JPH11323206A - Antifouling agent for fishing net - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain the subject antifouling agent capable of exerting excellent and long-term effects on adhesion of e.g. Coelenterata such as hydrozoans and having excellent workability for its application to fishing nets and fishing net accessories by including a specific complex compound as an active ingredient. SOLUTION: This antifouling agent includes a triphenylborane-(iso)nicotinic acid ester complex compound of formula I (R is a 8-20C alkyl or alkenyl; the COOR-substituted position is either 3rd or 4th position relative to the N atom of the pyridine cycle) as an active ingredient. It is preferable that this antifouling agent is obtained by further including silicone oil and/or a tetraalkylthiuram disulfide of formula II (R<1> is a 1-8C alkyl) as active ingredient(s). When the complex compound of formula I is used singly, it is preferable that its amount to be used is 0.1-50 wt.%, based on the total weight of the antifouling agent.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention prevents the attachment of aquatic fouling organisms to fishing nets for aquaculture or stationary use and fishing net accessories such as floats and ropes used therefor,
In addition, the present invention relates to a fishing net antifouling agent having a long-lasting effect.

[0002]

2. Description of the Related Art Since aquaculture or stationary fishing nets are installed in the sea for a long time, seaweeds, barnacles, serpula,
Marine fouling organisms, such as bryozoans and molluscs, are heavily attached, and maintenance of these organisms requires a great deal of labor and cost.

Conventionally, organotin polymers have been widely used to prevent the adhesion of these marine fouling organisms. However, organotin compounds cannot be used due to environmental considerations.

Therefore, various researches and proposals have been made as antifouling agents replacing organic tin compounds. Currently, copper compounds such as cuprous oxide and rhodan copper; thiocarbamate compounds such as zinc salt and manganese salt of ethylenebisdithiocarbamic acid; An organic compound such as tetraethylthiuram disulfide, tetrachloroisophthalonitrile, or dimethylphenyldichloromaleimide is used as an active ingredient, and an antifouling agent is used in which the compound is mixed with an oil-based or synthetic resin-based vehicle. At present, a compound that is satisfactory in terms of fouling has not been found yet.

As an antifouling active ingredient, a complex of triphenylborane and a (substituted) pyridine derivative has been proposed (US Pat. No. 3,211,679, JP-A-7-133207). However, these compounds
Since it is insoluble in a solvent, it becomes a dispersion-type antifouling agent, and has a drawback that the working efficiency is extremely poor, and it is not satisfactory in antifouling performance and physical properties. Further, a complex of a triarylborane having a substituent introduced into a phenyl group and a nicotinic acid ester of C _{1 to} C ₆ has been proposed (JP-A-8-295829). However, these compounds also have low solubility in solvents, become dispersible antifouling agents, have poor workability, and are not satisfactory from the viewpoint of antifouling performance and physical properties.

[0006]

SUMMARY OF THE INVENTION In view of the foregoing, it is an object of the present invention to provide a fishing net antifouling which has good coating workability to a fishing net and a fishing net accessory and can maintain an excellent antifouling effect for a long time. It is an object to provide an agent.

[0007]

Means for Solving the Problems From the above viewpoints, the present inventors have conducted intensive studies and as a result, have found that the triphenylborane / (iso) nicotinic acid ester complex compound represented by the general formula (I) is Excellent antifouling against the adhesion of helminths such as insects, shellfish such as barnacles, mussels, oysters, and serpula, and tubal polychaetes such as kansane kansashi, human kansetsu, yakko kansashii, and suzukigokai, or other organisms. Since it is effective and is soluble in organic solvents such as xylene, it has been found that it is possible to produce a practical preparation with extremely good workability, especially in screen dyeing. A silicone oil is used in combination with the nicotinic acid ester complex compound, and / or a tetraalkyl thiocyanate represented by the general formula (II) When used together with muzisulfide, the antifouling performance is dramatically improved, and not only does the antifouling effect against large organisms such as barnacles, serplas, ascidians, mosses and algae continue for a long period of time, but it also poses a problem in stationary sea areas. The present inventors have also found that the antifouling effect on hydros and oberia is dramatically improved, and the antifouling effect on slime is also dramatically improved, and the present invention has been completed.

