JPH08295608A - Fishing net antifouling agent containing triphenylborane-alkylamine complex compound - Google Patents

Abstract

(57) [Abstract] [PROBLEMS] The present invention greatly improves workability such as reticulation because it is a soluble type, and further, coelenterates such as hydrozoa, shellfish such as barnacles, mussels, oysters, and serpra, Also, to provide a fishing net antifouling agent that exhibits an excellent antifouling effect for a long period of time against all marine periphytic organisms including polychaetes such as Hawthorn scorpion, Hawthorn saccharinus, Hawthorn saccharinus, Hawthorn scallops, etc. With the goal. SOLUTION: One or more triphenylborane-alkylamine complex compounds are contained as an active ingredient,
Further, an organic solvent-soluble type fishing net antifouling agent characterized by comprising an organic solvent capable of dissolving them can solve the above problems.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention is used for aquaculture or stationary fishing nets, or materials such as floats and ropes used in fishing nets, to produce coelenterates, shellfish, and polychaetes. The present invention also relates to a fishing net antifouling agent, which prevents fouling caused by other marine attached organisms, and whose active ingredient is soluble in an organic solvent, thereby greatly improving the workability of net dyeing.

[0002]

2. Description of the Related Art Since fishing nets for aquaculture or stationary are kept in the sea for a long period of time, it is necessary to maintain the seawater such as coelenterates such as hydroids, shellfish, tubular polychaetes, seaweeds, bryozoans and molluscs. Habitat organisms attach violently. Since the attachment of fouling organisms causes a large economic loss to the fishing net, it is the current situation that efforts are made to maintain these fouled objects with great effort and cost.

Until now, various studies and proposals have been made as countermeasures against adherent organisms. It is known that a series of organotin compounds are practically effective. However, organotin compounds are generally highly toxic, and careless handling of products containing them may cause damage to the handler and may also cause environmental damage. For these reasons, the emergence of low-pollution underwater antifouling agents has been 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 another underwater antifouling compound are combined, as disclosed in JP-B-61-50984. Is an anti-contamination agent for marine structures containing a 3-isothiazolone compound as an active ingredient, which is disclosed in Japanese Patent Publication No. 1-20665.
JP-B-2-24242, JP-A-53-9320, JP-A-5-201804, and JP-A-6-10.
Japanese Patent Application Laid-Open No. 0405 and Japanese Patent Application Laid-Open No. 6-100408 disclose antifouling paints containing a maleimide compound as an active ingredient.

However, all of these antifouling agents have a weak effect of preventing adherence to coelenterates such as hydrozoa and cannot be used in the sea area where coelenterates are generated. The coelenterate region is mainly the Tohoku region and the coast of Hokkaido where set nets are used. Once attached to the fishing net, the hydrozoa propagates with tremendous force in a short period of time, completely blocking the mesh and making it useless as a fishing net. Also, if a part of the body of the hydro-insect remains in the net, the hydro-insect will reproduce again from that part, so the removal work must be done completely, but the hydro-insect adheres very firmly, so it is completely It is extremely difficult to remove.

[0005] For the reasons described above, hydrozoa are marine attached organisms that are the most damaging and difficult to counteract.
Therefore, in particular, recently, there has been earnestly desired to develop an antifouling agent for a set net which is effective against coelenterates such as hydrozoa. By the way, Japanese Unexamined Patent Publication (Kokai) No. 6-157219 discloses an underwater antifouling agent for preventing coelenterant adhesion, which comprises a water-insoluble metal salt of dithiocarbamic acid as an active ingredient. However, since these compounds are insoluble in organic solvents such as xylene, the obtained antifouling agent is a dispersion type in which the active ingredient is dispersed. Such a dispersion type fishing net antifouling agent does not exhibit its full effect unless it is thoroughly stirred and mixed before use, and therefore the workability during an antifouling treatment called net dyeing is very poor. In addition, if left for a long period of time, the active ingredient may settle, aggregate, and may not be redispersed.

On the other hand, of the organisms attached to the aquaculture net,
The antifouling agents described above have a weak effect of preventing the adhesion of these organisms to shellfish and polychaetes, and thus cannot prevent the adhesion of these organisms. The specific damage caused by the adhesion of shellfish and polychaete in the fishing net for aquaculture is, firstly, when the fishing net is lifted to the sea such as feeding and changing the net, the weight of the fishing net is reduced due to the adhesion of these organisms. Secondly, these adherent organisms are covered with hard calcareous matter, which may damage the fish and reduce the commercial value. Third, these adherent organisms It is very difficult to remove living organisms because they attach very strongly.

As described above, in the case of a fishing net for aquaculture, the damage caused by shellfish and avian polychaetes is particularly large as compared with the damage caused by other attached organisms, and the prevention of the attachment of these organisms is the conventional prevention. It's difficult with dirt. Therefore, development of an antifouling agent for aquaculture nets, which is effective against shellfish and polychaete, is strongly desired.
It is known that copper is effective against shellfish, and in fact, it was confirmed that a copper-based antifouling agent for fishing nets is effective against shellfish and polychaetes. However, copper-based fishing net antifouling agents have various drawbacks. For example, since heavy metal copper is used, it may have an adverse effect on the environment, and because the treated fishing net is hard and heavy, it has poor workability when feeding or changing nets, and it is expensive. However, if a fishing net that has been used once is treated with a copper-based fishing net antifouling agent again, its effectiveness will decrease. In addition, the biggest drawback of the copper-based fishing net antifouling agent is that the antifouling agent obtained is a dispersion type because the active ingredient does not dissolve in an organic solvent such as xylene. The drawbacks of the dispersed fishing net antifouling agent are as described above.

By the way, US Pat. No. 3,211,679 discloses an antifouling coating containing 25% by weight or more of a triphenylborane-alkylamine complex compound using an alkylamine having 4 to 20 carbon atoms as an active ingredient. Is listed. However, in the present patent specification, by dissolving the complex compound in an organic solvent such as xylene,
There is no suggestion of providing a fishing net antifouling agent with greatly improved workability of net dyeing. In addition, there is no suggestion of a fishing net antifouling agent which is particularly excellent in antifouling effect against coelenterates such as hydrozoa, which uses the complex compound as an active ingredient, or shellfish, and polychaetes.

The triphenylborane-hexadecylamine complex compound is a compound which is not described in the above-mentioned US Pat. No. 3,211,679 or other documents.

[0010]

DISCLOSURE OF THE INVENTION The present invention is mainly applied to coelenterants such as hydro worms attached to stationary fishing nets, and organisms attached to aquaculture fishing nets such as shellfish and polychaetes.
It is an object of the present invention to provide an organic solvent-soluble type fishing net antifouling agent which has an excellent antifouling effect and in which the active ingredient is dissolved in an organic solvent, and thus the workability of the net dyeing is remarkably improved.

It is also an object of the present invention to provide an antifouling agent having low pollution and containing no heavy metal.

