JP2002302494A - Triphenylboron derivative and its use - Google Patents

Abstract

(57) [Summary] (Modified) [Problem] To provide a fouling preventive agent containing an antifouling component having an excellent antifouling effect on aquatic fouling organisms such as coelenterates, shellfish, and tubal polychaetes. SOLUTION: The triphenylborondiamine adduct represented by the chemical formulas (1) and (2) forms a salt with an organic acid (hereinafter, referred to as the present compound) to form a salt with another antifouling component or a coating resin. Improves miscibility and solubility in solvents. The present compound is also useful as a raw material of a triphenylboron-containing polymer and as an antifouling component. [Wherein, when p = 0 and q = 1, X is a group having 1 to 1 carbon atoms.
8 represents an alkyl group having 8 carbon atoms, an alkenyl group having 2 to 18 carbon atoms, and when p = 1 and q = 1, X represents an alkylene group having 1 to 18 carbon atoms, an alkenylene group having 2 to 18 carbon atoms, or the like. , Y represents an alkylene group having 2 to 18 carbon atoms, n R ¹ represents a halogen atom or an alkyl group having 1 to 18 carbon atoms, and n represents an integer of 0 to 3. ]

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a triphenylboron derivative and its use, and more particularly, to a fishing net antifouling agent for preventing aquatic fouling organisms from adhering to and propagating on fishing nets for aquaculture or stationary use. Materials such as floats and ropes used for the bottom of ships, fishing nets, and underwater antifouling paints to prevent aquatic fouling organisms from adhering to and propagating on the condenser cooling waterways of nuclear and thermal power plants. The present invention also relates to an agent for preventing fouling caused by adhesion of aquatic fouling organisms (hereinafter, also referred to as a fouling preventive).

[0002]

2. Description of the Related Art Insects such as hydro-insects, oberia, and shellfish,
The attachment of aquatic organisms such as tubal polychaetes, seaweeds, bryozoans, molluscs, etc. causes great economic loss to ships and fishing nets, and these aquatic organisms are called aquatic fouling organisms.
For example, if barnacles and the like adhere to the fishing net, they block the mesh and obstruct the flow of the tide, and the lack of oxygen in the water can cause the cultured fish to suffocate, or the mesh can be closed and the wave resistance increases. During a typhoon, the net may be damaged. Also, if these aquatic fouling organisms adhere to the bottom of the ship, the propulsion efficiency of the ship is reduced, fuel efficiency is increased, and economic losses are incurred. For this reason, efforts are currently being made to maintain contaminated objects, and a great deal of labor and maintenance costs are being spent on reducing economic losses. Various studies and proposals have been made so far as measures to prevent the adhesion of aquatic fouling organisms. Practically, a series of organotin compounds are effective.However, organotin compounds are generally highly toxic, and careless handling of products containing them may cause harm to the handlers and reduce environmental pollution. It can be connected.

[0003] For these reasons, a low-polluting fishing net antifouling agent, a benzothiazole compound as an active ingredient is disclosed in Japanese Patent Publication No. 51-10849 as an antifouling agent due to the adhesion of aquatic fouling organisms such as antifouling paints. The underwater antifouling paint is disclosed in JP-A-60-38306, JP-A-63-284275 and JP-B-1-11606, in which a tetraalkylthiuram disulfide compound and another compound are combined. Various antifouling agents and antifouling paint compositions for fishing nets are disclosed in Japanese Patent Publication No. 61-50984, and a pollution control agent for marine structures containing a 3-isothiazolone compound as an active ingredient is disclosed in Japanese Patent Publication No. 1-20665. Fairness 2-2424
No. 2, JP-A-53-9320, and JP-A-5-25-2
JP-A-01804, JP-A-6-100405 and JP-A-6-100408 disclose underwater antifouling paints containing a maleimide compound as an active ingredient, respectively.

[0004] However, these antifouling agents have a weak effect of preventing adhesion to coelenterates such as hydroids and oberia, and cannot be used in the inhabiting areas of coelenterates such as the coasts of the Tohoku and Hokkaido regions. . In addition, in the eastern seas and western Japan waters where many shellfishes such as barnacles and mussels and tubal polychaetes such as kansane kansetsu live, the conventional antifouling agent has a weak adhesion prevention effect, and effectively adheres these aquatic fouling organisms. It could not be prevented.

