JP2002356475A - New addition salt of triphenyl(alkylenediamine) boron and pyrithione and application thereof - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a practical underwater antipollution agent improved in preservation stability and having low toxicity and a little fear of environmental pollution to aquatic pollution lives such as coelenterates such as hydrozoan and obelia, shellfishes and tubicolous polychaete adhered on a fixed shore net, a fishing net for culturing and a bottom of a ship and an active ingredient therefor. SOLUTION: The aquatic pollution lives are prevented from adhering and growing on the fixed shore net, the fishing net for culturing and the bottom of the ship by using the underwater antipollution agent comprising a new addition salt of a triphenyl(alkylenediamine) boron and pyrithione.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a novel addition salt of triphenyl (alkylenediamine) boron with pyrithione and an antifouling agent containing water as an active ingredient. More specifically, including fishing net antifouling agents to prevent aquatic fouling organisms from adhering to aquaculture or stationary fishing nets, ship bottoms, materials such as floats and ropes used for fishing nets, nuclear and thermal power plants The present invention relates to an underwater antifouling agent such as an antifouling paint for preventing underwater fouling organisms from adhering to and propagating in a condenser cooling water channel.

[0002]

2. Description of the Related Art Ship bottoms, aquaculture or stationary fishing nets are kept in the sea or in freshwater for a long period of time, and are used for worms such as hydroids and oberia, shellfish, tubal polychaetes, seaweeds, and the like. Aquatic organisms such as bryozoans and molluscs attach. At present, the attachment of these aquatic organisms requires a great deal of effort and cost to maintain the objects to be contaminated in order to reduce large economic losses.

Until now, various studies and proposals have been made as countermeasures against attached organisms. It is known that a series of organotin compounds are effective for practical use. However, organotin compounds are generally highly toxic, and careless handling of commodities containing them may cause harm to the handlers and may destroy the environment. For these reasons, the emergence of underwater antifouling agents such as low-polluting fishing net antifouling agents and antifouling paints has come to be desired.

For example, Japanese Patent Publication No. Sho 51-10849 discloses an antifouling paint in water containing a benzothiazole compound as an active ingredient.
Japanese Patent Publication No. 284275 and Japanese Patent Publication No. 1-1606 disclose various fishing net antifouling agents, antifouling paint compositions and fishing net antifouling agent solutions in which a tetraalkylthiuram disulfide compound is combined with other compounds. Kosho 54-14610
JP-A-54-15939 discloses an antibacterial agent and an underwater antifouling paint containing a pyrithione metal salt as an active ingredient, and Japanese Patent Publication No. Sho 61-50984 discloses a marine composition containing a 3-isothiazolone compound as an active ingredient. The antifouling agent for the construct is disclosed in Japanese Patent Publication No. Hei.
JP-A-53-9320, JP-A-5-201804
JP, JP-A-6-100405, JP-A-6-16-1
No. 00408 and the like each disclose an antifouling paint containing a maleimide compound as an active ingredient.

However, all of these antifouling agents have a weak effect of preventing adhesion to hydro-insects such as hydroids and oberia, shellfish and tubal polychaetes, and are found in the sea area where coelenterates occur and shellfish and tubal polychaeta. It could not be used in the outbreak area. The coelenterate outbreak area is mainly the Tohoku region and the coast of Hokkaido,
Shellfish and tubal polychaetes occur frequently in the eastern and western Japan waters.

In order to solve such a problem, it has recently been proposed to use a triphenylboronamine-added compound having a physiologically active effect particularly on a coelenterant.

For example, US Pat. No. 3,111,679 discloses, as antifouling active compounds, an addition compound of triphenylboron with a substituted or unsubstituted pyridine and an addition compound with an aliphatic amine. There is no description that there is. JP-A-8-295608 discloses a fishing net antifouling agent containing a triphenylboronamine-added compound as an active ingredient, and JP-A-8-295609 discloses a solution containing a triphenylboronoctadecylamine-added compound. In this specification, for coelenterates,
Fishing net antifouling agents exhibiting excellent antifouling effects over a long period of time have been proposed. International application WO 97/27254 discloses antifouling paints in water containing a triphenylboron rosinamine adduct, respectively.

However, these antifouling agents have an excellent antifouling effect on coelenterates, but have a weak anti-adhesion effect on shellfish and tubal polychaetes, and effectively prevent the adhesion of these organisms. At present, it cannot be prevented. The specific damage caused by the attachment of shellfish and tubal polychaete is, firstly, when lifting fishing nets to the sea, such as feeding and changing nets,
The attachment of these organisms increases the weight of the fishing net and makes it difficult to work.Secondly, these attached organisms are covered with hard calcareous material, which may damage the cultured fish and reduce its commercial value. Thirdly, it is extremely difficult to remove these attached organisms because they adhere very strongly.

