JPH06340504A - Underwater antifouling agent - Google Patents

Abstract

PURPOSE:To obtain the subject composition having low pollution, preventing adhesion of aquatic staining organisms on fishing nets, floats, ropes, the bottom of ships, underwater structures, etc., comprising a hydroxybenzoic ester compound or further a specific compound as active ingredients. CONSTITUTION:An underwater antifouling agent comprises a hydroxybenzoic ester compound of formula I (R<1> and R<2> are H, halogen or alkyl; R is alkyl, aryl or aralkyl) (e.g. methyl 4-hydroxybenzoate) as active ingredient. Or an underwater antifouling agent comprises the compound of formula I and a compound selected from (i) 2-(thiocyanomethylthio)benzothiazole, (ii) tetrachloroisophthalonitrile, (iii) a compound of formula II (X<1> and X<2> are H or halogen; R<3> is alkyl, cycloalkyl, etc.), (iv) a compound of formula III (R<9> is alkyl), (v) an isothiazolone compound of formula TV (X<3> and X<4> are H, halogen or alkyl; Y is alkyl, etc.), (vi) an insoluble metal salt of dithiocarbamate of formula V, formula VI or formula VII (R<10> to R<12> are alkyl; (n) is 2 or 3; M is Zn, etc.), (vii) a water-insoluble pyrithione metal salt of formula VIII and (viii) 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 hydroxybenzoic acid ester compound, which is useful as an antifouling component of a low-pollution underwater antifouling composition containing no heavy metal such as organic tin.

[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 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 operator, and are disadvantageous in terms of environmental measures.
Cuprous oxide is dissolved in seawater and remains as copper ions or copper compounds, which may adversely affect the environment.Because it does not dissolve in solvents, it is practical as a fishing net antifouling agent and has good workability. It has drawbacks such as difficulty in obtaining a good formulation.

For these reasons, the advent of a low-pollution underwater antifouling agent that does not contain heavy metals such as organic tin is desired. For example, Japanese Patent Publication No. 51-10849 discloses an underwater antifouling paint containing a benzothiazole compound as an active ingredient, and Japanese Patent Publication No. 60-38306, Japanese Patent Publication No. 63-284275, and Japanese Patent Publication No. 1-11606. Are various anti-fouling agents for fishing nets, anti-fouling paint compositions, and fishing net anti-fouling solutions in which a tetraalkyl thiuram disulfide compound and other underwater antifouling compound are combined, and JP-B-61-50984 discloses An anti-contaminant for marine constructs containing a 3-isothiazolone compound as an active ingredient is disclosed in Japanese Patent Publication No. 54-14610.
Japanese Patent Application Laid-Open No. 54-15939 discloses an antibacterial agent and an underwater antifouling paint containing a pyrithione metal salt as an active ingredient.
3889 and JP-A-54-78733 disclose underwater antifouling paints containing 2,2'-dithiobis (pyridine-1-oxide) as an antifouling active ingredient. However, all of these underwater antifouling agents have a weak effect of preventing adhesion to aquatic fouling organisms, and therefore are strong against a wide variety of fouling organisms, and are practical pesticides that exhibit a wide range of antifouling effects. Development is desired. Further, JP-A-52-93765 discloses 2,3-dichloro-N-
It is disclosed that a benzylmaleimide compound is used as an agricultural and horticultural fungicide. JP-A-53-9320
JP-A-2-24242 discloses that N-arylmaleimide is used as an aquatic repellent.
The publication 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 Examined Patent Publication 1-20665
In the publication, 2,3-dichloro-N-cyclohexylmaleimide and the like are disclosed as antifouling agents in water, but these compounds do not always have a sufficient antifouling effect, and further, good formulation characteristics. You can't say that you have. On the other hand, hydroxybenzoic acid esters are disclosed in Japanese Patent Publication No.
It is known as a plasticizer for polyamide resin in JP-A-1-10025 and as a developer for pressure-sensitive paper in JP-B-50-16969. Further, hydroxybenzoic acid lower alkyl esters are well known as preservatives for cosmetics and pharmaceuticals.