[0012]

Means for Solving the Problems The inventors of the present invention have made diligent research to overcome the above-mentioned drawbacks of the conventional antifouling agents in water, and as a result, they have low toxicity and thus may cause environmental pollution. The present invention has invented a fishing net antifouling agent which is less soluble and has improved workability because it is soluble. That is, triphenylborane-alkylamine complex compounds, coelenterates such as hydrozoa, barnacles, blue mussels, oysters, shellfish such as serpra, and Kasane kanzaku, human kanzaku,
It has an excellent antifouling effect against the adherence of tubular polychaetes such as Pleurotus japonicus and Pleurotus cornucopiae, or other organisms. In addition, it is soluble in an organic solvent such as xylene, so it is extremely workable, especially in mesh dyeing. It has been found that a good and practical preparation is possible, and has completed the present invention. The triphenylborane-amine complex compounds of methylamine and ethylamine have low solubility in xylene and do not meet the object of the present invention.

In addition to good workability at the time of net dyeing, organic solvent-soluble type fishing net antifouling agents have the following advantages. First, it consumes less antifouling agent and is economical.
Second, the weight of the treated net is almost the same as before the treatment, and the softness is maintained. Third, the effect does not decrease even if the fishing net used once is repeatedly treated, and fourth, long-term storage. It is suitable for.

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

[0015]

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(Wherein R ¹ represents an alkyl group having 3 to 30 carbon atoms), a triphenylborane-alkylamine complex compound (hereinafter also referred to as compound group (i)), or Contains two or more as active ingredients,
Furthermore, an organic solvent-soluble type fishing net antifouling agent comprising an organic solvent that dissolves these, (2): a total compounding amount of one or more triphenylborane-alkylamine complex compounds The fishing net antifouling agent according to (1), which is 1% by weight to less than 25% by weight, (3): (1)
An organic solvent-soluble coelenterate adhesion preventive method, comprising one or more of the triphenylborane-alkylamine complex compounds described in 1. as an active ingredient, and further comprising an organic solvent capable of dissolving these. Fishing net antifouling agent,
(4): Dissolved in an organic solvent, which contains one or more triphenylborane-alkylamine complex compounds described in (1) as an active ingredient, and further comprises an organic solvent that dissolves them. Type anti-fouling agent for aquaculture net,
(5): Among the triphenylborane-alkylamine complex compounds according to (1), the alkylamine has 3 carbon atoms,
Alternatively, an organic solvent-soluble type fishing net antifouling agent comprising one or more complex compounds of 8 to 18 as an active ingredient, and further comprising an aromatic hydrocarbon capable of dissolving these. (6): Among the triphenylborane-alkylamine complex compounds described in (1), the alkylamine is n-propylamine, n-octylamine, 2-ethylhexylamine, n-dodecylamine, n-hexadecylamine, Containing one or more complex compounds of n-octadecylamine as an active ingredient (5)
(7): One or more triphenylborane-alkylamine complex compounds according to (7): (1), (5) or (6), and 1,3-dicyanotetrachlorobenzene. (Hereinafter, also referred to as compound (ii)),
2- (thiocyanomethylthio) benzothiazole (hereinafter, also referred to as compound (iii)), general formula

[0017]

[Chemical 9]

(In the formula, R ² represents an alkyl group having 1 to 4 carbon atoms.) Tetraalkyl thiuram disulfides (hereinafter, also referred to as compound group (iv))
One or more of the general formulas

[0019]

[Chemical 10]

(In the formula, R ³ is hydrogen, an alkyl group, a halogen-substituted alkyl group, a cycloalkyl group, a phenyl group, an alkyl-substituted phenyl group, a halogen-substituted phenyl group, a benzyl group, an alkyl-substituted benzyl group or a halogen-substituted benzyl group. 1, 2, or more of 2,3-dichloromaleimides (hereinafter, also referred to as compound group (v)) represented by the general formula:

[0021]

[Chemical 11]

(In the formula, R ⁴ , R ⁵ and R ⁶ are the same or different and are hydrogen, an alkyl group, a halogen-substituted alkyl group,
A cycloalkyl group, a phenyl group, a halogen, an alkoxy group, a carbonyl group, an alkenyl group and an aralkyl group are shown. 1) or 2 or more compounds selected from the group consisting of 1 or 2 or more phenols (hereinafter, also referred to as compound group (vi)) represented by organic solvent soluble type of fishing net antifouling agent characterized by comprising an organic solvent which dissolves, (8): as an elution-adjusting agent, the general formula _{^{R 7 - (S) n -R}} 7 ( wherein, R ⁷ carbon Represents a number 1 to 20 alkyl groups,
n shows the integer of 2-10. ), Dialkyl polysulfides (hereinafter, also referred to as compound group (vii)), polybutene having an average molecular weight of 200 to 1000, paraffins, and petroleum jelly selected from the group consisting of one or more species. (1),
(2), (3), (4), (5), (6) or (7)
(9): triphenylborane-n
-Hexadecylamine complex compound, (10): Triphenylborane described in (9) -A fishing net antifouling agent containing an n-hexadecylamine complex compound, (11): Triphenylborane described in (9)- An organic solvent-soluble type fishing net antifouling agent, comprising an n-hexadecylamine complex compound as an active ingredient, and further comprising an organic solvent capable of dissolving the same, (12): the bird according to (9) Phenylborane
The fishing net antifouling agent according to (10) or (11), wherein the content of the n-hexadecylamine complex compound is 0.1% by weight to 30% by weight or less, (13): according to (9). An organic solvent-soluble type fishing net antifouling agent for preventing adherence of coelenterates, which comprises a triphenylborane-n-hexadecylamine complex compound as an active ingredient and further comprises an organic solvent capable of dissolving the compound, ( 14): For an organic solvent-soluble type aquaculture net, comprising the triphenylborane-n-hexadecylamine complex compound according to (9) as an active ingredient, and further comprising an organic solvent capable of dissolving the same. Antifouling agent, (15): triphenylborane-n-hexadecylamine complex compound described in (9), 1,3-dicyanotetrachlorobenzene, 2- (thiocyanomethylthio) benzothiazo , The general formula

[0023]

[Chemical 12]

(In the formula, R ² represents an alkyl group having 1 to 4 carbon atoms.) One or more tetraalkyl thiuram disulfides represented by the general formula

[0025]

[Chemical 13]

(In the formula, R ³ represents hydrogen, an alkyl group, a halogen-substituted alkyl group, a cycloalkyl group, a phenyl group, an alkyl-substituted phenyl group, a halogen-substituted phenyl group, a benzyl group, an alkyl-substituted benzyl group or a halogen-substituted benzyl group. 1) or 2 or more types of 2,3-dichloromaleimides represented by

[0027]

Embedded image

(In the formula, R ⁴ , R ⁵ and R ⁶ are the same or different and are hydrogen, an alkyl group, a halogen-substituted alkyl group,
A cycloalkyl group, a phenyl group, a halogen, an alkoxy group, a carbonyl group, an alkenyl group and an aralkyl group are shown. And one or more compounds selected from the group consisting of one or more of the phenols represented by), as an active ingredient, and further comprising an organic solvent capable of dissolving these. organic solvent soluble type of fishing net antifouling agent, (16): elution controlling general formula as agents R ⁷ - in (S) _n -R ⁷ (wherein, R ⁷ represents 1-20 alkyl group having a carbon number,
n shows the integer of 2-10. ), The dialkyl polysulfides having an average molecular weight of 200 to 1000
(10), (11), (12), (13), (14) characterized by containing one or more selected from polybutene, paraffins and petrolatum having
Alternatively, it relates to the fishing net antifouling agent as described in (15).