As described above, in the case of fishing nets for aquaculture, the damage caused by shellfish and tubal polychaete is particularly large as compared with the damage caused by other attached organisms, and prevention of the attachment of these organisms has attracted attention in recent years. At present, even triphenylboronamine adduct is difficult. Therefore, there is a strong demand for the development of an antifouling agent for aquaculture that is effective for shellfish and tubal polychaetes.

It is known that cuprous oxide is effective for shellfish. In fact, it has been confirmed that a copper-based antifouling agent is effective for shellfish. And other aquatic fouling organisms. However, copper-based antifouling agents have various disadvantages. For example, the use of copper, a heavy metal, may have an adverse effect on the environment. In fact, in some areas of pearl culture, the use of copper-based antifouling agents is prohibited. Furthermore, fishing nets treated with a copper-based antifouling agent are hard and heavy, so that workability at the time of feeding and changing nets is poor.

[0011]

DISCLOSURE OF THE INVENTION The present invention is superior to hydropests, worms such as oberia, and aquatic fouling organisms such as shellfish and tubal polychaete, which are mainly attached to fishing nets for stationary and aquaculture. It is an object of the present invention to provide a low-polluting, practical underwater antifouling agent exhibiting an antifouling effect and its active ingredient.

[0012]

Means for Solving the Problems The present inventors have made intensive studies to overcome the above-mentioned drawbacks of the conventional underwater antifouling agent, and as a result, have improved storage stability and low toxicity. We have invented an underwater antifouling agent that is less likely to cause environmental pollution. More specifically, a novel triphenyl (alkylenediamine) boron and pyrithione, which exhibit an excellent antifouling effect against the adhesion of coelenterates such as hydro worms and oberia, shellfish, tubal polychaete, and other organisms. The addition salt was found, and the present invention was completed.

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

Embedded image (Wherein n represents an integer of 2 or 3), a novel addition salt of triphenyl (alkylenediamine) boron and pyrithione, (2): addition of triphenyl (alkylenediamine) boron and pyrithione An underwater antifouling agent comprising a salt as an active ingredient, (3): an underwater antifouling agent, wherein the underwater antifouling agent is any of an underwater pest control agent, an underwater antifouling paint, and a fishing net antifouling agent. (4): an addition salt of triphenyl (alkylenediamine) boron and pyrithione, 1,3-dicyanotetrachlorobenzene (hereinafter also referred to as compound (i)), 2- (thiocyanomethylthio) benzothiazole (hereinafter, referred to as compound (i)) Compound (i
i)), general formula (2)

Embedded image (In the formula, R ¹ represents an alkyl group having 1 to 4 carbon atoms.) Tetraalkylthiuram disulfides (hereinafter, also referred to as compound group (iii)) represented by general formula (3)

Embedded image Or the general formula (4)

Embedded image (Wherein R ² and R ³ represent an alkyl group having 1 to 4 carbon atoms;
Represents an integer of 2 or 3, and M represents a metal of zinc, iron, manganese, or copper. )) (Hereinafter also referred to as compound group (iv)) represented by the general formula (5)

Embedded image (Where p is an integer of 2 or 3, and M is as defined above) (hereinafter also referred to as compound group (v)) represented by the following general formula (6):

Embedded image (In the formula, R ⁴ represents hydrogen, an alkyl group, a halogen-substituted alkyl group, a cycloalkyl group, a phenyl group, a halogen-substituted phenyl group, an alkyl-substituted phenyl group, a benzyl group, a halogen-substituted benzyl group, or an alkyl-substituted benzyl group. 2,3-dichloromaleimide compound (hereinafter also referred to as compound group (vi)) represented by general formula (7)

Embedded image (Wherein X ¹ and X ² are the same or different and each represent a hydrogen, a halogen or an alkyl group, and R ⁵ represents an alkyl group, a substituted phenyl group or a substituted benzyl group). (Also referred to as (vii)) or the like. (5): General formula (8) as an elution modifier

Embedded image (Wherein R ⁶ represents an alkyl group having 1 to 20 carbon atoms, and q represents 2
And an integer of 10 to 10. A) selected from the group consisting of dialkyl polysulfides (hereinafter also referred to as compound group (viii)) represented by the formula (1), polybutene having an average molecular weight of 200 to 1,000, paraffin, vaseline and silicone oil.
(2)-characterized by containing a species or two or more species
(4) The underwater antifouling agent according to (4).

[0014]

BEST MODE FOR CARRYING OUT THE INVENTION An addition salt of triphenyl (alkylenediamine) boron represented by the general formula (1) and pyrithione, which is used as an active ingredient of the underwater antifouling agent of the present invention, is produced by the following method. be able to.

Embedded image

Embedded image (In the formula, n represents an integer of 2 or 3.)