Conventionally, cuprous oxide has been known to be effective against shellfish, and it has been confirmed that an organic copper-based antifouling agent such as copper pyrithione is effective against shellfish and tubal polychaete. Have been. However, cuprous oxide has a weak effect in preventing adhesion of tubal polychaetes and coelenterates, and organic copper-based antifouling agents often thicken and gel the paint when mixed with the paint. There is a disadvantage that it is difficult to mix with the paint.

JP-A-8-295608 discloses a fishing net antifouling agent containing a triphenylborane alkylamine-added compound as an active ingredient, and JP-A-8-295609 contains a triphenylborane octadecylamine-added compound. The solution to be used is a triphenylboron-containing allylamine-type polymer in WO98 / 33892, a triarylboron-containing polymer in JP-A-11-199801, and a tri-substituted borane-containing polymer in JP-A-11-302571. The resin to which the amine complex compound is bound,
Each is disclosed.

[0007]

SUMMARY OF THE INVENTION The present invention relates to a coelenterate animal,
Triphenylboron derivative and triphenyl, which have an excellent anti-adhesion effect on aquatic fouling organisms such as shellfish and tubal polychaete, and have excellent miscibility with other antifouling components, paint resins, etc., and have little adverse effect on the environment. An object of the present invention is to provide a raw material for a boron-containing polymer and a fouling inhibitor containing the component.

[0008]

Means for Solving the Problems The present inventors have made intensive studies to overcome the above-mentioned drawbacks of the conventional antifouling agents for fishing nets and antifouling paints in water, and as a result, have found that A novel triphenylboron derivative and a fouling inhibitor containing the same have been invented, which are less likely to cause contamination and exhibit an excellent antifouling effect on aquatic fouling organisms. That is, the novel triphenylboron derivative is a coelenterate such as a hydroid or an oberia; a shellfish such as a barnacle, a mussel, an oyster, or a serpula; Have been found to exhibit an excellent adhesion-preventing effect on aquatic fouling organisms, and have completed the present invention.

That is, the present invention is as follows. General formula (1):

Embedded image Or, the general formula (2):

Embedded image [In the formula, p and q are not simultaneously 0 and each represent 0 or 1. When p = 0 and q = 1, X is an alkyl group having 1 to 18 carbon atoms, and 2 to 18 carbon atoms. Alkenyl group, aryl group, aralkyl group, aralkenyl group,-
CH (= O) groups, -C (= O) -R ² group, -C (= O)
-OR ^{2 group,} -R 3 ^{-O-R 4 group,} -R 3 -C (= O)
-R indicates ^four, when p = 1 and q = 1, X is an alkylene group having 1 to 18 carbon atoms, an alkenylene group having 2 to 18 carbon atoms, an arylene group, aralkylene group, Ararukeniren group, -R ⁵ —OR ⁶ — group, —R ⁵ —C (＝ O) —R
⁶ represents a ⁶ -group, Y represents an alkylene group having 2 to 18 carbon atoms, an arylene group, an aralkylene group or a cycloalkylene group, and n R ^{1 s} are the same or different and are each a halogen atom or a C 1-18 Represents an alkyl group represented by
² represents an alkyl group having 1 to 18 carbon atoms, an alkenyl group having 2 to 18 carbon atoms, an aryl group, an aralkyl group, and an aralkenyl group, wherein R ³ , R ⁵ , and R ⁶ are the same or different and each have the same number of carbon atoms; Alkylene group of 1 to 18, carbon number of 2 to 18
Represents an alkenylene group, an arylene group, an aralkylene group, or an arkenenylene group, wherein R ⁴ is a hydrogen atom,
8 represents an alkyl group, an alkenyl group having 2 to 18 carbon atoms, an aryl group, an aralkyl group, or an aralkenyl group;
And represents an integer of from 1 to 3, and represented by the general formula (3):

Embedded image The group represented by represents an N-containing heterocyclic ring substituted with an amino group. ] The triphenylboron derivative represented by these. 3. The triphenylboron derivative according to claim 1, wherein the carboxyl group-containing compound in formulas (1) and (2) is rosin. Or a composition containing the triphenylboron derivative described. The composition according to the above description, further comprising at least one selected from the group consisting of a silicone oil, an elution modifier, and a known antifouling component. Or a fouling inhibitor containing the triphenylboron derivative described above. The antifouling agent according to claim, further comprising at least one selected from the group consisting of a silicone oil, an elution modifier, and a known antifouling component. An antifouling agent for or used as an antifouling for fishing nets. An antifouling agent for underwater antifouling paints or as described.

