-dicyano-1,4-dicyanoanthraquinone; phthalimide compounds such as N-trichloromethylthiotetrahydrophthalimide, N-trichloromethylthiophthalimide, N-fluorodichloromethylthiophthalimide; trichloromethylthiomethanesulfone -Anilide compounds such as p-chloroanilide; methylenebisthiocyanate,
Examples thereof include (iso) thiocyanate compounds such as ethylenebisthiocyanate, phenylisothiocyanate, benzylisothiocyanate, allylisothiocyanate, and 3,4-dichlorophenylisothiocyanate, but are not limited thereto.

Further, the compound represented by the general formula R ^7- (S) m-R ⁷ used as an elution regulator is, for example, diethyl pentasulfide, dipropyl tetrasulfide, ditertiary. Butyl disulfide, ditertiary butyl tetrasulfide, ditertiary amyl tetrasulfide, ditertiary nonyl pentasulfide, ditertiary dodecyl pentasulfide, dinonadecyl tetra Examples thereof include sulfid, but are not limited to these. It may also be a mixture thereof.

The 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, V-100, HV-
15, HV-35, HV-50, HV-100 and the like are mentioned, but the products are not particularly limited to these products, and a mixture thereof may be used.

Examples of the paraffins used as the elution regulator include liquid paraffin, paraffin wax, chlorinated paraffin, and the like, but are not particularly limited to these and a mixture thereof. Good.

Further, petrolatum used as an elution regulator includes white petrolatum and yellow petrolatum.

The general formula R ⁷ -used as a dissolution modifier
The amount of one or more dissolution regulators of the compound (S) m-R ⁷ selected from the group consisting of polybutene, paraffins and petrolatum is 3 to 20% by weight, preferably 5%, based on the total amount of the antifouling agent in water. 10 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, an antifouling agent for fishing nets includes N-benzyldichloromaleimide of [Chemical Formula 9] alone or N-benzyldichloromaleimide of [Chemical Formula 9], 2- (thiocyanomethylthio) benzothiazole, and a compound of [Chemical Formula 10]. 1 or more, tetrachloroisophthalonitrile, 1 or more of the compound of [Chemical formula 11], 1 of the compound of [Chemical formula 12], [Chemical formula 13], [Chemical formula 14]
One or more, one or more compounds of [Chemical Formula 15] and 2,2 ′
-One or more compounds selected from dithiobis (pyridine-N-oxide), represented by the general formula R ⁷
The resin may be added to at least one selected from the compound of (S) m-R ⁷ , polybutene, paraffins and petrolatum, and dissolved in a solvent. Resins used here, for example, rosin resin, acrylic resin, polybutene resin,
Examples thereof include a chlorinated rubber resin, a vinyl chloride resin, an alkyd resin, a coumarone resin, a polybutadiene resin, and an ethylene-vinyl acetate resin, and one or more of them may be used in combination. Further, as a solvent or a viscosity modifier,
Examples include xylene, solvent naphtha, pseudocumene, butanol, isopropyl alcohol, methyl isobutyl ketone, methyl ethyl ketone, acetone, butyl acetate, diethylbenzene, triethylbenzene, mesitylene, toluene, alkyl cellosolves (such as methyl cellosolve and ethyl cellosolve). When applied to the bottom of a ship, cuprous oxide, valve, talc, barium sulfate, tricresyl phosphate and the like can be further added to be used in the form of paint.

[0021]

The N-benzyl chloromaleimide compound of the present invention has a lower toxicity than conventional antifouling agents in water, and has a better solubility in a solvent such as xylene than known maleimide compounds, and it is a paint or a solution. In this state, the underwater antifouling composition can be easily put into practical use and has good workability.
Furthermore, the N-benzyldichloromaleimide compound or the underwater antifouling composition thereof of the present invention is applied to a fishing net for aquaculture or stationary, and materials used for these such as floats and ropes, as well as ship bottoms and underwater structures. By doing so, it exhibits an excellent effect in preventing adhesion of aquatic fouling organisms such as barnacles, magnolia, ascidians, ascidians, mussels, serpras, bryozoans, hydra, and other algae such as sea lettuce and aonomori, and has excellent long-term sustainability. Shows the antifouling effect of.