[0029]

BEST MODE FOR CARRYING OUT THE INVENTION The triphenylborane-alkylamine complex compound of the present invention can be synthesized by the following general formula.

[0030]

[Chemical 15]

(In the formula, R ¹ is as described above.) That is, the target triphenylborane-alkylamine is obtained by reacting sodium hydroxide adduct of triphenylborane with the corresponding alkylamine in an aqueous solution. Complex compounds can be synthesized. Since the obtained complex compound is insoluble in water, it is immediately separated. When the separated complex compound crystallizes, it may be collected by filtration, washed with water, and then dried. If it does not crystallize, it is extracted with an organic solvent such as toluene or xylene, washed with water, dried over anhydrous magnesium sulfate or the like, and the solvent is distilled off under reduced pressure to obtain an oily complex compound. To be The reaction temperature may be room temperature, but can be changed from 0 ° C. to 60 ° C. if necessary. The reaction time is 30 minutes to 2 days.

The object can also be obtained by the method described in Berichte, Volume 57B, page 813 (1924). R ¹ of the compound (i) used in the present invention is not particularly limited, but n-
A propyl group or an alkyl group having 8 to 18 carbon atoms is preferable. The alkyl group having 8 to 18 carbon atoms includes, for example, 2-ethylhexyl, octyl, nonyl, decyl, dodecyl, tetradecyl, hexadecyl, octadecyl, 3-ethylhexyl, 2,2-dimethylhexyl, 2,3-dimethylhexyl, etc. Is.

The compound (i) used in the present invention is a triphenylborane-alkyl compound synthesized by using an alkylamine composition containing two or more alkylamine compounds having 3 to 18 carbon atoms. It is also desirable to be an amine composition. The reason why an alkyl group having 8 to 18 carbon atoms is preferable as R ¹ is that the amine is inexpensive and economical, and the synthetic yield is high. The main reason is that the antifouling effect is high. It is a thing. Specifically, as shown in Examples described later, the antifouling agent for aquaculture nets containing a complex compound of a higher amine having 8 to 18 carbon atoms as an active ingredient has a shelf life of 6 months or more and a carbon number of The antifouling agent for aquaculture nets using a complex compound of a lower amine of 7 or less has a long-lasting period of more than 4 months, and is excellent in sustainability. Is 3 or 8 to 1
The efficacy of the amine complex compound of No. 8 is superior to that of the amine complex compound having 19 or more carbon atoms. However, the n-propylamine complex compound exceptionally showed the same durability as the higher amine complex compound having 8 to 18 carbon atoms. Further, even an amine complex compound having 3 or 8 to 18 carbon atoms can be used as an active ingredient of an antifouling agent because it has an antifouling effect for at least 4 months. Examples of R ¹ of an amine complex compound having 3 or 8 to 18 carbon atoms include, for example, butyl, pentyl, hexyl, heptyl, icosyl, docosyl, tetracosyl, hexacosyl, octacosyl, triacontyl, secondary butyl and tertiary. Examples include pentyl, 1-methylpentyl, 2-methylpentyl and the like.

R of the compound group (iv) used in the present invention
² includes methyl, ethyl, propyl, isopropyl and butyl, and compounds include tetramethylthiuram disulfide, tetraethylthiuram disulfide,
Tetraisopropyl thiuram disulfide, tetra-
Examples thereof include n-butyl thiuram disulfide.

Further, the alkyl group in R ³ of the compound group (v) is ethyl, isopropyl, butyl, tertiary butyl, octyl and the like, and the halogen-substituted alkyl group is dichloromethyl, dichloroethyl, trichloroethyl and the like, Cycloalkyl groups are cyclohexyl, etc., alkyl-substituted phenyl groups are dimethylphenyl, diethylphenyl, methylethylphenyl, etc., halogen-substituted phenyl groups are dichlorophenyl, etc., and alkyl-substituted benzyl groups are methylbenzyl, dimethylbenzyl, diethyl, etc. Examples of the halogen-substituted benzyl group include chlorobenzyl, dichlorobenzyl, and the like. Examples of the compound include 2,3-dichloro-N-
Ethyl maleimide, 2,3-dichloro-N-isopropyl maleimide, 2,3-dichloro-Nn-butyl maleimide, 2,3-dichloro-N-tertiary butyl maleimide, 2,3-dichloro-Nn -Octyl maleimide,
2,3-dichloro-N-cyclohexylmaleimide,
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- (2,4-dimethylbenzyl) maleimide, 2,3-dichloro-N-
(3,4-Dimethylbenzyl) maleimide, 2,3-dichloro-N-α-methylbenzylmaleimide, 2,3-
Dichloro-N- (2,4-dichlorobenzyl) maleimide, 2,3-dichloro-N- (2-ethyl-6-methylphenyl) maleimide, 2,3-dichloro-N- (2,2
6-dimethylphenyl) maleimide, 2,3-dichloro-N- (2,6-diethylphenyl) maleimide, 2,
Examples thereof include 3-dichloro-N- (2,4-diethylphenyl) maleimide, 2,3-dichloro-N- (2,4,6-trimethylphenyl) maleimide and the like or a mixture thereof.

Further, R ⁴ , R ⁵ and R of the compound group (vi) are
The alkyl group in ⁶ is methyl, ethyl, isopropyl, butyl, tertiary butyl, nonyl, etc., the halogen-substituted alkyl group is dichloromethyl, dichloroethyl, trichloroethyl, etc., and the cycloalkyl group is cyclohexyl, etc. Is fluorine, chlorine, bromine, iodine, an alkoxy group is methoxy, ethoxy, propoxy, etc., an alkenyl group is vinyl, allyl, isopropenyl, etc., an aralkyl group is cumyl, etc., and nonylphenol as a compound, Cumylphenol, 4,6-ditertiary butyl-m-cresol, 1-cyclohexyl-5-methylphenol, 2,6-ditertiary
Butyl-p-cresol, 2-phenylphenol,
2-Butyl-6-ethyl-4-isopropylphenol, 2-bromo-6-chloro-4-dichloromethylphenol, 2-fluoro-4-iodo-3-trichloroethylphenol, 3-hydroxy-5-methoxy. Examples thereof include benzoic acid and 4-ethoxy-2-vinylphenol.

The compounding amount of the triphenylborane-alkylamine complex compound of the present invention can be arbitrarily changed depending on the environment in which the fishing net antifouling agent is applied, but it is usually 1% by weight to less than 25% by weight, preferably 3% by weight to 25% by weight. It is less than wt%. Antifouling agents having a triphenylborane-alkylamine complex compound content of 1% by weight or less do not exhibit sufficient effects. On the other hand, an antifouling agent having a compounding amount of 25% by weight or more does not show a difference in effect from an antifouling agent having a compounding amount of 25% by weight, which is uneconomical because the cost increases. The blending amount of other active ingredients can be arbitrarily changed, but usually 1 to 30% by weight, preferably 3 to 2
It is 5% by weight.