That is, the present invention provides (1) a compound represented by the general formula (I):

[0009]

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(Wherein, R represents a linear or branched alkyl or alkenyl group having 8 to 20 carbon atoms. However, the substitution position of the COOR group is 3 or 4 with respect to the N atom of the pyridine ring. The present invention relates to a fishing net antifouling agent comprising, as an active ingredient, a triphenylborane / (iso) nicotinic acid ester complex compound represented by any of the following:

Further, the present invention relates to (2) a fishing net antifouling agent comprising the triphenylborane / (iso) nicotinic acid ester complex compound described in the above item (1) and silicone oil as active ingredients. .

The present invention further provides (3) a triphenylborane / (iso) nicotinic acid ester complex compound as described in the above item (1), and a compound represented by the general formula (II):

[0013]

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Wherein R ¹ represents an alkyl group having 1 to 8 carbon atoms, and a tetraalkylthiuram disulfide compound as an active ingredient.

Further, the present invention provides (4) (A) the above (1)
(C) a triphenylborane / (iso) nicotinic acid ester complex compound described in (1), (B) a silicone oil,
A fishing net antifouling agent comprising the tetraalkylthiuram disulfide compound described in the above (3) as an active ingredient.

[0016]

BEST MODE FOR CARRYING OUT THE INVENTION The compound used as an essential component in the present invention is a triphenylborane / (iso) nicotinic acid ester complex compound represented by the general formula (I). Here, (iso) nicotinic acid ester means nicotinic acid ester or isonicotinic acid ester.

In the general formula (I), the straight-chain or branched alkyl or alkenyl group having 8 to 20 carbon atoms represented by R is not particularly restricted but includes, for example, an octyl group, 2-ethylhexyl group, isooctyl group, tert-octyl group, octylenyl group,
Isooctenylenyl, 2-ethylhexenyl, nonyl, isononyl, tert-nonyl, nonenyl,
Isononenyl group, decyl group, isodecyl group, tert-
Decyl group, decenyl group, undecyl group, isoundecyl group, tert-undecyl group, undecenyl group, dodecyl group, isododecyl group, tert-dodecyl group, dodecenyl group, tridecyl group, tridecenyl group, tetradecyl group, tetradecenyl group, pentadecyl group, pentadecenyl Group, hexadecyl group, hexadecenyl group, octadecyl group, isooctadecyl group, tert-octadecyl group, octadecenyl group (oleyl group), eicosyl group and the like. These triphenylborane ・ (iso)
The nicotinic acid ester complex compounds may be used alone or in combination of two or more.

In the present invention, the above-mentioned triphenylborane / (iso) nicotinic acid ester complex compound may be used alone as an active ingredient, but it may be used in combination with silicone oil and / or a compound represented by the general formula (II). The combined use of the represented tetraalkylthiuram disulfide compound significantly improves the antifouling effect.

Examples of the silicone oil used in the present invention include polydimethylsiloxane, polymethylphenylsiloxane, methylphenylsiloxane-dimethylsiloxane copolymer, polyether-modified polydimethylsiloxane, and polyether-modified polyalkyl (methyl).
Examples include, but are not limited to, siloxane, polyester-modified polydimethylsiloxane, fluorosilicone oil, amino-modified silicone oil, and silicone oil modified with various functional groups. Among these silicone oils, preferred are polydimethylsiloxane, methylphenylsiloxane-dimethylsiloxane copolymer, polyether-modified polydimethylsiloxane, and the like. These silicone oils may be used alone or in combination of two or more. The silicone oil used in the present invention is
From the viewpoint of the physical properties of the fishing net antifouling agent, those having a viscosity in the range of 10,000 to 10,000 poise, preferably 50 to 500 poise are preferred.