That is, the novel addition salt of triphenyl (alkylenediamine) boron and pyrithione of the present invention is obtained by reacting 1 mol of triphenyl (alkylenediamine) boron with 1 mol of pyrithione in an organic solvent. Can be manufactured. Here, triphenyl (alkylenediamine) boron is disclosed in JP-A-2000-143.
It can be produced according to Synthesis Example 4 of Japanese Patent Publication No. 672.

The production method of the above reaction formula will be described in more detail. First, triphenyl (alkylenediamine)
Boron is synthesized by a method according to Synthesis Example 4 of JP-A-2000-143672, and then triphenyl (alkylenediamine) boron and pyrithione are mixed at a molar ratio of 1: 1 in an organic solvent such as xylene. 5 hours at 90 ° C for 2 hours
By heating and stirring for an hour, the desired addition salt of triphenyl (alkylenediamine) boron with pyrithione precipitates as an insoluble salt. Next, after cooling to room temperature, the crystals are separated by filtration, washed with an organic solvent such as xylene, and dried to obtain an addition salt of triphenyl (alkylenediamine) boron and pyrithione with high purity and high yield.

The resulting addition salt of triphenyl (alkylenediamine) boron with pyrithione can be used as an antifouling agent in water by a conventional method.

For example, as the antifouling agent for fishing nets, an addition salt of triphenyl (alkylenediamine) boron of the present invention with pyrithione, and if necessary, other active ingredients shown below, acrylic resin, synthetic rubber, Rosin, silicone resin,
Various resins such as polybutene and a dispersant may be added, and dialkyl polysulfides, polybutene, paraffin, vaseline and silicone oil may be added as dissolution regulators, and the mixture may be dispersed with an organic solvent such as xylene.
Further, a paint may be added by adding cuprous oxide, red iron oxide, talc, barium sulfate as an extender pigment, and tricresyl phosphate, dioctyl phthalate, etc. as a plasticizer.

In the present invention, the addition amount of the addition salt of triphenyl (alkylenediamine) boron represented by the general formula (1) and pyrithione in an underwater antifouling agent, for example, a fishing net antifouling agent is determined by the amount of the underwater antifouling agent. It can be arbitrarily changed depending on the application object and the application environment, and is not particularly limited.

When the addition salt of triphenyl (alkylenediamine) boron represented by the general formula (1) and pyrithione in the present invention is used as an active ingredient of an underwater antifouling agent such as a fishing net antifouling agent, The compound alone exhibits an excellent antifouling effect on aquatic fouling organisms,
1,3-dicyanotetrachlorobenzene (hereinafter also referred to as compound (i)), 2- (thiocyanomethylthio) benzothiazole (hereinafter also referred to as compound (ii)) and compound groups (iii) to (vii) described below By blending a known antifouling component, a dissolution regulator of the compound group (viii), and the like, a more excellent anti-adhesion effect can be exhibited.

The tetraalkylthiuram disulfide compound of the compound group (iii) used in the present invention includes tetramethylthiuram disulfide, tetraethylthiuram disulfide, tetraisopropylthiuram disulfide, -N-butylthiuram disulfide and the like.

The metal dithiocarbamate of the compound group (iv) includes zinc dimethyldithiocarbamate, iron dimethyldithiocarbamate, copper dimethyldithiocarbamate, manganese dimethyldithiocarbamate, zinc diethyldithiocarbamate, and zinc di-n-butyldithiocarbamate. And zinc bis (dimethyldithiocarbamoyl) ethylenebisdithiocarbamate.

The pyrithione metal salts of the compound group (v) include zinc pyrithione, copper pyrithione and the like.

The 2,3-dichloromaleimide compounds of the compound group (vi) include 2,3-dichloro-N-
Ethyl maleimide, 2,3-dichloro-N-isopropylmaleimide, 2,3-dichloro-Nn-butylmaleimide, 2,3-dichloro-N-tert-butylmaleimide, 2,3-dichloro-Nn -Octylmaleimide,
2,3-dichloro-N-cyclohexylmaleimide,
2,3-dichloro-N- (2-chlorophenyl) maleimide, 2,3-dichloro-N- (4-chlorophenyl)
Maleimide, 2,3-dichloro-N- (2-ethyl-6
-Methylphenyl) maleimide, 2,3-dichloro-N
-(2,6-dimethylphenyl) maleimide, 2,3-
Dichloro-N- (2,6-diethylphenyl) maleimide, 2,3-dichloro-N- (2,4-diethylphenyl) maleimide, 2,3-dichloro-N- (2,4,6
-Trimethylphenyl) maleimide, 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,
3-dichloro-N- (2,4-dimethylbenzyl) maleimide, 2,3-dichloro-N- (3,4-dimethylbenzyl) maleimide, 2,3-dichloro-N-α-methylbenzylmaleimide, 3-dichloro-N- (2,
4-dichlorobenzyl) maleimide and the like.