[0004]

DISCLOSURE OF THE INVENTION The present invention provides a practical underwater antifouling agent which does not contain heavy metals such as organic tin and has a low pollution property and an excellent antifouling effect against a wide variety of attached organisms. The purpose is to provide.

[0005]

DISCLOSURE OF THE INVENTION The present inventors, except for the above-mentioned drawbacks of conventional underwater antifouling agents, do not contain heavy metals such as organotin, which are low in toxicity and less likely to cause environmental pollution, and are safe. As a result of earnest research on an underwater antifouling agent having high workability, it has been shown that a certain hydroxybenzoic acid ester compound has an excellent antifouling effect against aquatic fouling organisms, and further has excellent formulation properties. They have found the present invention and completed the present invention.

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

[Chemical 12] (In the formula, R ¹ and R ² are the same or different and each represents hydrogen, halogen, or alkyl having 1 to 4 carbons, and R is 1 to 1 carbons.
Up to 22 linear or branched alkyl, aryl, aralkyl are indicated. ) An underwater antifouling agent containing a hydroxybenzoic acid ester compound represented by
(2) A hydroxybenzoic acid ester compound represented by the general formula [Chemical Formula 12], (i) 2- (thiocyanomethylthio) benzothiazole, (ii) tetrachloroisophthalonitrile, (ii)
i) general formula

[Chemical 13] [Wherein, X ¹ and X ² are the same or different and each represents hydrogen or halogen, R ³ is linear or branched alkyl, cycloalkyl and the following groups (a) and (b))

[Chemical 14]

[Chemical 15] (However, R ⁴ , R ⁵ , and R ⁶ are the same or different and are hydrogen,
Halogen and alkyl, R ⁷ and R ⁸ are the same or different and each is hydrogen or alkyl, and p is 1 or 2. )] One or more maleimide compounds represented by the formula (iv)

[Chemical 16] (Wherein R ⁹ represents alkyl having 1 to 4 carbon atoms), one or more compounds represented by the formula (v)

[Chemical 17] Wherein, X ³ and X ⁴ are the same or different and represent a hydrogen, halogen or alkyl of 1 to 4 carbon atoms (provided that at least one of X ³ and X ⁴ is a halogen, more X ³ and X ^When one of ⁴ is other than halogen, the solubility of the compound measured by UV method is 0.5-50.
Y is (a) unsubstituted alkyl having 1 to 18 carbon atoms, (b) at least one hydrogen is halogen,
Substituted alkyl substituted by hydroxy, cyano, alkylamino, dialkylamino, phenylamino, halophenylamino, carboxy, alkoxycarbonyl, alkoxy, aryloxy, morpholino, piperidino, pyrrolidonyl, carbamoyloxy or isothiazolonyl, provided that Does not exceed 18), (c) C2-C18 unsubstituted alkenyl or halo-substituted alkenyl, (d) C2-C18 unsubstituted alkynyl or halo-substituted alkynyl, (e ) Unsubstituted cycloalkyl or alkyl-substituted cycloalkyl having a hydrocarbon ring having 3 to 6 carbon atoms and having a total carbon number of 12 or less, and (f) the total number of carbon atoms in aralkyl does not exceed 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

[Chemical 18]

[Chemical 19]

[Chemical 20] (In the formula, R ¹⁰ , R ¹¹ , and R ¹² each represent an alkyl having 1 to 4 carbon atoms, n represents 2 or 3, and M ¹ represents a water-insoluble metal salt of zinc, manganese, copper, iron, or nickel. Represents a metal to be formed, and M ² represents a metal forming a water-insoluble metal salt excluding iron in M ¹ ), one or more insoluble dithiocarbamate metal compounds represented by the formula (vii)

[Chemical 21] (In the formula, M ¹ and n have the same meanings as described above), one or more water-insoluble pyrithione metal salts represented by the formula (viii) 2,
(3) An underwater antifouling agent, which comprises, as an active ingredient, one or more compounds (i) to (viii) selected from 2'-dithiobis (pyridine-N-oxide).
(A) the general formula ^{R 13 - (S) m-} R 13 ( wherein, R ¹³ represents from 1 to 20 alkyl carbon atoms, m
Represents an integer of 2 to 10. 1) of the compounds represented by
Or more, (b) one or more polybutenes having an average molecular weight of 200 to 1,000, (c) one or more paraffins, and (d) one or more selected from (a) to (d) selected from petrolatum. It relates to the underwater antifouling agent as described in (1) or (2) above, which is contained as a regulator.