[0022]

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 1 2,3-Dichloromaleic anhydride 43 was placed in a four-necked flask equipped with a cooling tube equipped with a water separator, a thermometer and a stirrer.
4.1 g and 200 ml of toluene were charged, and 278.6 g of benzylamine was added dropwise at room temperature in about 30 minutes. Liquid temperature 1
The temperature was raised to 10 ° C., the produced water was removed by azeotropic distillation, and then toluene was concentrated and distilled off to obtain 651.0 g of crude crystals. 90
Recrystallized with% isopropyl alcohol, melting point 112-1
2,3-dichloro-N-benzylmaleimide 6 at 13 ° C
01 g was obtained as white crystals. Production Example 2 In the same apparatus as in Production Example 1, 447 g of 2,3-dichloromaleic anhydride and 750 ml of glacial acetic acid were charged, and 284.3 g of benzylamine was added dropwise under ice cooling in about 40 minutes. The liquid temperature was gradually raised to react at 100 ° C. for 2 hours. Liquid temperature after cooling down to 67 ° C
Seed crystals were put in and crystallized and cooled to 4 ° C. and filtered. 90%
Recrystallized with isopropyl alcohol, melting point 112-11
2,3-dichloro-N-benzylmaleimide 62 at 3 ° C
5.3 g was obtained as white crystals. Table 1 shows N-benzyldichloromaleimide compounds represented by the above [Chemical Formula 9] produced by the same method.

[0024]

[Table 1]

Example 1 According to the formulation example, the components were mixed and dissolved to prepare an antifouling agent for fishing nets. Formulation Example 1 Compound 1 15% Acrylic resin (50% xylene solution) 50% Xylene 35% Formulation example 2 Compound 2 15% Acrylic resin (50% xylene solution) 50% Rosin resin 3% Xylene 32% Formulation example 3 Compound 1 10 % Tetraethylthiuram disulfide 5% Ditertiary nonylpentasulfide 5% Acrylic resin (50% xylene solution) 48% Xylene 32% Formulation Example 4 Compound 3 5% Tetraethylthiuram disulfide 10% Rosin resin 40% Ditertiary Nonyl pentasulfide 5% Xylene 40% Formulation example 5 Compound 4 8% Tetraethylthiuram disulfide 7% Rosin resin 40% Ditertiary nonylpentasulfide 5% Xylene 40% Formulation example 6 Compound 5 7% Tetraethylthiuram disulfide 8% acrylic resin (50% Silen solution) 20% ditertiary nonylpentasulfide 5% rosin resin 20% xylene 40% Formulation example 7 compound 1 10% 2- (thiocyanomethylthio) benzothiazole 5% ditertiary nonylpentasulfide 5% Acrylic resin (50% xylene liquid) 40% Xylene 40% Formulation example 8 Compound 3 8% Tetrachloroisophthalonitrile 6% Ditertiary nonylpentasulfide 5% Acrylic resin (50% xylene liquid) 40% Pseudocumene 41% Formulation Example 9 Compound 1 5% Tetraethylthiuram disulfide 6% 4,5-Dichloro-2-n-octyl-3-isothiazolone 4% Ditertiary nonylpentasulfide 5% Acrylic resin (50% xylene solution ) 40% xylene 40% Formulation example 10 Compound 8 8% 2-thiocyanomethylthio Benzothiazole 6% 4,5-Dichloro-2-n-octyl-3-isothiazolone 6% Ditertiary nonylpentasulfide 5% Rosin resin 40% Xylene 35% Formulation Example 11 Compound 18% Bis (dimethyldithio) Carbamoyl) Ethylenebisdithio zinc carbamate 8% Ditertiary nonylpentasulfide 5% Liquid paraffin 5% Acrylic resin (50% xylene solution) 40% Xylene 34% Formulation example 12 Compound 1 8% Zinc pyrithione (ZPT) 8 % Polybutene (LV-50) 5% Vaseline 5% Acrylic resin (50% xylene solution) 40% Xylene 34% Formulation Example 13 Compound 1 15% Acrylic resin (50% xylene solution) 40% Ditertiary nonylpentasulfite Do 5% Liquid paraffin (reagent) 5% Xylene 35% Formula 14 Compound 1 8% Tetraethyl thiuram disulfide 8% Acrylic resin (50% xylene solution) 40% Ditertiary nonylpentasulfide 5% Liquid paraffin (reagent) 5% Xylene 34% Formulation example 15 Compound 18 % Tetraethyl thiuram disulfide 8% Acrylic resin (50% xylene solution) 40% Polybutene (LV-50) 5% Vaseline 5% Xylene 34% Formulation Example 16 Compound 2 8% 2- (Thiocyanomethylthio) benzothiazole 8 % Acrylic resin (50% xylene solution) 40% Ditertiary nonylpentasulfide 5% Liquid paraffin (reagent) 5% Xylene 34% Formulation example 17 Compound 4 6% Tetrachloroisophthalonitrile 6% Acrylic resin (50 % Xylene solution) 22% Ditertiary nonyl pentasulfide 5% Vaseline 5% Pseudocumene 22% Solvent K-73 34% Formulation Example 18 Compound 5 8% 4,5-Dichloro-2-n-octyl-3-isothiazolone 5% Tetraethylthiuram disulfide 5% Acrylic resin (50% xylene Liquid) 40% Ditertiary nonylpentasulfide 5% Polybutene (LV-10) 5% Xylene 32% Formulation Example 19 Compound 38 8% Bis (dimethyldithiocarbamoyl) ethylenebisdithio zinc carbamate 8% Acrylic resin ( 50% xylene liquid) 40% polybutene (HV-35) 5% liquid paraffin (reagent) 5% xylene 34% Formulation example 20 Compound 6 8% Zinc pyrithione (ZPT) 8% Acrylic resin (50% xylene liquid) 40% Di-daily Tertiary nonyl pentasulfide 5% Vaseline 5% Xylene 34% Formulation Example 21 Compound 8 8% 2,2-dithiobis (pyridine-N-oxide) 8% Acrylic resin (50% xylene solution) 40% Polybutene (LV-50) 5% Liquid paraffin (reagent) 5% Xylene 34 %