The isothiazolone compounds of the compound group (vii) include 4,5-dichloro-2-n-hexyl-3-isothiazolone and 4,5-dichloro-2-n-
Octyl-3-isothiazolone, 5-chloro-2-decyl-3-isothiazolone, 4,5-dichloro-2- (4
-Chlorobenzyl) -3-isothiazolone, 4,5-dichloro-2- (2-methoxy-3-chlorophenyl)-
3-isothiazolone, 4,5-dibromo-2- (4-chlorobenzyl) -3-isothiazolone, 4-methyl-5
-Chloro-2- (4-hydroxyphenyl) -3-isothiazolone, 5-chloro-2- (3,4-dichlorophenyl) -3-isothiazolone and the like.

The addition salt of triphenyl (alkylenediamine) boron represented by the general formula (1) of the present invention with pyrithione, the compound (i), (ii), the compound group (iii) to (viii) The weight ratio of the underwater antifouling agent can be arbitrarily changed depending on the application environment, but is preferably 1:25 to 25: 1, more preferably 1:10.
It is in the range of 10: 1. These compounds (i), (i
i), compound groups (iii) to (vii) alone or
You may mix and use more than one kind.

Furthermore, known antifouling components other than those described here may be blended, and a more balanced effect on various fouling organisms can be expected.

Known antifouling components to be blended include cuprous thiocyanate, copper naphthenate, copper abietate,
Copper compounds such as copper oxyquinoline and copper oleate; 2-
Benzimidazole compounds such as (4-thiazolyl) benzimidazole, 2-thiocyanomethylthiobenzimidazole, 2- (methoxycarbonylamino) benzimidazole; 5-chloro-2,4-difluoro-6
Isophthalonitrile compounds such as 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;
4-dichloro- ( ₀ -chloroanilino) -1,3,5-
Triazine, 2-chloro-4-methylamino-6-isopropylamino-1,3,5-triazine, 2-chloro-4,6-bis (ethylamino) -1,3,5-triazine, 2-methylthio- 4,6-bis (ethylamino)
Triazine compounds such as -1,3,5-triazine, 2-methylthio-4-ethylamino-6-isopropylamino-1,3,5-triazine; 3- (3,4-dichlorophenyl) -1,1- Dimethyl urea, 3- (3,4
Urea compounds such as -dichlorophenyl) -1-methoxy-1-methylurea and 1- (2-methylcyclophenyl) -3-phenylurea; 2-amino-3-chloro-1,
4-naphthoquinone, 2,3-dichloro-1,4-naphthoquinone, 2,3-dicyano-1,4-dithia-1,4-
Quinone compounds such as dihydroanthraquinone; phthalimide compounds such as N-trichloromethyltetrahydrophthalimide, N-trichloromethylthiophthalimide, N-fluorodichloromethylthiophthalimide; anilide compounds such as trichloromethylthiomethanesulfone-p-chloroanilide; methylenebis Examples include thiocyanate-based compounds such as thiocyanate, ethylenebisthiocyanate, phenylisothiocyanate, benzylisothiocyanate, and arylisothiocyanate, but are not particularly limited thereto.

The polysulfide compounds of the compound group (viii) used as the elution modifier include diethyl pentasulfide, di-tert-butyl disulfide, di-tert-butyl tetrasulfide, and di-tert-butyl tetrasulfide. Tertiary amyltetrasulfide, ditertiary octyl pentasulfide, ditertiary nonylpentasulfide, ditertiary dodecylpentasulfide, dinonadecyltetrasulfide, etc. However, the present invention is not particularly limited to these. Further, a mixture thereof may be used.

Examples of polybutene having an average molecular weight of 200 to 1000 used as an elution modifier include, for example, LV-5, LV-10, and LV-10 manufactured by Nippon Oil Co., Ltd.
-25, LV-50, LV-100, HV-15, HV
-35, HV-50, HV-100, HV-300, etc., but are not particularly limited thereto. Further, a mixture thereof may be used.

Examples of the paraffin used as the dissolution controlling agent include liquid paraffin, paraffin wax, and paraffin chloride, but are not particularly limited thereto.

Further, as the vaseline used as the dissolution controlling agent, white vaseline, yellow vaseline and the like can be mentioned.

Examples of the silicone oil used as an elution modifier include dimethyl silicone oil, methyl hydrogen silicone oil, (higher) fatty acid-modified silicone oil, alkyl (aralkyl) -modified silicone oil, polyether-modified silicone oil, Examples thereof include amino-modified silicone oil, epoxy-modified silicone oil, and methylphenyl silicone oil, but are not particularly limited thereto, and they may be used alone or as a mixture of two or more.

Compounds (v
iii) The total amount of the components in the underwater antifouling agent such as polybutene, paraffins, petrolatum and silicone oil can be arbitrarily changed depending on the application environment, but is preferably 1 to 20% by weight, more preferably 3 to 20% by weight. 15% by weight. Further, the mixing ratio of each elution modifier can be arbitrarily changed depending on the application environment.