The hydroxybenzoic acid ester compound of [Chemical Formula 12] of the present invention includes, for example, methyl 4-hydroxybenzoate, ethyl 4-hydroxybenzoate, butyl 4-hydroxybenzoate and octyl 4-hydroxybenzoate.
Nonyl 4-hydroxybenzoate, lauryl 4-hydroxybenzoate, myristyl 4-hydroxybenzoate, 4-
Stearyl hydroxybenzoate, docosyl 4-hydroxybenzoate, methyl 4-hydroxy-3,5-di-tert-butylbenzoate, methyl 3-chloro-4-hydroxybenzoate, 3,5-dichloro-4-hydroxybenzoic acid. Methyl acid, methyl 2-hydroxybenzoate, ethyl 2-hydroxybenzoate, butyl 2-hydroxybenzoate, 2-
Octyl hydroxybenzoate, methyl 2-hydroxy-5-tert-butyl benzoate, 2-hydroxy-3,5-
Methyl ditertiary butyl benzoate, 5-chloro-2-hydroxy-3-methyl tertiary butyl benzoate, methyl 5-chloro-2-hydroxybenzoate, 3,5-dichloro-
Methyl 2-hydroxybenzoate, 3,5-dibromo-2
Examples include, but are not limited to, methyl hydroxybenzoate and the like. The blending amount of the hydroxybenzoic acid ester 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 usually 3 to 30% by weight, preferably 5 Is about 20% by weight.

The compound represented by the chemical formula 13 is, for example, N-octylmaleimide, N-cyclohexylmaleimide, N-phenylmaleimide, N-benzylmaleimide, N- (1-phenylethyl) maleimide, N-
(2-Phenylethyl) maleimide, 2,3-dichloro-N-butylmaleimide, 2,3-dichloro-N-octylmaleimide, 2,3-dichloro-N-cyclohexylmaleimide, 2,3-dichloro-N -Phenylmaleimide, 2,3-dichloro-N- (2,6-dimethylphenyl) maleimide, 2,3-dichloro-N- (2-ethyl-6-methylphenyl) maleimide, 2,3-dichloro-N- (2,6-dichlorophenyl) maleimide,
2,3-dichloro-N-benzylmaleimide, 2,3-
Dichloro-N- (1-phenylethyl) maleimide,
2,3-dichloro-N- (2-phenylethyl) maleimide, 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-methylbenzyl) maleimide, 2,3-dichloro-N- (2,4-dichlorobenzyl) maleimide, 2,3-dichloro-N- (2,4,6)
-Trimethylbenzyl) maleimide and the like, but not limited thereto.

The compound represented by [Chemical Formula 16] includes, for example, tetramethylthiuram disulfide, tetraethylthiuram disulfide, tetraisopropylthiuram disulfide, tetra-n-butylthiuram disulfide and the like, but is not limited thereto. is not.

The compound represented by [Chemical Formula 17] 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.

Examples of the compound represented by [Chemical Formula 18] include zinc bis (dimethyldithiocarbamate), iron tris (dimethyldithiocarbamate), copper bis (dimethyldithiocarbamate), nickel bis (dimethyldithiocarbamate), and bis ( Examples thereof include zinc diethyldithiocarbamate and zinc bis (dibutyldithiocarbamate), but are not particularly limited thereto.

Examples of the compound represented by [Chemical Formula 19] include zinc ethylenebisdithiocarbamate and manganese ethylenebisdithiocarbamate.
It is not particularly limited to these.

The compound represented by [Chemical Formula 20] includes, for example, zinc bis (dimethyldithiocarbamoyl) ethylenebisdithiocarbamate, manganese bis (dimethyldithiocarbamoyl) ethylenebisdithiocarbamate, and the like. Not something.