Examples of the tetraalkylthiuram disulfide compound represented by the general formula (II) used in the present invention include tetramethylthiuram disulfide, tetraethylthiuram disulfide, tetrapropylthiuram disulfide, tetraisopropylthiuram disulfide, tetrabutylthiuram disulfide, tetrabutylthiuram disulfide and tetrabutylthiuram disulfide. −s
ec-butyl thiuram disulfide, tetraisobutyl thiuram disulfide, tetra-tert-butyl thiuram disulfide, tetrapentyl thiuram disulfide, tetrahexyl thiuram disulfide, tetraheptyl thiuram disulfide, tetraoctyl thiuram disulfide, tetra (2-ethylhexyl) thiuram disulfide and the like But not limited to these. Among these tetraalkylthiuram disulfide compounds, preferred are tetraethylthiuram disulfide and tetrabutylthiuram disulfide. These tetraalkylthiuram disulfide compounds may be used alone or in combination of two or more. Further, it can be used in combination with one or more of the above silicone oils.

In addition, an oil-based and / or synthetic resin-based vehicle is usually used for the fishing net antifouling agent of the present invention. Oil-based or synthetic resin-based vehicles include, for example, linseed oil, hemp oil, boil oil such as tung oil, vinyl resins such as vinyl chloride resins, alkyd resins, acrylic resins,
Examples include urethane-based resins, polyester-based resins, synthetic rubber, and synthetic resins such as chlorinated polyethylene. The molecular weight of these oil-based or synthetic resin-based vehicles is usually 1,000,000 or less in terms of weight average molecular weight, particularly 200 to 2
A range of 00,000 is preferred.

The fishing net antifouling agent of the present invention usually contains a solvent. The solvent is not particularly limited and various solvents can be used, for example, aromatic hydrocarbon solvents such as benzene, toluene, xylene and trimethylbenzene, alcohol solvents such as ethanol, isopropanol and n-butanol, and acetone. And ketone solvents such as diethyl ketone and methyl isobutyl ketone. These solvents may be used alone,
Two or more kinds may be used in combination.

In the fishing net antifouling agent of the present invention, when a triphenylborane / (iso) nicotinic acid ester complex compound is used alone as an active ingredient,
Although not particularly limited, with respect to the total amount of the antifouling agent,
Usually 0.1 to 50% by weight, preferably 1 to 15% by weight.
% By weight. If the amount of the triphenylborane / (iso) nicotinic acid ester complex compound is less than the above range, the antifouling property is not sufficient, while if it exceeds the above range, the physical properties of the coating film tend to be insufficient.

Further, when the silicone oil is used in combination with the triphenylborane / (iso) nicotinic acid ester complex compound in the fishing net antifouling agent of the present invention, the mixing ratio thereof is not particularly limited. The weight ratio of the triphenylborane / (iso) nicotinic acid ester complex compound to the silicone oil is usually in the range of 1:99 to 99: 1, and preferably 1:50 to 50:
1, particularly preferably in the range of 1:10 to 10: 1. The total blending amount of these compounds with respect to the total amount of the antifouling agent is not particularly limited, but is usually 0.1 to 50.
%, Preferably in the range of 3 to 20% by weight. If the total amount of the compounds is less than the above range, the antifouling property is deteriorated. On the other hand, if it exceeds the above range, the coating properties and coating properties as a fishing net antifouling agent tend to be insufficient.

Furthermore, in the case of using the tetraalkylthiuram disulfide compound in combination with the triphenylborane / (iso) nicotinic acid ester complex compound in the fishing net antifouling agent of the present invention, the mixing ratio thereof is not particularly limited. However, the weight ratio of the triphenylborane / (iso) nicotinic acid ester complex compound to the tetraalkylthiuram disulfide compound is generally in the range of 1:99 to 99: 1, and preferably 1:50 to 100 from the viewpoint of antifouling properties. 50:
1, particularly preferably in the range of 1:10 to 10: 1. The total blending amount of these compounds with respect to the total amount of the antifouling agent is not particularly limited, but is usually 0.1 to 50.
%, Preferably in the range of 3 to 20% by weight. If the total amount of the compounds is less than the above range, the antifouling property is deteriorated. On the other hand, if it exceeds the above range, the coating properties and coating properties as a fishing net antifouling agent tend to be insufficient.