The resin used in the underwater antifouling agent of the present invention includes, for example, rosin resin, acrylic resin, polybutene resin, chlorinated rubber resin, vinyl chloride resin, alkyd resin, cumarone resin, ethylene-vinyl acetate resin,
Epoxy resins, silicone resins, synthetic rubbers and the like can be mentioned. These resins may be used alone and
You may mix and use more than one kind.

As the dispersing agent, fatty acid amide wax (manufactured by Kusumoto Kasei Co., Ltd., trade name: Dispalon A63)
0-20XN).

Examples of the organic solvent include aromatic compound-based organic solvents, ketone compound-based organic solvents, and aliphatic compound-based organic solvents. More specifically, xylene,
Examples include toluene, pseudocumene, diethylbenzene, triethylbenzene, mesitylene, solvent naphtha, butanol, isopropanol, methyl isobutyl ketone, hexane, and propylene glycol monomethyl ether. These solvents may be used alone,
Also, two or more kinds may be used as a mixture.

The underwater antifouling agent of the present invention is low in toxicity and high in safety with improved storage stability, and is used for a long period of time, such as worms such as hydro insects, shellfish such as barnacles, mussels, oysters, and serplas; It shows an excellent antifouling effect against tubal polychaetes such as kansane kansashi, human kansetsu, yakko kansashi, and suzuki kansai, and other fouling organisms.

[0039]

[Examples] Synthesis examples and examples are shown below, but the examples are not limited thereto. In addition, the composition in an Example shows a weight%. Synthesis Example 1 Triphenyl (ethylenediamine) boron
Synthesis of addition salt with pyrithione To a 1 L four-necked flask equipped with a mechanical stirrer, a cooling tube, a dropping funnel, and a thermometer, 60.4 g (0.2 mol) of triphenyl (ethylenediamine) boron and 400 ml of xylene were added. Start stirring and raise the temperature to 80 ° C
To a homogeneous solution. Next, a mixed solution of 25.4 g (0.2 mol) of pyrithione (Aldrich reagent) and 100 ml of xylene is dropped into the dropping funnel over 30 minutes. As the reaction proceeds, the target substance precipitates as an insoluble salt. The mixture was reacted at the same temperature for 2 hours, cooled to 20 ° C, filtered, washed with 100 ml of xylene, and dried. Addition of light yellow to slightly yellow triphenyl (ethylenediamine) boron having a melting point of 157 to 158 ° C with pyrithione. 84 g (yield 98%) of the salt were obtained. It was confirmed from IR (infrared absorption spectrum) and elemental analysis that the product was the target compound.

Synthesis Example 2 Triphenyl (propylene dia
(Min) Synthesis of Addition Salt of Boron and Pyrithione In the same manner as in Synthesis Example 1 , an addition salt of triphenyl (propylenediamine) boron and pyrithione having a melting point of 155 to 157 ° C. was obtained at a yield of 96%. Was. It was confirmed to be the target substance by IR (infrared absorption spectrum) and elemental analysis.

Example 1 According to the following formulation example, each component was mixed to prepare an underwater antifouling agent. Since the compound of the present invention is insoluble in xylene, the disparone A630-20X and the resin are pre-dispersed by despar stirring and the disparone A630-20X is mixed in advance, and then the respective components are mixed to form an underwater antifouling agent having good dispersibility. It was adjusted.