The compound represented by [Chemical Formula 21] is, for example, zinc pyrithione (zinc pyrithione, ZPT),
Examples thereof include copper pyrithione, manganese pyrithione, iron pyrithione, nickel pyrithione, and the like, but are not particularly limited thereto.

The hydroxybenzoic acid ester compound of [Chemical Formula 12] of the present invention, one or more compounds of [Chemical Formula 13], 2- (thiocyanomethylthio) benzothiazole, tetrachloroisophthalonitrile, and [Chemical Formula 16]. One or more compounds, one or more compounds of [Chemical Formula 17], [Chemical Formula 18],
One or more compounds of [Chemical Formula 19] and [Chemical Formula 20];
1] In an underwater antifouling agent containing one or more compounds and one or more compounds selected from 2,2′-dithiobis (pyridine-N-oxide), the amount of the active ingredient used is 3 to 40% by weight. %, Preferably 10 to 30% by weight
Is. Further, the mixing ratio of each of the active ingredients can be arbitrarily changed depending on the conditions of the required antifouling performance and use environment. 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- (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-
Triazine-based compounds such as methylthio-4-ethylamino-6-isopropylamino-s-triazine; 3-
(3,4-Dichlorophenyl) -1,1-dimethylurea, 3- (3,4-dichlorophenyl) -1-methoxy-1-methylurea, 1- (2-methylcyclophenyl)
Urea-based compounds such as 3-phenylurea; 2-amino-
3-chloro-1,4-naphthoquinone, 2,3-dichloro-1,4-naphthoquinone, 2,3-dicyano-1,4-
Quinone compounds such as dicyanoanthraquinone; phthalimide compounds such as N-trichloromethylthiotetrahydrophthalimide, N-trichloromethylthiophthalimide, N-fluorodichloromethylthiophthalimide; anilide compounds such as trichloromethylthiomethanesulfone-p-chloroanilide; methylenebis Examples thereof include (iso) thiocyanate compounds such as thiocyanate, ethylenebisthiocyanate, phenylisothiocyanate, benzylisothiocyanate, allylisothiocyanate, and 3,4-dichlorophenylisothiocyanate, but are not particularly limited thereto.

The compound represented by the general formula R ^13- (S) m-R ¹³ used as an elution regulator is, for example, diethyl pentasulfide, dipropyl pentasulfide, 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, LV-100, HV
-15, HV-35, HV-50, HV-100 and the like are mentioned, but not limited to these products. It may also be a mixture thereof.

The paraffins used as the dissolution modifier include, for example, liquid paraffin, paraffin wax, chlorinated paraffin, etc., but are not particularly limited thereto. It may also be a mixture thereof.

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

The general formula R ¹³ used as a dissolution modifier
-(S) m-R ¹³ compound, polybutene, a compound selected from paraffins and petrolatum, and the amount of one or more dissolution regulators used is 3 to 20% by weight, preferably 3 to 20% by weight, based on the total amount of the antifouling agent in water. It is 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, an antifouling agent for fishing nets may be a hydroxybenzoic acid ester compound of [Chemical Formula 12] alone or a hydroxybenzoic acid ester compound of [Chemical Formula 12] and 2- (thiocyanomethylthio).
Benzothiazole, tetrachloroisophthalonitrile,
One or more compounds of [Chemical Formula 13], one or more compounds of [Chemical Formula 16], one or more compounds of [Chemical Formula 17], compounds of [Chemical Formula 18], [Chemical Formula 19], and [Chemical Formula 20] One or more of
One or more compounds of [Chemical Formula 21] and 2,2′-dithiobis (pyridine-N-oxide), as an elution regulator,
The resin may be added to at least one selected from the compound of the general formula R ^13- (S) m-R ¹³ , polybutene, paraffins and petrolatum, and dissolved or mixed and dispersed in a solvent. Examples of the resin used here include rosin resin, acrylic resin, polybutene resin, chlorinated rubber resin,
Examples thereof include vinyl chloride resin, alkyd resin, coumarone resin, polybutadiene resin, and ethylene-vinyl acetate resin, and one or more of them may be used in combination.
Further, as the solvent or viscosity modifier, xylene, solvent naphtha, pseudocumene, butanol, isopropyl alcohol, methyl isobutyl ketone, methyl ethyl ketone, acetone, butyl acetate, diethylbenzene,
Examples thereof include triethylbenzene, mesitylene, toluene, alkyl cellosolve (methyl cellosolve, ethyl cellosolve, etc.). When it is used on the bottom of a ship, cuprous oxide, rouge, talc, barium sulfate, tricresyl phosphate and the like may be further added to be used in the form of paint.