Further, in the present invention, triphenylborane
The silicone oil can be used in combination with the (iso) nicotinic acid ester complex compound and the tetraalkylthiuram disulfide compound mixed in the above ratio. In this case, the mixing ratio of these is not particularly limited, but a mixture of triphenylborane. (Iso) nicotinic acid ester complex / tetraalkylthiuram disulfide (mixing ratio 1:99 to 99: 1, preferably 1: 1) 5
0 to 50: 1, particularly preferably 1:10 to 10: 1)
The weight ratio of silicone oil to silicone oil is usually from 1:99 to 99: 1.
From the viewpoint of antifouling property, preferably from 1:50 to
It is in the range of 50: 1, particularly preferably 1:10 to 10: 1. The total amount of these compounds is not particularly limited with respect to the total amount of the antifouling agent, but is usually 1 to 60.
%, Preferably from 3 to 30% by weight, particularly preferably from 5 to 20% by weight. If the total amount of the compounds is less than the above range, the antifouling property is deteriorated. On the other hand, if it exceeds the above range, the coating properties and coating properties as a fishing net antifouling agent tend to be insufficient.

Other antifouling agents may be added to the fishing net antifouling agent of the present invention. These antifouling agents include, for example, dithiocarberte-based antifouling agents, carbamate-based antifouling agents, maleimide-based antifouling agents, isothiazolone-based antifouling agents, and tetrachloroisophthalonitrile. Further, a plasticizer such as polybutene, vaseline, chlorinated paraffin, liquid paraffin, ditertiary nonyl pentasulfide (TNPS), and tricresyl phosphate can be added to the fishing net antifouling agent of the present invention. Further, the fishing net antifouling agent of the present invention includes pigments and other additives, for example, dispersing agents such as polyamide phosphoric acid type, polyamide type, unsaturated polycarboxylic acid type, defoaming agents, anti-sagging agents, surfactants and the like. Can be added. In the fishing net antifouling agent of the present invention, other antifouling agents, plasticizers, pigments, other additives,
It can be contained at any mixing ratio within a range that does not impair the purpose of the present invention.

The fishing net antifouling agent of the present invention can be produced by mixing the above-mentioned components, blending various additives as necessary, and mixing. The method of mixing each component and the method of adding various additives are not particularly limited, and can be performed by various methods, and the mixing order and the addition order can be performed in various mixing orders and the addition order.

According to the present invention, a fishing net antifouling agent of the present invention is applied to a fishing net to prevent the adhesion of aquatic fouling organisms,
It is also possible to provide an antifouling method for fishing nets exhibiting excellent antifouling properties. As a method of applying the fishing net antifouling agent to fishing net implements, various coating methods such as dip coating and spray coating can be applied, but dip coating is preferred. In the case of a fishing net, the attached amount is preferably in the range of 1 to 20% by weight of the weight of the fishing net.

[0030]

EXAMPLES Next, the present invention will be described with reference to Production Examples, Examples and Test Examples of a triphenylborane / (iso) nicotinic acid ester complex compound. The percentages and parts in each example indicate% by weight and parts by weight, respectively.

Production Example 1 Production of triphenylborane / dodecyl nicotinate complex In a 300 ml four-necked flask equipped with a condenser and a stirrer, 24.2 g (0.10 mol) of triphenylborane (special grade reagent, manufactured by Aldrich) was added. Dodecyl nicotinate (J. Am. Chem. Soc., 67 , 1135)
(Synthesized by the method described in (1945)) 29.1 g (0.1
0 mol), dehydrated tetrahydrofuran (THF) 100
After reacting at room temperature for 4 hours under a N ₂ stream, THF was distilled off under reduced pressure. The residue was recrystallized from methanol to obtain 50.1 g (94% yield) of a triphenylborane-nicotinic acid dodecyl complex. The result of the following elemental analysis confirmed that this compound was a triphenylborane-dodecyl nicotinate complex.

C (%) H (%) N (%) B (%) O (%) Measured value 81.3 8.4 2.4 2.1 5.8 Theoretical value 81.1 8.3 2. 6 2.0 6.0 Production Example 2 Production of octadecyl triphenylborane / nicotinic acid complex
In Production Example 1, octadecyl nicotinate (J. Am. Chem. Soc., 67 ,
17.6 (synthesized by the method described in 1945)) 37.6 g
(0.10 mol), and in the same manner as in Production Example 1, triphenylborane / octadecyl nicotinate complex 48.8.
g (79% yield). This compound was confirmed to be triphenylborane-octadecyl nicotinate by the following elemental analysis.