Formulation Example 1 Compound of Synthesis Example 1 10% Ditertiary nonylpentasulfide 5% Liquid paraffin 5% Silicone oil (TSF-410) 2% Disparone A630-20X 1% Acrylic resin (50% xylene liquid) 20% Xylene 57% Formulation Example 2 Compound of Synthesis Example 2 10% Ditertiary nonyl pentasulfide 5% Liquid paraffin 5% Silicone oil (TSF-410) 2% Dispalon A630-20X 1% Acrylic resin (50) % Xylene solution) 20% xylene 57% Formulation Example 3 Compound of Synthesis Example 1 8% 1,3-dicyanotetrachlorobenzene 8% ditertiary nonyl pentasulfide 5% liquid paraffin 5% silicone oil (TSF-410) 2% Dispalon A630-20X 1% Acrylic resin (50% 20% Xylene 51% Formulation Example 4 Compound of Synthesis Example 8 8% 1,3-dicyanotetrachlorobenzene 8% Ditertiary nonyl pentasulfide 5% Liquid paraffin 5% Silicone oil (TSF-410) 2 % Dispalon A630-20X 1% Acrylic resin (50% xylene liquid) 20% Xylene 51% Formulation Example 5 Compound of Synthesis Example 1 8% 2- (Thiocyanomethylthio) benzothiazole 8% Polybutene (LV-50) 5% Yellow Vaseline 5% Silicone oil (TSF-410) 2% Disparone A630-20X 1% Acrylic resin (50% xylene solution) 20% Xylene 51% Formulation Example 6 Compound of Synthesis Example 2 8% 2- (thiocyanomethylthio) benzothiazole 8% Polybutene (LV-50) 5% Yellow Vaseline 5% Silicone oil (TSF-410) 2% Dispalon A630-20X 1% Acrylic resin (50% xylene solution) 20% Xylene 51% Formulation Example 7 Compound of Synthesis Example 1 8% Tetraethylthiuram disulfide 8% Polybutene ( LV-50) 5% Yellow petrolatum 5% Silicone oil (TSF-410) 2% Disparone A630-20X 1% Acrylic resin (50% xylene solution) 20% Xylene 51% Formulation Example 8 Compound of Synthesis Example 2 8% Tetraethylthiuram Disulfide 8% Polybutene (LV-50) 5% Yellow petrolatum 5% Silicone oil (TSF-410) 2% Disparone A630-20X 1% Acrylic resin (50% xylene solution) 20% Xylene 51% Formulation Example 9 Synthesis Compound of Example 1 8% dimethyldithi Zinc octocarbamate 8% Ditertiary nonyl pentasulfide 5% Yellow petrolatum 5% Silicone oil (TSF-410) 2% Disparon A630-20X 1% Acrylic resin (50% xylene solution) 20% Xylene 51% Formulation examples 10 Compound of Synthesis Example 8 8% Zinc dimethyldithiocarbamate 8% Ditertiary nonyl pentasulfide 5% Yellow petrolatum 5% Silicone oil (TSF-410) 2% Disparone A630-20X 1% Acrylic resin (50% xylene Liquid) 20% Xylene 51% Formulation Example 11 Compound of Synthesis Example 1 8% Zinc pyrithione 8% Ditertiary nonyl pentasulfide 5% Polybutene (LV-50) 5% Silicone oil (TSF-410) 2% Disparone A630-20X 1% acrylic resin (5 20% Xylene 51% Formulation Example 12 Compound of Synthesis Example 8 8% Zinc pyrithione 8% Ditertiary nonyl pentasulfide 5% Polybutene (LV-50) 5% Silicone oil (TSF-410) 2 % Dispalon A630-20X 1% Acrylic resin (50% xylene solution) 20% Xylene 51% Formulation Example 13 Compound of Synthesis Example 1 8% 2,3-Dichloro-N-benzylmaleimide 8% Ditertiary nonylpentasulfite 5% Polybutene (LV-50) 5% Silicone oil (TSF-410) 2% Disparone A630-20X 1% Acrylic resin (50% xylene liquid) 20% Xylene 51% Formulation Example 14 Compound of Synthesis Example 2 8% 2 , 3-Dichloro-N-benzylmaleimide 8% Ditertiary nonyl pentasulfide 5 % Polybutene (LV-50) 5% Silicone oil (TSF-410) 2% Dispalon A630-20X 1% Acrylic resin (50% xylene liquid) 20% Xylene 51% Formulation Example 15 Compound of Synthesis Example 1 8% 4,5 -Dichloro-2-n-octyl-3-isothiazolone 8% Ditertiary nonyl pentasulfide 5% Liquid paraffin 5% Silicone oil (TSF-410) 2% Disparone A630-20X 1% Acrylic resin (50% xylene Liquid) 20% Xylene 51% Formulation Example 16 Compound of Synthesis Example 8 8% 4,5-Dichloro-2-n-octyl-3-isothiazolone 8% Ditertiary nonyl pentasulfide 5% Liquid paraffin 5% Silicone Oil (TSF-410) 2% Dispalon A630-20X 1% Acrylic tree (50% xylene solution) 20% xylene 51%

Example 2 A ship bottom antifouling paint was pulverized and kneaded with a ball mill in accordance with the following formulation example and adjusted.

Formulation Example 17 Compound of Synthesis Example 1 20% Petal 15% Talc 3% Barium sulfate 5% Rosin resin 15% Chloride rubber resin 5% Ditertiary nonyl pentasulfide 3% Polybutene (LV-50) 3% Silicone oil (TSF-410) 2% Xylene 29% Formulation Example 18 Compound of Synthesis Example 8 8% Petal 15% Talc 3% Barium sulfate 5% Rosin resin 15% Chloride rubber resin 5% Ditertiary nonyl penta Sulfide 3% Polybutene (LV-50) 3% Silicone oil (TSF-410) 2% Xylene 29% Formulation Example 19 Compound of Synthesis Example 1 10% 1,3-dicyanotetrachlorobenzene 10% Red stalk 15% Talc 3 % Barium sulfate 5% Rosin resin 15% Chloride rubber resin 5% Ditertiary nonyl pentasulfide 3% Polybut (LV-50) 3% Silicone oil (TSF-410) 2% Xylene 29% Formulation Example 20 Compound of Synthesis Example 2 10% Zinc pyrithione 10% Red stalk 15% Talc 3% Barium sulfate 5% Rosin resin 15% Chloride Rubber resin 5% Polybutene (LV-50) 3% Yellow petrolatum 3% Silicone oil (TSF-410) 2% Xylene 29% Formulation Example 21 Compound of Synthesis Example 1 10% 4,5-dichloro-2-n-octyl- 3-Isothiazolone 10% Petal 15% Talc 3% Barium sulfate 5% Rosin resin 15% Chloride rubber resin 5% Ditertiary nonyl pentasulfide 3% Liquid paraffin 3% Silicone oil (TSF-410) 2% Xylene 29%