[0023]

The hydroxybenzoic acid ester compound of the present invention has low toxicity and high safety as compared with conventional antifouling agents in water, and has good solubility in a solvent such as xylene. The underwater antifouling agent composition can be practical and has good workability. Furthermore, the hydroxybenzoic acid ester compound of the present invention or its underwater antifouling composition should be applied to fishing nets for aquaculture or stationary, and materials used for these such as floats and ropes, as well as ship bottoms and underwater structures. Shows outstanding effects in preventing the attachment of aquatic fouling organisms such as barnacles, maggots, ascidians, mussels, serpras, bryozoans, and hydra, and algae such as sea lettuce and aonori. Shows a dirty effect.

[0024]

EXAMPLES Examples will be shown below, but the present invention is not limited thereto. In addition, the compounding in an Example shows weight%.

Example 1 According to the following formulation example, the components were mixed and dissolved or mixed and dispersed to prepare an antifouling agent for fishing nets. Formulation Example 1 Lauryl 4-hydroxybenzoate 15% Acrylic resin (50% xylene solution) 40% Polybutene (LV-50) 5% Vaseline 5% Xylene 35% Formulation example 2 Lauryl 4-hydroxybenzoate 8% 2,3- Dichloro-N-benzylmaleimide 8% Acrylic resin (50% xylene solution) 40% Ditertiary nonylpentasulfide 5% Liquid paraffin (reagent) 5% Xylene 34% Formulation example 3 Lauryl 4-hydroxybenzoate 8% Tetraethyl thiuram disulfide 8% Acrylic resin (50% xylene solution) 40% Polybutene (LV-50) 5% Vaseline 5% Xylene 34% Formulation example 4 Octyl 4-hydroxybenzoate 8% 2- (Thiocyanomethylthio) benzothiazole 8 % Acrylic resin (50% xylene solution) 40% Di Tertiary nonyl pentasulfide 5% Liquid paraffin (reagent) 5% Xylene 34% Formulation example 5 Stearyl 4-hydroxybenzoate 6% Tetrachloroisophthalonitrile 6% Acrylic resin (50% xylene liquid) 22% Di3rd Grade Nonylpentasulfide 5% Vaseline 5% Pseudocumene 20% Solvent K-73 36% Formulation Example 6 Methyl 2-hydroxybenzoate 8% 4,5-Dichloro-2-n-octyl-3-isothiazolone 5% Tetraethylthiuram Disulfide 5% Acrylic resin (50% xylene solution) 40% Ditertiary nonylpentasulfide 5% Polybutene (LV-10) 5% Xylene 32% Formulation example 7 5-Chloro-2-hydroxy-3-third Grade butyl benzoate methyl 8% bis (dimethyldithiocarbamoyl) ethyl Zinc bisdithio zinc carbamate 8% Acrylic resin (50% xylene solution) 40% Polybutene (HV-35) 5% Liquid paraffin (reagent) 5% Xylene 34% Formulation example 8 4-Hydroxy-3,5-ditertiary butyl Methyl benzoate 8% Zinc pyrithione (ZPT) 8% Acrylic resin (50% xylene solution) 40% Ditertiary nonylpentasulfide 5% Vaseline 5% Xylene 34% Formulation example 9 Lauryl 4-hydroxybenzoate 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 An antifouling paint for ship bottom was pulverized and kneaded in a ball mill according to the following formulation example to prepare. Formulation Example 10 Lauryl 4-hydroxybenzoate 15% Tetramethylthiuram disulfide 15% Rouge 15% Talc 3% Barium sulfate 5% Rosin resin 11% Chlorinated rubber resin 5% Ditertiary nonylpentasulfide 3% Liquid paraffin (Reagent) 3% Xylene 25% Formulation Example 11 Octyl 4-hydroxybenzoate 15% Tetrachloroisophthalonitrile 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 12 Methyl 3,5-dichloro-4-hydroxybenzoate 10% 4,5-Dichloro-2-n-octyl-3-isothiazolone 10% Zinc pyrithione (ZPT) 10% Rouge 15% Talc 3% Barium sulfate 5% Rosin tree Fat 11% Chlorinated rubber resin 5% Ditertiary nonylpentasulfide 3% Polybutene (LV-10) 3% Xylene 25% Formulation example 13 3,5-Dichloro-2-hydroxybenzoate methyl 15% 2- ( Thiocyanomethylthio) benzothiazole 15% Rouge 15% Talc 3% Barium sulfate 5% Rosin resin 11% Chlorinated rubber resin 5% Ditertiary nonylpentasulfide 3% Vaseline 3% Xylene 25% Prescription example 14 4- Lauryl hydroxybenzoate 15% Bis (dimethyldithiocarbamoyl) ethylenebisdithiocarbamate zinc 15% Rouge 15% Talc 3% Barium sulfate 5% Rosin resin 11% Polybutene (LV-50) 3% Liquid paraffin (reagent) 3% Xylene 30% Formulation Example 15 3,5-dibromo-2-hydroxybenzox Methyl acid 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 16 Lauryl 4-hydroxybenzoate 30% Rouge 15% Talc 3% Barium sulfate 5% Rosin resin 11% Polybutene (LV-50) 3% Liquid paraffin (reagent) 3% Xylene 30% Formulation example 174 -Lauryl hydroxybenzoate 15% 2,3-dichloro-N-benzylmaleimide 15% Rouge 15% Talc 3% Barium sulfate 5% Rosin resin 11% Polybutene (LV-50) 3% Liquid paraffin (reagent) 3% Xylene 30%