C (%) H (%) N (%) B (%) O (%) Measured value 81.7 9.0 2.2 1.6 5.5 Theoretical value 81.6 9.1 2. 3 1.8 5.2 Production Example 3 Production of Triphenylborane / Oleic Acid Nicotinate Complex In Production Example 1, instead of dodecyl nicotinate, oleyl nicotinate (J. Am. Chem. Soc., 67 , 11) was used.
35 (synthesized according to the method described in 1945) 37.3
g (0.10 mol), and in the same manner as in Production Example 1,
Triphenylborane / nicotinic acid oleyl complex 56.0
g (yield 91%) was obtained. This compound was confirmed to be a triphenylborane-nicotinic acid oleyl complex by the following elemental analysis.

C (%) H (%) N (%) B (%) O (%) Measured value 81.8 8.9 2.4 1.9 5.0 Theoretical value 81.9 8.8 2. 3 1.8 5.2 Production Example 4 2-Ethylhexyl triphenylborane / isonicotinate
Production of Complexes in Preparation Example 1 Instead of dodecyl nicotinate, 2-ethylhexyl isonicotinate (J. Am. Chem. So
c. , 67 , 1135 (1945)) in the same manner as in Production Example 1 using 23.5 g (0.10 mol) of 43.5 g of 2-phenylhexyl triphenylborane-isonicotinate ( Yield 93%). From the results of the following elemental analysis, it was confirmed that this compound was a triphenylborane-isonicotinic acid 2-ethylhexyl complex.

C (%) H (%) N (%) B (%) O (%) Measured value 80.3 7.6 3.0 2.2 6.9 Theoretical value 80.5 7.6 2. 9 2.3 6.7 Production Example 5 Production of triphenylborane / dodecyl isonicotinate complex
In Production Example 1, dodecyl isonicotinate (J. Am. Chem. Soc., 67 ,
1135 (1945)).
Using 9.1 g (0.10 mol), in the same manner as in Production Example 1, 47.5 g (89% yield) of triphenylborane-donicosyl isonicotinate was obtained. The result of the following elemental analysis confirmed that this compound was a triphenylborane / dodecyl isonicotinate complex.

C (%) H (%) N (%) B (%) O (%) Measured value 81.3 8.5 2.4 2.0 5.8 Theoretical value 81.1 8.3 2. 6 2.0 6.0 Production Example 6 Triphenylborane / octadecyl isonicotinate complex
In Production Example 1, octadecyl isonicotinate (J. Am. Chem. Soc., 6) was used instead of dodecyl nicotinate.
7 , 1135 (1945))
Using 7.6 g (0.10 mol), in the same manner as in Production Example 1, 43.3 g (yield 70%) of triphenylborane / octanodecyl isonicotinate complex was obtained. From the results of the following elemental analysis, it was confirmed that this compound was a triphenylborane / octadecyl isonicotinate complex.

C (%) H (%) N (%) B (%) O (%) Measured value 81.8 9.4 2.1 1.7 5.0 Theoretical value 81.6 9.1 2. 3 1.8 5.2 Comparative Production Example 1 Production of methyl tri (p-tolyl) borane / nicotinic acid complex
Concrete condenser, birds 300ml four-necked flask equipped with a stirrer (p- tolyl) borane (DE 265177
No. 5, synthesized (28.4 g, 0.10 g)
mol), 13.7 g (0.10 mol) of methyl nicotinate (reagent grade, manufactured by Tokyo Chemical Industry Co., Ltd.) and 100 ml of dehydrated tetrahydrofuran (THF), and reacted at room temperature for 6 hours under a stream of N ₂ . THF was distilled off under reduced pressure to obtain 36.4 g (96% yield) of methyl tri (p-tolyl) borane / nicotinic acid complex.