Compound group (v
R ^{7 in} ii) is ethyl, propyl, tertiary butyl, tertiary
Preferred are amyl, tertiary nonyl, tertiary dodecyl, and nonadecyl. As compounds, diethyl pentasulfide, dipropyl tetrasulfide, ditertiary butyl disulfide, ditertiary butyl tetra Sulfid,
Examples thereof include ditertiary amyltetrasulfide, ditertiary nonylpentasulfide, ditertiary dodecylpentasulfide, and dinonadecyltetrasulfide. Also, a mixture of these may be used.

Further, as the polybutene having an average molecular weight of 200 to 1000 used as an elution regulator,
For example, LV-5, LV-10, L manufactured by Nippon Oil Co., Ltd.
V-25, LV-50, LV-100, HV-15, H
Examples thereof include V-35, HV-50, HV-100, HV-300, etc., and a mixture thereof may be used. Also,
Examples of the paraffins used as the dissolution modifier include liquid paraffin, paraffin wax, chlorinated paraffin, and the like, and may be a mixture thereof.

Furthermore, white petrolatum and yellow petrolatum can be used as the petrolatum used as the elution regulator.
The compounding amount of the compound (vii) used as the dissolution modifier, polybutene, paraffins, and petrolatum is 3 to 20% by weight, preferably 5 to 10% by weight.
% By weight. The mixing ratio of each elution regulator can be arbitrarily changed depending on the use conditions.

The anti-fouling agent for fishing nets of the present invention can be easily produced by a usual method. For example, one kind or two or more kinds of triphenylborane-alkylamine complex compounds which are active ingredients, or with them, compound (ii), compound (iii), compound group (iv), compound group (v) and compound group (vi).
To one or more compounds selected from the group consisting of one or more compounds selected from the group of compounds (vii) selected as an elution regulator, polybutene, paraffins and petrolatum, and a resin, and added with an organic solvent. It may be dissolved.

Examples of the resin used here include rosin resin, acrylic resin, polybutene resin, chlorinated rubber resin, vinyl chloride resin, alkyd resin, coumarone resin, ethylene-vinyl acetate resin and the like. One of these resins may be used, or two or more thereof may be used in combination. The resin is not particularly limited to these.

As the organic solvent, a triphenylborane-alkylamine complex compound which is the active ingredient of the present invention, or a compound (ii), compound (iii), compound group (iv), compound group (v) and compound Group (vi)
It is possible to use a solvent that dissolves a compound selected from, for example, xylene, toluene, pseudocumene,
Diethylbenzene, triethylbenzene, mesitylene,
Solvent naphtha, butanol, isopropanol, methyl isobutyl ketone, hexane and the like can be mentioned. Also, a mixture of these may be used. However, since the triphenylborane-alkylamine complex compound of the present invention has a higher solubility in aromatic hydrocarbons than aliphatic hydrocarbons such as hexane, aromatic hydrocarbons are desirable as the solvent. In particular, xylene dissolves the complex compound in an amount of 25% by weight or more, and is most suitable for the solvent of the present invention.

The fishing net antifouling agent of the present invention has low toxicity, high safety, and long-term coelenterates such as hydrozoa,
It exhibits an excellent antifouling effect against the adhesion of shellfish such as barnacles, mussels, oysters, and serpras, staghorn hazelnuts, halibut hazelnuts, octopus hazelnuts, hagfish, and other living organisms, and other organisms. Further, since the active ingredient is dissolved in the organic solvent, a uniform soluble type fishing net antifouling agent can be obtained, and the workability of the net dyeing is further improved.

[0045]

EXAMPLES Synthesis examples and examples are shown below, but the present invention is not limited thereto. In addition, the compounding in an Example shows weight%. Synthesis Example 1 Triphenylborane-n-propylamine complex
To a 1 L four-necked flask equipped with a compound mechanical stirrer, cooling tube, dropping funnel, and thermometer, aqueous solution of triphenylborane sodium hydroxide adduct (reagent of Tokyo Kasei Co., Ltd .; triphenylborane sodium hydroxide addition) 461.0 g of the product content rate (9.6%) was added, and stirring was started. When 10.8 g of n-propylamine (a reagent of Kishida Chemical Co., Ltd.) was slowly added dropwise at room temperature (20 ° C.) over 30 minutes, crystals were immediately precipitated. The reaction was allowed to proceed by stirring at room temperature for 3 hours. After the crystals are collected by suction filtration, they are washed with water to remove excess sodium hydroxide and unreacted n.
-Propylamine was removed. 42.2g when dried
White crystals (yield 90%) were obtained. From IR (infrared absorption spectrum) and elemental analysis values, it was confirmed that the product was the desired product. Synthesis Example 2 Triphenylborane-n-hexadecylami
N -Hexadecylamine (reagent of Wako Pure Chemical Industries, Ltd.) (50.0 g) was placed in a 1 L four-necked flask equipped with a mechanical complex stirrer, cooling tube, dropping funnel, and thermometer. Raise to 75 ° C. After the crystals were completely dissolved, 648.9 g of an aqueous sodium hydroxide adduct solution of triphenylborane (reagent described in Synthesis Example 1) was stirred for 1 hour while maintaining the internal temperature at 70 ° C to 75 ° C. , Drop. After completion of the dropping, the mixture is stirred at 70 ° C. for 3 hours to be reacted. Then, when it was cooled to 30 ° C. or lower, crystals were precipitated.
The crystals were collected by suction filtration, washed with water to remove excess sodium hydroxide and unreacted n-hexadecylamine, and then dried to obtain 90.1 g (yield 90%) of white crystals. . From IR (infrared absorption spectrum) and elemental analysis values, it was confirmed that the product was the desired product. Synthesis Example 3 Triphenylborane-alkylamine complexation
In a 1 L four-necked flask equipped with a mechanical stirrer, cooling tube, dropping funnel, and thermometer, Farmin 80
(Product of Kao Corporation; aliphatic alkylamine having 16 carbon atoms: 6%, aliphatic alkylamine having 18 carbon atoms: 92
%, Alkylamine composition containing 2% of other alkylamine) and 42.8 g are added, and the internal temperature is raised to 75 ° C. After the crystals were completely dissolved, 500.0 g of an aqueous sodium hydroxide adduct solution of triphenylborane (reagent described in Synthesis Example 1) was stirred for 1 hour to bring the internal temperature to 70%.
While maintaining the temperature at ℃ to 75 ℃, add dropwise. 70 after the dropping
Stir at 0 ° C. for 3 hours to react. Then, when it was cooled to 30 ° C. or lower, crystals were precipitated. The crystals were collected by suction filtration, washed with water to remove excess sodium hydroxide and unreacted amine, and then dried to obtain 74.5 g (yield 91%) of white crystals.

The obtained white crystals include triphenylborane-n-hexadecylamine complex compounds and other triphenylborane-C16 aliphatic alkylamine complex compounds, triphenylborane-n-octadecylamine complex compounds and the like. The triphenylborane-C18 aliphatic alkylamine complex compound and other triphenylborane-alkylamine complex compounds corresponding to the raw materials are contained.