Example 2 A ship bottom antifouling paint was prepared by crushing and kneading with a ball mill according to the formulation example. Formulation Example 22 Compound 1 15% Tetramethylthiuram disulfide 15% Rouge 15% Talc 3% Barium sulfate 5% Rosin resin 11% Chlorinated rubber resin 5% Tricresyl phosphate 3% Xylene 28% Formulation example 23 Compound 6 10% Tetra Methyl thiuram disulfide 20% Rouge 13% Talc 3% Barium sulfate 5% Rosin resin 13% Chrominated rubber resin 5% Tricresyl phosphate 3% Xylene 28% Formulation example 24 Compound 7 20% Tetraethylthiuram disulfide 10% Cuprous oxide 15 % Rouge 5% Talc 10% Barium sulfate 5% Rosin resin 11% Chrominated rubber resin 5% Tricresyl phosphate 3% Xylene 16% Formulation 25 Compound 8 30% Cuprous oxide 20% Rouge 7% Talc 5% Sulfuric acid Barium 5% Rosin resin 11% Rubber resin 5% tricresyl phosphate 3% xylene 14% Formulation example 26 compound 1 15% 2- (thiocyanomethylthio) benzothiazole 15% rouge 15% talc 3% barium sulfate 5% rosin resin 11% chloride rubber resin 5% tricresyl phosphate 3% xylene 28% Formulation example 27 Compound 1 15% Tetrachloroisophthalonitrile 15% Rouge 15% Talc 3% Barium sulfate 5% Rosin resin 11% Chlorinated rubber resin 5% Tricresyl phosphate 3 % Xylene 28% Formulation Example 28 Compound 6 15% 2- (thiocyanomethylthio) benzothiazole 10% 4,5-dichloro-2-n-octyl-3-isothiazolone 10% Cuprous oxide 15% Rouge 5% Talc 10 % Barium sulfate 5% Rosin resin 11% Chlorinated rubber resin 5 % Tricresyl phosphate 3% Xylene 11% Formulation example 29 Compound 4 15% Tetraethyl thiuram disulfide 15% 4,5-Dichloro-2-n-octyl-3-isothiazolone 10% Rouge 13% Talc 3% Barium sulfate 5% Rosin Resin 13% Chlorinated Rubber Resin 5% Tricresyl Phosphate 3% Xylene 18% Formulation Example 30 Compound 1 15% Tetramethylthiuram Disulfide 15% Rouge 15% Talc 3% Barium Sulfate 5% Rosin Resin 11% Chloride Rubber resin 5% Ditertiary nonylpentasulfide 3% Liquid paraffin (reagent) 3% Xylene 25% Formulation example 31 Compound 3 15% Tetrachloroisophthalylonitrile 15% Rouge 15% Talc 3% Barium sulfate 5 % Rosin resin 11% Chlorinated rubber resin 5% Polybutene HV-35) 3% Vaseline 3% Xylene 25% Formulation Example 32 Compound 5 15% 4,5-Dichloro-2-n-octyl-3-isothiazolone 10% Zinc pyrithione (ZPT) 10% Rox 15% Talc 3% Sulfate Barium 5% Rosin resin 11% Chlorinated rubber resin 5% Ditertiary nonylpentasulfide 3% Polybutene (LV-10) 3% Xylene 20% Formulation example 33 Compound 7 15% 2- (Thiocyanomethylthio) benzothiazole 15% Bengal 15% Talc 3% Barium sulfate 5% Rosin resin 11% Chlorinated rubber resin 5% Di-tertiary nonylpentasulfide 3% Vaseline 3% Xylene 25% Formulation example 34 Compound 1 15% Bis (dimethyldithio) Carbamoyl) ethylenebisdithio zinc carbamate 15% Rouge 15% Talc 3% Barium sulfate 5% Rosin resin 11% Polybutene (LV-50) 3% Liquid paraffin (reagent) 3% Xylene 30% Formulation example 35 Compound 4 15% 2,2-Dithiobis (pyridine-N-oxide) 15% Rouge 15 % Talc 3% Barium sulfate 5% Rosin resin 11% Polybutene (LV-50) 3% Liquid paraffin (reagent) 3% Xylene 30% Formulation Example 36 Compound 1 15% Cuprous oxide 15% Rouge 15% Talc 3% Sulfate Barium 5% Rosin resin 11% Polybutene (LV-50) 3% Liquid paraffin (reagent) 3% Xylene 30%

[0027]

【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 2.