Comparative Production Example 2 Production of triphenylborane-pyridine complex (US Pat. No. 3,111,679 and JP-A-7-133207)
(Compound described in Japanese Patent Application Laid-Open Publication No. 2000-209) Instead of dodecyl nicotinate in Production Example 1, 7.9 g (0.1 m) of pyridine (special reagent grade, manufactured by Kishida Chemical Co., Ltd.)
ol) in the same manner as in Production Example 1 to obtain 27.6 g of a triphenylborane-pyridine complex in a yield of 86%.

Examples 1 to 9 and Combined Examples 1 to 23 and Comparative Examples 1 to 2 and Comparative Examples 1 to 4 Using the compounds obtained in Production Examples 1 to 6 and Comparative Production Examples 1 and 2, Examples 1 to 4
9 and Comparative Examples 1-2 were obtained. Further, the compounds obtained in Production Examples 1 to 6 were used, and a silicone oil or a tetraalkylthiuram disulfide represented by the general formula (II) was used in combination therewith, and the components described in Tables 2 to 4 were further added and used in combination. Examples 1 to 23 and Comparative Example 1 for Combination
~ 4 fishing net antifouling agents were obtained.

[0040]

[Table 1]

[0041]

[Table 2]

[0042]

[Table 3]

[0043]

[Table 4]

Test Examples 1 to 38 (Anti-fouling test) The fishing net anti-fouling agents obtained in Examples 1 to 9 and Comparative Examples 1 and 2 were made of polyethylene (400 denier, 40 tubes, section 8).
Was dipped and dried (dry adhesion amount: 6.3 to 8.9% by weight of the fishing net weight). The fishing net coated with the antifouling agent was fixed to a frame of a 40 cm × 60 cm iron rod, and immersed in a water raft at a depth of about 1 to 2 m from an underwater raft in Owase Bay, Mie Prefecture. Over time. Table 5 shows the results. In addition, the fishing net antifouling agents obtained in Combination Examples 1 to 23 and Comparative Comparative Examples 1 to 4 were similarly immersed in Owase Bay, Mie Prefecture, and their antifouling performance was periodically observed for 12 months. Table 6 shows the results.

The symbols in the table indicate the following.

◎: no marine animals and plants attached, slime attached ○: no marine animals and plants attached, but slime adhered ×: 10% or less of marine animals and plants attached ×× mark: marine animals and plants attached 10% to 50% adhered ××× mark: 50% or more adhered to marine animals and plants

[0047]

[Table 5]

[0048]

[Table 6]

[0049]

As is clear from the results shown in Table 5, the antifouling agent for fishing nets of the present invention using the triphenylborane / (iso) nicotinic acid ester complex compound represented by the general formula (I) is useful for aquatic fouling organisms. Adhesion can be effectively prevented. Further, as is clear from the results in Table 6, the present invention using (A) a triphenylborane / (iso) nicotinic acid ester complex compound and (B) a silicone oil and / or (C) a tetraalkylthiuram disulfide compound in combination. Can prevent aquatic fouling organisms and slime from adhering for a long time.

Claims (4)

[Claims] 1. A compound of the general formula (I): (In the formula, R represents a linear or branched alkyl group or an alkenyl group having 8 to 20 carbon atoms.
The substitution position of the R group indicates either the 3-position or the 4-position with respect to the N atom of the pyridine ring.) A fishing net comprising, as an active ingredient, a triphenylborane / (iso) nicotinic acid ester complex compound represented by the formula: Antifouling agent. 2. The triphenylborane according to claim 1,
A fishing net antifouling agent comprising an (iso) nicotinic acid ester complex compound and silicone oil as active ingredients. 3. The triphenylborane according to claim 1,
An (iso) nicotinic acid ester complex compound represented by the general formula (I
I): (Wherein R ¹ represents an alkyl group having 1 to 8 carbon atoms) and a tetraalkylthiuram disulfide compound as an active ingredient. 4. A triphenylborane / (iso) nicotinic acid ester complex compound according to claim 1, and (B)
An antifouling agent for fishing nets, comprising a silicone oil and (C) the tetraalkylthiuram disulfide compound according to claim 3 as active ingredients.