By the same method as in Synthesis Example 1 or 2, triphenylborane-alkylamine complex compounds corresponding to all alkylamines having 3 to 30 carbon atoms can be synthesized. Further, a triphenylborane-alkylamine composition can be synthesized by the same method as in Synthesis Example 3 using an alkylamine composition containing two or more alkylamine compounds having 3 to 30 carbon atoms. .
The alkylamine composition that can be used may contain any proportion of alkylamine, may contain other compounds, and may contain any proportion of various alkylamine compounds. Table 1 summarizes the melting points or shapes of the triphenylborane-alkylamine compounds or compositions synthesized by these methods and their solubilities in xylene at 20 ° C.

Table 1 ──────────────────────────────────── Synthesized compound Melting point or shape Solubility in xylene (20 ℃) ──────────────────────────────────── Triphenylborane-205.4-209.5 ℃ (decomposition) ) 1.0 wt% methylamine complex compound triphenylborane-167.0 to 174.0 ° C (decomposition) 3.5 wt% ethylamine complex compound triphenylborane-154.0 to 161.0 ° C 4.5 wt% isopropylamine complex compound triphenylborane- 107.4-108.4 ° C 30% by weight or more n-propylamine complex compound triphenylborane-109.5-111.5 ° C 27% by weight n-butylamine complex compound triphenylborane-81.3-85.7 ° C 30% by weight or more n-hexylamine complex compound Triphenylborane-79.0 to 80.5 ° C 30% by weight or more n-octylamine complex compound triphenylborane-60.5 to 61.3 ° C 30% by weight or more n-dodecylamine complex compound triphenylborane-63.0 to 65.5 ° C 30% by weight or more n- Hexadecylamine complex compound triphenylborane-63.0 to 64.0 ° C 30% by weight or more n-octadecylamine complex compound triphenylborane-111.0 to 112.5 ° C 25% by weight Secondary butylamine complex compound triphenylborane-oil 30% by weight 2-Ethylhexylamine complex compound Reaction composition of Synthesis Example 3 57.0 to 60.3 ° C 30% by weight or more ──────────────────────────── Example 1 An antifouling agent for fishing nets was prepared by mixing the components according to the following formulation example. The antifouling agents obtained in any of the following formulation examples were uniform solutions containing no insoluble matter. Prescription example 1
To 20 are triphenylborane-n-propylamine complex compound, triphenylborane-n-octylamine complex compound, triphenylborane-2-ethylhexylamine complex compound, triphenylborane-n-dodecylamine complex compound, triphenylborane-n-dodecylamine complex compound, Any of phenylborane-n-octadecylamine complex compounds is contained as an active ingredient, and Formulation Examples 21 to 30 include triphenylborane-alkylamine complex compounds other than the 5 complex compounds and the following 1 complex compound. Is contained as an active ingredient. In addition, Formulation Examples 31 to 40 contain the triphenylborane-n-hexadecylamine complex compound or the reaction composition of Synthesis Example 3 as an active ingredient. Formulation Example 1 Triphenylborane-n-propylamine complex compound 10% Polybutene (LV-50) 7.5% Yellow petrolatum 7.5% Acrylic resin (50% xylene liquid) 20% Xylene 55% Formulation example 2 Triphenylborane -N-octylamine complex compound 10% Polybutene (LV-50) 7.5% Liquid paraffin (reagent) 7.5% Acrylic resin (50% xylene solution) 20% Xylene 55% Formulation example 3 Triphenylborane-2- Ethylhexylamine complex compound 10% Polybutene (LV-50) 7.5% Yellow petrolatum 7.5% Acrylic resin (50% xylene solution) 20% Xylene 55% Formulation example 4 Triphenylborane-n-dodecylamine complex compound 10% Polybutene (LV-50) 7.5% White petrolatum 7.5% Acrylic resin (50% Xylene liquid) 20% xylene 55% Formulation example 5 Triphenylborane-n-octadecylamine complex compound 10% Polybutene (LV-50) 7.5% Yellow petrolatum 7.5% Acrylic resin (50% xylene liquid) 20% Xylene 55% Formulation example 6 Triphenylborane-n-propylamine complex compound 8% Triphenylborane-2-ethylhexylamine complex compound 8% Polybutene (LV-50) 5% White petrolatum 5% Acrylic resin (50% xylene solution) 20 % Xylene 54% Formulation Example 7 Triphenylborane-n-propylamine complex compound 8% Triphenylborane-n-dodecylamine complex compound 8% Polybutene (LV-50) 5% Yellow petrolatum 5% Acrylic resin (50% xylene liquid ) 20% xylene 54% Formulation Example 8 Triphenyl Bora -N-Propylamine complex compound 8% Triphenylborane-n-octadecylamine complex compound 8% Polybutene (LV-50) 5% Yellow petrolatum 5% Acrylic resin (50% xylene liquid) 20% Xylene 54% Prescription example 9 Tri Phenylborane-2-ethylhexylamine complex compound 8% Triphenylborane-n-dodecylamine complex compound 8% Polybutene (LV-50) 5% White petrolatum 5% Acrylic resin (50% xylene liquid) 20% Xylene 54% Prescription example 10 Triphenylborane-2-ethylhexylamine complex compound 8% Triphenylborane-n-octadecylamine complex compound 8% Polybutene (LV-50) 5% White petrolatum 5% Acrylic resin (50% xylene liquid) 20% Xylene 54% Prescription example 11 Triphenylborane- -Octadecylamine complex compound 8% Triphenylborane-n-dodecylamine complex compound 8% Polybutene (LV-50) 5% White petrolatum 5% Acrylic resin (50% xylene solution) 20% Xylene 54% Formulation example 12 Triphenylborane -N-Propylamine complex compound 8% Triphenylborane-Secondary butylamine complex compound 8% Ditertiary nonylpentasulfide 5% Yellow petrolatum 5% Acrylic resin (50% xylene solution) 20% Xylene 54% Formulation Example 13 Triphenylborane-2-ethylhexylamine complex compound 8% Triphenylborane-secondary butylamine complex compound 8% Ditertiary nonylpentasulfide 5% Liquid paraffin (reagent) 5% Acrylic resin (50% xylene Liquid) 20% xylene 54% Formulation Example 14 Triphe Nylborane-n-dodecylamine complex compound 8% Triphenylborane-secondary butylamine complex compound 8% Polybutene (LV-50) 5% White petrolatum 5% Acrylic resin (50% xylene liquid) 20% Xylene 54% Formulation example 15 Triphenylborane-n-octadecylamine complex compound 8% Triphenylborane-secondary butylamine complex compound 8% Polybutene (LV-50) 5% White petrolatum 5% Acrylic resin (50% xylene liquid) 20% Xylene 54% Formula Example 16 Triphenylborane-n-propylamine complex compound 8% 1,3-dicyanotetrachlorobenzene 8% Polybutene (LV-50) 5% Yellow petrolatum 5% Acrylic resin (50% xylene solution) 20% Pseudocumene 19% Solvent naphtha 35% Prescription Example 17 Trif Nylborane-n-octylamine complex compound 8% 2,3-dichloro-N-benzylmaleimide 8% Polybutene (LV-50) 5% Yellow petrolatum 5% Acrylic resin (50% xylene liquid) 20% Xylene 54% Formulation example 18 Triphenylborane-2-ethylhexylamine complex compound 8% 2,3-dichloro-N- (2-ethyl-6-methylphenyl) maleimide 8% Ditertiary nonylpentasulfide 5% Yellow petrolatum 5% Acrylic resin (50% xylene solution) 20% xylene 54% Formulation Example 19 Triphenylborane-n-dodecylamine complex compound 8% Nonylphenol 8% Ditertiary nonylpentasulfide 5% White petrolatum 5% Acrylic resin (50% xylene Liquid) 20% xylene 54% Formulation Example 20 Triphenylborane-n- Octadecylamine complex compound 8% 4,6-Ditertiary butyl-m-cresol 8% Ditertiary nonylpentasulfide 5% Liquid paraffin (reagent) 5% Acrylic resin (50% xylene liquid) 20% Xylene 54% Formulation example 21 Triphenylborane-n-butylamine complex compound 10% Ditertiary nonylpentasulfide 7.5% Liquid paraffin (reagent) 7.5% Acrylic resin (50% xylene solution) 20% Xylene 55 % Formulation Example 22 Triphenylborane-n-hexylamine complex compound 10%
Ditertiary nonylpentasulfide 7.5% Yellow petrolatum 7.5% Acrylic resin (50% xylene solution) 20% Xylene 55% Formulation example 23 Triphenylborane-secondary butylamine complex compound 10% Polybutene (LV -50) 7.5% Yellow petrolatum 7.5% Acrylic resin (50% xylene solution) 20% Xylene 55% Formulation example 24 Triphenylborane-n-butylamine complex compound 8% 2- (Thiocyanomethylthio) benzothiazole 8 % Polybutene (LV-50) 5% Yellow petrolatum 5% Acrylic resin (50% xylene solution) 20% Xylene 54% Formulation example 25 Triphenylborane-n-hexylamine complex compound 8% Tetraethyl thiuram disulfide 8% Polybutene (LV-50) 5% Yellow petrolatum 5% Acrylic resin (5 % Xylene solution) 20% xylene 54% Formulation example 26 Triphenylborane-secondary butylamine complex compound 8% 2,3-dichloro-N- (2,6-diethylphenyl) maleimide 8% Polybutene (LV-50) 5 % White petrolatum 5% Acrylic resin (50% xylene solution) 20% Xylene 54% Formulation example 27 Triphenylborane-n-butylamine complex compound 8% Triphenylborane-n-hexylamine complex compound 8% Polybutene (LV-50) 5% Yellow petrolatum 5% Acrylic resin (50% xylene solution) 20% Xylene 54% Formulation example 28 Triphenylborane-secondary butylamine complex compound 8% Tetraethylthiuram disulfide 8% Polybutene (LV-50) 5% Yellow Vaseline 5% Acrylic resin (50% xylene solution) 20% Siren 54% Formulation Example 29 Triphenylborane-n-hexylamine complex compound 8% 2,3-Dichloro-N-benzylmaleimide 8% Polybutene (LV-50) 5% Yellow petrolatum 5% Acrylic resin (50% xylene solution) 20% Xylene 54% Formulation Example 30 Triphenylborane-n-butylamine complex compound 8% 4,6-Ditertiary butyl-m-cresol 8% Ditertiary nonylpentasulfide 5% Liquid paraffin (reagent) 5% Acrylic resin (50% xylene liquid) 20% Xylene 54% Formulation example 31 Triphenylborane-n-hexadecylamine complex compound 10% Polybutene (LV-50) 7.5% Yellow petrolatum 7.5% Acrylic resin ( 50% xylene solution) 20% xylene 55% Formulation Example 32 Triphenylborane-n-hexade Ruamine complex compound 2% Triphenylborane-n-octadecylamine complex compound 14% Polybutene (LV-50) 5% Liquid paraffin 5% Acrylic resin (50% xylene solution) 20% Xylene 54% Prescription example 33 Triphenylborane-n -Hexadecylamine complex compound 8% Triphenylborane-n-dodecylamine complex compound 8% Polybutene (LV-50) 5% White petrolatum 5% Acrylic resin (50% xylene liquid) 20% Xylene 54% Prescription example 34 Triphenyl Borane-n-hexadecylamine complex compound 8% 1,3-didianotetrachlorobenzene 4% Ditertiary nonylpentasulfide 8% Liquid paraffin 6% Acrylic resin (50% xylene liquid) 20% Fusudocumene 20% Solvent Naphtha 34% Prescription Example 35 Trif Phenylborane-n-hexadecylamine complex compound 8% Tetraethylthiuram disulfide 8% Polybutene (LV-50) 5% Liquid paraffin 5% Acrylic resin (50% xylene liquid) 20% Xylene 54% Formulation example 36 Triphenylborane -N-hexadecylamine complex compound 8% 2,3-dichloro-N-benzylmaleimide 8% polybutene (LV-50) 5% yellow petrolatum 5% acrylic resin (50% xylene solution) 20% xylene 54% Formulation Example 37 Triphenylborane-n-hexadecylamine complex compound 8% Nonylphenol 8% Ditertiary nonylpentasulfide 5% White petrolatum 5% Acrylic resin (50% xylene solution) 20% Xylene 54% Formulation example 38 Synthesis example 3 Reaction composition synthesized by 10% polybutene (L -50) 7.5% Yellow petrolatum 7.5% Acrylic resin (50% xylene solution) 20% Xylene 55% Formulation example 39 Reaction composition synthesized by Synthesis example 3 10% Polybutene (LV-50) 7.5% Liquid paraffin (reagent) 7.5% Acrylic resin (50% xylene solution) 20% Xylene 55% Formulation example 40 Reaction composition synthesized according to Synthesis Example 3 8% 1,3-Didianotetrachlorobenzene 4% Ditertiary Nonylpentasulfide 8% Liquid paraffin 6% Acrylic resin (50% xylene solution) 20% Fusoidcumene 20% Solvent naphtha 34% Experiment 1 The antifouling agent for fishing nets of Example 1 (Formulation Examples 1-26) of the present invention After dip-coating each on Tetoron knotless net (1000/26 3rd dimension) and air-drying, 4 from August 1993
For a month, the sea was maintained at a depth of about 10 m below the sea level in the sea near Konbumori, Hokkaido. The state of fouling of the net was evaluated according to the criteria in Table 2, and the results are summarized in Table 3.