Experiment 1 [Test for confirming the efficacy as a fishnet antifouling agent] Each of the underwater antifouling agents of Example 1 of the present invention (Formulation Examples 1 to 16) was manufactured by Tetron without knots (1000/263 third dimension).
After immersion coating and air-drying, it was immersed and held about 10 m below the sea surface near the seashore of Kombumori in Hokkaido for three months from August 2000. This area is a frequent area of hydro insects, and after 3 months, the antifouling effect on hydro insects was observed. Table 1 shows the test results.
Summarized in In Table 1, the attached area (%) indicates the proportion of each attached organism.

Experiment 2 [Test for confirming efficacy as a fishnet antifouling agent] Each of the underwater antifouling agents of Example 1 of the present invention (Formulation Examples 1 to 16) was treated with a polyethylene knotless net (section 6, 400 denier / 60). After dip-coating and air-drying the book, it was dried below sea level in Sukumo Bay, Sukumo City, Kochi Prefecture for 6 months from May 2000.
It was kept in the sea at 5 m. After 3 months and 6 months, the antifouling effect on fouling organisms such as tubal polychaetes, shellfish, bryozoans and algae was observed. Table 2 summarizes the test results. In Table 2, the attached area (%) indicates the composition ratio of each attached organism.

The formulas of the comparative examples of Experiments 1 and 2 are as follows. For the formulations of Comparative Examples 3 and 4, the underwater antifouling agent was prepared by the preparation method of Example 1. In Comparative Examples 1 and 2, each component was mixed and dissolved to prepare an antifouling agent in water.

Comparative Example 1 Tetraethylthiuram disulfide 10% Ditertiary nonylpentasulfide 5% Liquid paraffin 5% Silicone oil (TSF-410) 2% Acrylic resin (50% xylene solution) 20% Xylene 58 Comparative Example 2 2,3-Dichloro-N-benzylmaleimide 10% Ditertiary nonylpentasulfide 5% Liquid paraffin 5% Silicone oil (TSF-410) 2% Acrylic resin (50% xylene liquid) 20% Xylene 58% Comparative Example 3 Bis (dimethyldithiocarbamoyl) ethylenebisdithiocarbamate 10% Ditertiary nonyl pentasulfide 5% Liquid paraffin 5% Silicone oil (TSF-410) 2% Dispalon A630-20X 1% Acrylic Resin (50% xylene liquid) 0% Xylene 57% Comparative Example 4 Triphenyl (pyridine) boron 10% Ditertiary nonyl pentasulfide 5% Liquid paraffin 5% Silicone oil (TSF-410) 2% Disparone A630-20X 1% Acrylic resin (50 % Xylene solution) 20% xylene 57%

[0049]

[Table 1]

From Table 1, it was found that the underwater antifouling agent of the present invention had an effect equal to or higher than Comparative Examples 3 and 4. In other words, the compound of the present invention has an extremely strong and practical effect on coelenterates such as hydro insects, which is at least as powerful as zinc bis (dimethyldithiocarbamoyl) ethylenebisdithiocarbamate and triphenyl (pyridine) boron. It has been found that it shows a great effect.

[0051]

[Table 2]

From Table 2, it can be seen that, in all of Formulation Examples 1 to 16, no attachment of attached organisms of tubal polychaete, shellfish, bryozoan and algae was observed in 3 months, and the antifouling effect was maintained for a long period of time. You can see that. In particular, it can be seen that the adhesion area after 10 months is 10% or less regardless of the type of the target organism, and the total adhesion area is 20% or less. It was also found that triphenyl (pyridine) boron used in Comparative Example 4 exhibited a much better antifouling effect than the antifouling effect.

Experiment 3 [Test for Efficacy as Antifouling Paint] An anticorrosive paint was previously applied to a sandplast-treated steel sheet, and the dried paint film was applied to Example 2 of the present invention (Formulation Example 1).
7-21) Bottom antifouling paint is brushed twice, and a test plate (100 mm × 300 m) having a dry film thickness of about 100 μm
m) was prepared. Approximately 1 plate from February 2000
It was kept immersed 1.5 m below sea level in Sukumo Bay, Sukumo City, Kochi Prefecture. After 6 months and 12 months, the antifouling effect on fouling organisms such as tubal polychaetes, shellfish, bryozoans and algae was observed. Table 3 summarizes the test results. In Table 3, the attached area (%) indicates the proportion of each attached organism.