[0027]

EFFECT OF THE INVENTION Experiment 1 The antifouling agents for fishing nets of Example 1 of the present invention were respectively applied by dip coating to a polyethylene knotless net (section 6, 400 denier / 60 pieces), air-dried, and then April 1992. The water was kept in the sea about 50 cm below the sea level in Kii Tanabe Bay, Wakayama Prefecture, and the state of attachment of fouling organisms to the net was investigated. The results were evaluated according to the criteria shown in Table 1.

[0028]

[Table 1] 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 2.

[Table 2] As described above, as shown in Table 2, the hydroxybenzoic acid ester compound of the present invention alone or the hydroxybenzoic acid ester compound and 2- (thiocyanomethylthio) benzothiazole, tetrachloroisophthalonitrile, [Chemical Formula 1
3], [Chemical 16], [Chemical 17], [Chemical 20], [Chemical 2
[1] A fishing net antifouling agent containing at least one compound represented by the formula [1] and 2,2′-dithiobis (pyridine-N-oxide) as an active ingredient exhibits a sustainable and practical effect and has low toxicity. It was found that an antifouling agent having high safety and good storage stability can be provided.

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 to which an anticorrosive paint had been applied in advance and air dried. The obtained test steel sheets were kept in the sea at a depth of 1.5 m in Kitabewan, Wakayama Prefecture for one year from March 1992, and the state of adhesion of fouling organisms was investigated every two months for each test steel sheet. Comparative Example 2 Cuprous oxide 40% Rouge 8% Talc 5% Rosin 10% Chlorinated rubber 6% Tricresyl phosphate 3% Xylene 28% The results are shown in Table 3. The numbers in the table represent the area of fouling organism attachment area.

[0030]

[Table 3] As described above, as shown in Table 3, the hydroxybenzoic acid ester compound of the present invention alone or the hydroxybenzoic acid ester compound and 2- (thiocyanomethylthio) benzothiazole, tetrachloroisophthalonitrile, [Chemical Formula 1
3], [Chemical 16], [Chemical 17], [Chemical 20], [Chemical 2
[1] A bottom antifouling paint containing one or more compounds represented by 1] and 2,2′-dithiobis (pyridine-N-oxide) as an active ingredient shows a sustainable and practical effect, and
It was found that a highly safe antifouling agent with low toxicity can be provided.