The formulation of the comparative example of Experiment 1 is as follows. The antifouling agents obtained by the formulations of Comparative Examples 2 and 3 are dispersion liquids of solid fine particles. Comparative Example 1 Tetraethyl thiuram disulfide 15% Acrylic resin (50% xylene solution) 50% Xylene 35% Comparative Example 2 Zinc bis (dimethyldithiocarbamoyl) ethylenebisdithiocarbamate 10% Polybutene (LV-50) 5% Yellow petrolatum 5% Acrylic resin (50% xylene solution) 20% Xylene 55% Comparative Example 3 Triphenylborane-pyridine complex compound 10% Polybutene (LV-50) 5% Yellow petrolatum 5% Acrylic resin (50% xylene solution) 20% Xylene 55% Table 2 ─────────────────────────────────────Rating status ──── ──────────────────────────────────────── A No deposit (0% of the area of the fishing net is contaminated) B Slight deposit With However, there is no problem in practical use. (Fouling area of fishing net is 0 to 10%) C: There are many deposits and it can no longer be used as a fishing net (Fouling area of fishing net is 10 to 50%) D: A large amount of deposits are deposited ( (Fouling area of fishing nets 50% or more) ──────────────────────────────────────────── ──────────────────────────────── Aging 1 month 2 months 3 months 4 months ──── ──────────────────────────────── Prescription example 1 A A A A Prescription example 2 A A A B Prescription example 3 A A A A Prescription example 4 A A A A Prescription example 5 A A A A Prescription example 6 A A A A Prescription example 7 A A A A Prescription example 8 A A A A A Prescription example 9 A A A A Prescription example 10 A A A A Prescription example 11 A A A B Formulation Example 12 A A A A Formulation Example 13 A A A B Formulation Example 14 A A A A Formulation Example 15 A A A A Formulation Example 16 A A A A Formulation Example 17 A A A B Formulation Example 18 A A A B Formulation Example 19 A A A A Formulation Example 20 A A A A Formulation Example 21 A A A B Formulation Example 22 A A A A Formulation Example 23 A A A A Formulation Example 24 A A A A Formulation Example 25 A A A B Prescription Example 26 A A A B ──────────────────────────────────── Comparative Example 1 D Comparative Example 2 A A A B Comparative Example 3 A A A B ───────────────────────────────────── Untreated net D ──────────────────────────────────── Most of the attached organisms are hydrozoa. It was