The prescription of the comparative example of Experiment 3 is as follows. Comparative Example 5 Cuprous oxide 20% Petal 15% Talc 3% Barium sulfate 5% Rosin resin 15% Chloride rubber resin 5% Ditertiary nonyl pentasulfide 3% Polybutene (LV-50) 3% Silicone oil ( TSF-410) 2% Xylene 29%

[0055]

[Table 3]

As can be seen from Table 3, in all of Formulation Examples 17 to 21, no adherent organisms of tubal polychaete, shellfish, bryozoan and algae were observed after 6 months, and the antifouling effect was maintained for a long time. You can see that. In particular, in the state of adhesion after 12 months, it can be seen that the adhesion area is 10% or less irrespective of the type of target organism, and the total adhesion area is 20% or less.

[0057]

According to the results of Experiments 1, 2 and 3, the underwater antifouling agent of the present invention containing an addition salt of triphenyl (alkylenediamine) boron and pyrithione as an active ingredient is effective against all kinds of marine fouling organisms. It was found to have an excellent antifouling effect. In particular, conventional antifouling agents are extremely effective against coelenterates such as hydro insects, which are extremely difficult to prevent adhesion when attached, and tubal polychaetes such as kansane kansashi and shellfish such as barnacles. Turned out to be. In addition, it has been confirmed that the present underwater antifouling agent has improved storage stability, low toxicity and high safety.

[0058]

[Brief description of the drawings]

FIG. 1 is an infrared absorption spectrum (IR chart) of an addition salt of triphenyl (ethylenediamine) boron and pyrithione obtained in Synthesis Example 1.

FIG. 2 is an infrared absorption spectrum (IR chart) of an addition salt of triphenyl (propylenediamine) boron and pyrithione obtained in Synthesis Example 2.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) A01N 43/80 102 A01N 43/80 102 47/14 47/14 AD 55/08 55/08 C07D 275 / 02 C07D 275/02 277/74 277/74 C07F 5/02 C07F 5/02 D (72) Inventor Yuji Koga 955, Oji, Yoshitomi-cho, Chikugami-gun, Fukuoka Yoshitomi Fine Chemical Co., Ltd. (Reference) 4C033 AE12 4C055 AA17 BA46 CA01 DA01 GA01 4H011 AA02 AD01 BA01 BA06 BB06 BB09 BB10 BB13 BB16 BC01 BC03 BC18 BC19 BC20 DA16 DA17 DD01 DD07 DH02 DH07 DH13 4H048 AA01 AB03 VA30 VA32 VA40 VA75 V

Claims (5)

[Claims] 1. A compound of the general formula (1) (Wherein n represents an integer of 2 or 3). An addition salt of triphenyl (alkylenediamine) boron and pyrithione. 2. An underwater antifouling agent comprising the addition salt of triphenyl (alkylenediamine) boron according to claim 1 and pyrithione as an active ingredient. 3. The underwater antifouling agent according to claim 2, wherein the underwater antifouling agent is any one of an underwater pest control agent, an underwater antifouling paint and a fishing net antifouling agent. 4. The addition salt according to claim 1, and 1,3-dicyanotetrachlorobenzene, 2- (thiocyanomethylthio) benzothiazole, a compound of the general formula (2) (Wherein, R ¹ represents an alkyl group having 1 to 4 carbon atoms), a tetraalkylthiuram disulfide represented by the general formula (3): Or the general formula (4): (Wherein R ² and R ³ represent an alkyl group having 1 to 4 carbon atoms;
Represents an integer of 2 or 3, and M represents a metal of zinc, iron, manganese, or copper. A metal salt of dithiocarbamic acid represented by the general formula (5): (Wherein p is an integer of 2 or 3, and M is as defined above), a pyrithione metal salt represented by the following general formula (6): (In the formula, R ⁴ represents hydrogen, an alkyl group, a halogen-substituted alkyl group, a cycloalkyl group, a phenyl group, a halogen-substituted phenyl group, an alkyl-substituted phenyl group, a benzyl group, a halogen-substituted benzyl group, or an alkyl-substituted benzyl group. 2,3-dichloromaleimide compound represented by the general formula (7): (Wherein X ¹ and X ² are the same or different and each represent hydrogen, halogen or an alkyl group, and R ⁵ represents an alkyl group, a nucleus-substituted phenyl group, or a nucleus-substituted benzyl group). An underwater antifouling agent comprising one or more compounds selected from compounds. 5. An elution controlling agent represented by the following general formula (8): (In the formula, R ⁶ represents an alkyl group having 1 to 20 carbon atoms, and q represents 2
And an integer of 10 to 10. The dialkyl polysulfides represented by the formula (1), polybutene having an average molecular weight of 200 to 1,000, paraffin, vaseline, and silicone oil, or one or more selected from the group consisting of silicone oils. Underwater antifouling agent.