[0028]

[Table 2]

The comparative formulation is as follows. Comparative Example 1 Tetraethylthiuram disulfide 15% Acrylic resin (50% xylene solution) 50% Xylene 35% The results are shown in Table 3.

[0030]

[Table 3]

As shown in Table 3, N-benzyldichloromaleimide of the present invention alone and N-benzyldichloromaleimide [Chemical Formula 10], [Chemical Formula 11], [Chemical Formula 14],
A fishing net containing one or more compounds represented by [Chemical Formula 15], 2- (thiocyanomethylthio) benzothiazole, tetrachloroisophthalonitrile and 2,2′-dithiobis (pyridine-N-oxide) as active ingredients. It has been revealed that the antifouling agent can provide a long-lasting and practical effect, a highly safe antifouling agent with low toxicity and good storage stability.

Experiment 2 The ship bottom antifouling paint of Example 2 of the present invention was uniformly 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 4. The numbers in the table represent the fouling organism attached area percentage.

[0033]

[Table 4]

As shown in Table 4, N-benzyldichloromaleimide of the present invention alone and N-benzyldichloromaleimide with [Chemical Formula 10], [Chemical Formula 11], [Chemical Formula 14],
A ship bottom containing one or more compounds represented by [Chemical Formula 15], 2- (thiocyanomethylthio) benzothiazole, tetrachloroisophthalonitrile and 2,2'-dithiobis (pyridine-N-oxide) as active ingredients. It has been found that the antifouling paint can provide a highly effective antifouling agent having a long-term practical effect and low toxicity.

 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Naoki Kumagai, 955, Shoji, Yoshitomi-cho, Tsukigami-gun, Fukuoka Prefecture Central Research Laboratory, Yoshitomi Pharmaceutical Co., Ltd.

Claims (3)

[Claims] 1. A general formula: (Wherein R ¹ and R ² are the same or different and each represents hydrogen, halogen, or an alkyl having 1 to 4 carbon atoms), and the underwater protection is characterized by containing an N-benzyldichloromaleimide compound. Dirt. 2. A general formula: (In the formula, R ¹ and R ² are the same or different and each represents hydrogen, halogen or alkyl having 1 to 4 carbon atoms.), And (i) 2
(Thiocyanomethylthio) benzothiazole, (ii) tetrachloroisophthalonitrile, (iii) general formula: 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) C2-C18 unsubstituted alkenyl or halo-substituted alkenyl, (d) C2-C18 unsubstituted alkynyl 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 aralkyl substituted with lower alkoxy, or (g) substituted with unsubstituted aryl or halogen, phenoxy, hydroxy, trihalomethyl, nitro, lower alkyl, lower alkoxy or lower alkoxycarbonyl whose total number of carbons in aryl does not exceed 10. The aryl is shown. ] One or more isothiazolone compounds represented by the formula (iv) (In the formula, R ³ represents alkyl having 1 to 4 carbon atoms, and p represents 1 or 2.)
(v) General formula (In the formula, R ⁴ is an 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.) One or more water-insoluble dithiocarbamate represented by (vi)
General formula: (Wherein M ² represents a metal that forms a water-insoluble metal salt of zinc, manganese, copper, or nickel), and one or more water-insoluble dithiocarbamate salts represented by the formula (vii) (In the formula, R ⁵ and R ⁶ are alkyl having 1 to 4 carbons,
² represents a metal forming a water-insoluble metal salt of zinc, manganese, copper or nickel. ), One or more water-insoluble dithiocarbamate salt represented by the formula (viii). (Wherein M ¹ and n have the same meanings as defined above), and one or more water-insoluble pyrithione metal salts represented by the formula (ix) 2,2 ′.
-Dithiobis (pyridine-N-oxide) from (i) to (i
An underwater antifouling agent comprising one or more compounds of x) as an active ingredient. (A) General formula R ^7- (S) m-R ⁷ (wherein, R ⁷ represents alkyl having 1 to 20 carbon atoms, m
Represents an integer of 2 to 10. 1) of the compounds represented by
1 or more, (b) 1 or more of polybutene having an average molecular weight of 200 to 1000, (c) 1 or more of paraffins, and (d) 1 of (a) to (d) selected from petrolatum.
The underwater antifouling agent according to claim (1) or (2), which contains at least one species as an elution regulator.