From Table 3, it was found that, in all of Formulation Examples 1 to 26, no hydro worms adhered to the fishing net invaded for at least 3 months, and the efficacy was equal to or higher than that of Comparative Examples 2 and 3. That is, the triphenylborane-alkylamine complex compound of the present invention is equivalent to or more than the bis (dimethyldithiocarbamoyl) ethylene zinc bisdithiocarbamate zinc and the triphenylborane-pyridine complex compound for coelenterates such as hydrozoa. It has been found to have a very strong and lasting practical effect. Experiment 2 The antifouling agents for fishing nets of Example 1 (formulation examples 1 to 30) of the present invention were each applied by dip coating to a polyethylene knotless net (6 nodes, 400 denier / 60) and air-dried. 0.5 months below sea level in Tanabe Bay, Wakayama Prefecture, for 6 months from April 2014
The sea was kept at m. The state of fouling of the net was evaluated according to the criteria in Table 2, and the results are summarized in Table 4.

The formulation of the comparative example is as follows. Comparative Example 1 Tetraethyl thiuram disulfide 15% Acrylic resin (50% xylene liquid) 50% Xylene 35% Table 4 ────────────────────────── ──────────── Date 1 month 2 months 3 months 4 months 5 months 6 months ────────────────── ────────────────── Prescription Example 1 A A A A A A A Prescription Example 2 A A A A A A A Prescription Example 3 A A A A A A A Prescription Example 4 A A A A A A Prescription example 5 A A A A A A A Prescription example 6 A A A A A A Prescription example 7 A A A A A A Prescription example 8 A A A A A A Prescription example 9 A A A A A A Prescription Example 10 A A A A A A A Formulation Example 11 A A A A A A A Formulation Example 12 A A A A A A A A Formulation Example 13 A A A A A A A Formulation Example 14 A A A A A Formulation Example 15 A A A A A A A Formulation Example 16 A A A A A A A Formulation Example 17 A A A A A A A Formulation Example 18 A A A A A A A Formulation Example 19 A A A A A A Formulation Example 20 A A A A A A Formulation Example 21 A A A A B B Formulation Example 22 A A A A B C Formulation Example 23 A A A A B C Formulation Example 24 A A A A A B B Formulation Example 25 A A A A A B Formulation Example 26 A A A A A B B Formulation Example 27 A A A A A B Formulation Example 28 A A A A A B B Formulation Example 29 A A A A A B B B Formulation Example 30 A A A A B C --- ──────────────────────────────── Comparative Example 1 B C D ───────────── ──────────────────────── Untreated net D ────────────────────── ─────── ────── Comparative Example 1, and, in the non-processing network, a number of fouling organisms, including barnacles and Kasanekanzashi is attached. On the other hand, in Formulation Examples 1 to 20, no adhesion of shellfish, tubular polychaetes, and other organisms was observed on all nets that had been invaded for 6 months. Experiment 3 The antifouling agents for fishing nets of Example 1 (Formulation Examples 31 to 40) of the present invention were each applied by dip coating to a polyethylene knotless net (6 sections, 400 denier / 60 pieces) and air-dried.
For six months from April 2014, it was about 0 below sea level in Tanabe Bay, Wakayama Prefecture.
The sea was maintained at 5 m. The state of fouling of the net was evaluated according to the criteria in Table 2, and the results are summarized in Table 5.

The formulation of the comparative example is as follows. Comparative Example 1 Tetraethyl thiuram disulfide 15% Acrylic resin (50% xylene solution) 50% Xylene 35% Table 5 ───────────────────────── ──────────── Date 1 month 2 months 3 months 4 months 5 months 6 months ────────────────── ────────────────── Formulation Example 31 A A A A A A A Formulation Example 32 A A A A A A A Formulation Example 33 A A A A A A A Formulation Example 34 A A A A A A Formulation Example 35 A A A A A A A Formulation Example 36 A A A A A A A Formulation Example 37 A A A A A A A Formulation Example 38 A A A A A A Formulation Example 39 A A A A Formulation Example 40 A A A A A A A ──────────────────────────────────── Comparative Example 1 B C ──────────────────────────────────── Untreated net D ─────────── ────────────────────────── Comparative Example 1 and the untreated net contain many adherent organisms including barnacles and magnolias It adhered. On the other hand, in all of Prescription Examples 31 to 40, at least 6
No shellfish, polychaete, or other organisms were attached to any nets that had been invaded for months. It was found that both the triphenylborane-alkylamine complex compound synthesized from the reagent alkylamine compound and the triphenylborane-alkylamine composition synthesized from the industrial product alkylamine composition exhibited extremely strong effects.

That is, a triphenylborane-alkylamine complex compound in which R ¹ is n-octyl, 2-ethylhexyl, n-dodecyl, n-hexadecyl, n-octadecyl, in other words, R ¹ has 8 carbon atoms. ^No. 18 to a fishing net antifouling agent containing a complex compound as an active ingredient, and a fishing net antifouling agent containing a complex compound in which R ¹ is n-propylamine as an active ingredient, alone or in combination with other active ingredients. It was found that even when used in combination, it exhibits a very strong and lasting practical effect. In addition, it has been found that the triphenylborane-alkylamine composition synthesized from the alkylamine composition also exhibits a very strong and lasting practical effect, similar to the above-mentioned active ingredients.

In Prescription Examples 21 to 30, after 4 months,
Adhesion of some organisms was observed. But at least 4
It was found that no organisms adhered to the net for a month, which had a sufficiently practical effect. That is, a triphenylborane-alkylamine complex compound in which R ¹ is n-butyl, n-hexyl, or secondary butyl, in other words, a complex in which the carbon number of R ¹ is not 3 or 8 to 18 It has been found that even a fishing net antifouling agent containing a compound as an active ingredient exhibits a sufficiently practical effect. In particular, the fact that it was very effective for the adhesion of shellfish such as barnacles and polychaetes such as magnolias is remarkable.