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁵ Identification code Internal reference number FI Technical display area A01N 43/80 102 9159-4H 47/14 A 9159-4H B 9159-4H 55/02 Z 9159- 4H (72) Inventor Toshihiro Usu Address: 955, Shoji, Yoshitomi-cho, Tsukigami-gun, Fukuoka Prefecture Yoshitomi Pharmaceutical Co., Ltd. Chemicals Research Laboratory

Claims (3)

[Claims] 1. 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 carbons, and R is 1 to 1 carbons.
22 straight chain or branched alkyl, aryl and aralkyl are shown. ) An underwater antifouling agent comprising a hydroxybenzoic acid ester compound represented by 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 carbons, and R is 1 to 1 carbons.
22 straight chain or branched alkyl, aryl and aralkyl are shown. ), A hydroxybenzoic acid ester compound, (i) 2- (thiocyanomethylthio) benzothiazole, (ii) tetrachloroisophthalonitrile, (i)
ii) General formula: [Wherein X ¹ and X ² are the same or different and each represents hydrogen or halogen, R ³ is linear or branched alkyl, cycloalkyl and the following groups (a) and (b): [Chemical 5] (However, R ⁴ , R ⁵ , and R ⁶ are the same or different and are hydrogen,
Halogen and alkyl, R ⁷ and R ⁸ are the same or different and each is hydrogen or alkyl, and p is 1 or 2. )] One or more maleimide compounds represented by the formula (iv) (Wherein R ⁹ represents alkyl having 1 to 4 carbon atoms), one or more compounds represented by the formula (v): Wherein, X ³ and X ⁴ are the same or different and represent a hydrogen, halogen or alkyl of 1 to 4 carbon atoms (provided that at least one of X ³ and X ⁴ is a halogen, more X ³ and X ^When one of ⁴ is other than halogen, the solubility of the compound measured by UV method is 0.5-50.
Y is (a) unsubstituted alkyl having 1 to 18 carbon atoms, (b) at least one hydrogen is halogen,
Substituted alkyl substituted by hydroxy, cyano, alkylamino, dialkylamino, phenylamino, halophenylamino, carboxy, alkoxycarbonyl, alkoxy, aryloxy, morpholino, piperidino, pyrrolidonyl, carbamoyloxy or isothiazolonyl, provided that Does not exceed 18), (c) C2-C18 unsubstituted alkenyl or halo-substituted alkenyl, (d) C2-C18 unsubstituted alkynyl or halo-substituted alkynyl, (e ) Unsubstituted cycloalkyl or alkyl-substituted cycloalkyl having a hydrocarbon ring having 3 to 6 carbon atoms and having a total carbon number of 12 or less, and (f) the total number of carbon atoms in aralkyl does not exceed 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 (vi) [Chemical 9] [Chemical 10] (In the formula, R ¹⁰ , R ¹¹ , and R ¹² each represent an alkyl having 1 to 4 carbon atoms, n represents 2 or 3, and M ¹ represents a water-insoluble metal salt of zinc, manganese, copper, iron, or nickel. Represents a metal to be formed, and M ² represents a metal forming a water-insoluble metal salt other than iron among M ¹⁾ , and at least ^one insoluble metal dithiocarbamate represented by the formula (vii) (In the formula, M ¹ and n have the same meanings as described above), one or more water-insoluble pyrithione metal salts represented by the formula (viii) 2,
An underwater antifouling agent comprising, as an active ingredient, one or more compounds (i) to (viii) selected from 2'-dithiobis (pyridine-N-oxide). (A) General formula R ^13- (S) m-R ¹³ (wherein R ¹³ represents alkyl having 1 to 20 carbon atoms, m
Represents an integer of 2 to 10. 1) of the compounds represented by
Or more, (b) one or more polybutenes having an average molecular weight of 200 to 1,000, (c) one or more paraffins, and (d) one or more selected from (a) to (d) selected from petrolatum. The underwater antifouling agent according to claim 1, which is contained as a regulator.