[0055]

From the results of Experiments 1, 2 and 3, the fishing net antifouling agent containing the triphenylborane-alkylamine complex compound of the present invention as an active ingredient exhibits excellent effects on all marine periphytic organisms. I found it to have. In particular, with conventional antifouling agents, it is difficult to prevent adhesion, and if it adheres, it is very damaging to coelenterants such as hydro worms, shellfish such as barnacles, and polychaetes such as magnolia Proved to be effective. Furthermore, since the complex compound of the present invention is soluble in an organic solvent such as xylene, a uniform soluble type fishing net antifouling agent can be prepared, and the workability of net dyeing is remarkably improved, and thus the dispersion type Superior to fishing net antifouling agents. That is, the present invention is effective against all periphytic organisms, including coelenterates such as hydrozoa, shellfish such as barnacles, and tubular polychaetes such as magnolia japonicus, and an organic solvent with good workability. It is intended to provide a soluble type fishing net antifouling agent. Further, it has been confirmed that the antifouling agent has low toxicity and high safety.

 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Kazuki Katsuyama 1-6-7 Yushima, Bunkyo-ku, Tokyo Yoshitomi Pharmaceutical Co., Ltd. Tokyo branch office

Claims (16)

[Claims] 1. A compound of the general formula (In the formula, R ¹ represents an alkyl group having 3 to 30 carbon atoms.) One or more triphenylborane-alkylamine complex compounds represented by the formula (1) is contained as an active ingredient, and these are further contained. An organic solvent-soluble type fishing net antifouling agent, which comprises an organic solvent that dissolves. 2. A triphenylborane-alkylamine complex compound is used in an amount of 1% by weight based on the total amount of one or more triphenylborane-alkylamine complex compounds.
To less than 25% by weight, the fishing net antifouling agent according to claim 1. 3. The triphenylborane according to claim 1.
An organic solvent-dissolving type fishing net antifouling agent for preventing adherence of coelenterates, which comprises one or more alkylamine complex compounds as an active ingredient, and further comprises an organic solvent capable of dissolving these. 4. The triphenylborane according to claim 1.
An organic solvent-soluble antifouling agent for aquaculture nets, comprising one or more alkylamine complex compounds as active ingredients, and further comprising an organic solvent capable of dissolving these. 5. The triphenylborane according to claim 1.
Of the alkylamine complex compounds, one or more complex compounds having an alkylamine having 3 or 8 to 18 carbon atoms are contained as an active ingredient, and further, an aromatic hydrocarbon capable of dissolving these An organic solvent-soluble type fishing net antifouling agent. 6. The triphenylborane according to claim 1.
Of the alkylamine complex compounds, alkylamine is n-
The propylamine, n-octylamine, 2-ethylhexylamine, n-dodecylamine, n-hexadecylamine, n-octadecylamine complex compound of 1 type or 2 types or more is contained as an active ingredient. Fishing net antifouling agent. 7. One or more triphenylborane-alkylamine complex compounds according to claim 1, 5 or 6, and 1,3-dicyanotetrachlorobenzene, 2-
(Thiocyanomethylthio) benzothiazole, a general formula: (In the formula, R ² represents an alkyl group having 1 to 4 carbon atoms.) One or more tetraalkyl thiuram disulfides represented by the general formula: (In the formula, R ³ represents hydrogen, an alkyl group, a halogen-substituted alkyl group, a cycloalkyl group, a phenyl group, an alkyl-substituted phenyl group, a halogen-substituted phenyl group, a benzyl group, an alkyl-substituted benzyl group, or a halogen-substituted benzyl group.) One or more of 2,3-dichloromaleimides represented by the general formula: (In the formula, R ⁴ , R ⁵ , and R ⁶ are the same or different and each represents hydrogen, an alkyl group, a halogen-substituted alkyl group, a cycloalkyl group, a phenyl group, a halogen, an alkoxy group, a carbonyl group, an alkenyl group, or an aralkyl group. (1) or (2) or more of the phenols represented by the formula (1) or (2) or more, as an active ingredient, and an organic solvent capable of dissolving these. An organic solvent-soluble type fishing net antifouling agent. 8. A general formula R ⁷ — (S) _n —R ⁷ (wherein R ⁷ represents an alkyl group having 1 to 20 carbon atoms,
n shows the integer of 2-10. ), The dialkyl polysulfides having an average molecular weight of 200 to 1000
The fishing net antifouling agent according to claim 1, characterized in that the fishing net antifouling agent comprises one or more selected from polybutene, paraffins and petroleum jelly having the formula (1). 9. A triphenylborane-n-hexadecylamine complex compound. 10. A fishing net antifouling agent containing the triphenylborane-n-hexadecylamine complex compound according to claim 9. 11. An organic solvent-soluble type fishing net comprising the triphenylborane-n-hexadecylamine complex compound according to claim 9 as an active ingredient, and further comprising an organic solvent capable of dissolving the compound. Antifouling agent. 12. The compounding amount of the triphenylborane-n-hexadecylamine complex compound according to claim 9 is 0.1% by weight to 30% by weight or less, and the compounding amount according to claim 10 or 11. Fishing net antifouling agent. 13. An organic solvent-soluble cavity containing the triphenylborane-n-hexadecylamine complex compound according to claim 9 as an active ingredient, and further comprising an organic solvent capable of dissolving the compound. A fishing net antifouling agent for preventing the adhesion of intestinal animals. 14. An organic-solvent-type aquaculture comprising the triphenylborane-n-hexadecylamine complex compound according to claim 9 as an active ingredient, and further comprising an organic solvent capable of dissolving this. Antifouling agent for nets. 15. The triphenylborane-n-hexadecylamine complex compound according to claim 9, 1,3-dicyanotetrachlorobenzene, 2- (thiocyanomethylthio) benzothiazole, and a compound represented by the general formula: (In the formula, R ² represents an alkyl group having 1 to 4 carbon atoms.) One or more tetraalkyl thiuram disulfides represented by the general formula: (In the formula, R ³ represents hydrogen, an alkyl group, a halogen-substituted alkyl group, a cycloalkyl group, a phenyl group, an alkyl-substituted phenyl group, a halogen-substituted phenyl group, a benzyl group, an alkyl-substituted benzyl group, or a halogen-substituted benzyl group.) One or more of 2,3-dichloromaleimides represented by the general formula: (In the formula, R ⁴ , R ⁵ , and R ⁶ are the same or different and each represents hydrogen, an alkyl group, a halogen-substituted alkyl group, a cycloalkyl group, a phenyl group, a halogen, an alkoxy group, a carbonyl group, an alkenyl group, or an aralkyl group. (1) or (2) or more of the phenols represented by the formula (1) or (2) or more, as an active ingredient, and an organic solvent capable of dissolving these. An organic solvent-soluble type fishing net antifouling agent. 16. A compound represented by the general formula R ⁷ — (S) _n —R ⁷ (wherein R ⁷ represents an alkyl group having 1 to 20 carbon atoms,
n shows the integer of 2-10. ), The dialkyl polysulfides having an average molecular weight of 200 to 1000
The fishing net antifouling agent according to claim 10, 11, 12, 13, 14 or 15, containing one or more selected from polybutene, paraffins, and petrolatum having.