[0010]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention will be described in detail.
General formula (1) of the present invention:

Embedded image (Wherein each symbol is as defined above) (hereinafter also referred to as triphenylboron derivative (1)) represented by general formula (4):

Embedded image (Wherein each symbol is as defined above), and a compound having a carboxyl group represented by the general formula (5):

Embedded image (Wherein each symbol has the same meaning as described above).

In formula (4), X has 1 to 18 carbon atoms.
Examples of the alkyl group include methyl, ethyl, n-
Examples thereof include linear or branched alkyl groups such as propyl, isopropyl, n-butyl, 2-methylpropyl, 3-methylpropyl, tert-butyl, n-octyl, n-dodecyl, and n-octadecyl.

In formula (4), X has 2 to 18 carbon atoms.
Examples of the alkenyl group include, for example, vinyl, 1-propenyl, allyl, isopropenyl, 1-butenyl, 2-butenyl, 2-methylpropenyl, 3-methylpropenyl, 1-octenyl, 1-dodecenyl, 1-octadecenyl and the like A straight-chain or branched-chain alkyl group is exemplified. As the aryl group of X in the general formula (4), for example,
An aryl group which may have a substituent such as phenyl, naphthyltolyl, and xylyl is exemplified.

The aralkyl group of X in the general formula (4) is -Ar-Alk or -Alk-Ar (where Ar represents an aryl group, -Ar represents an arylene group, Alk represents an alkyl group, Alk represents an alkylene group), for example, benzyl (—C ₆ H ₄ —CH ₃₎
Or _-CH 2 _-C 6 _H 5), phenethyl _(-C 6 _{H 4}
-C ₂ H ₅ or _{-C 2 H 4 -C 6 H 5} ) , and the like.

The aralkenyl group of X in the general formula (4) is -Ar-Alke or -Alke-Ar (where Ar is an aryl group, -Ar is an arylene group, Alke is an alkenyl group, -Alke Represents an alkenylene group), for example, styryl (—C ₆ H ₄₎
-CH = CH ₂ or _{-CH = CH-C 6 H 5} ), cinnamyl _{(-C 6 H 4 -CH = CH} -CH 3 or -CH
_{2 -CH = CH-C 6 H} 5) , and the like.

Examples of the alkyl group having 1 to 18 carbon atoms of R ² and R ⁴ in the general formula (4) include, for example, methyl, ethyl, n-propyl, isopropyl, n-butyl, 2-methylpropyl, 3-methyl Examples include straight-chain or branched-chain alkyl groups such as propyl, tert-butyl, n-octyl, n-dodecyl, and n-octadecyl.

The alkenyl group having 2 to 18 carbon atoms for R ² and R ⁴ in the general formula (4) includes, for example, vinyl, 1
Straight-chain or branched-chain alkyl groups such as -propenyl, allyl, isopropenyl, 1-butenyl, 2-butenyl, 2-methylpropenyl, 3-methylpropenyl, 1-octenyl, 1-dodecenyl, 1-octadecenyl and the like.

The aryl group of R ² and R ⁴ in the general formula (4) includes, for example, an aryl group which may have a substituent such as phenyl, naphthyltolyl and xylyl. As the aralkyl group for R ² and R ⁴ in the general formula (4), -Ar-Alk or -Alk-Ar (where Ar represents an aryl group and -Ar represents an arylene group;
Alk represents an alkyl group, and -Alk represents an alkylene group. ) Refers to, for example, benzyl _{(-C 6} H 4 -CH
₃ or _-CH 2 _-C 6 _H 5), phenethyl _(-C 6 H
₄ -C ₂ H ₅ or _{-C 2 H 4 -C 6 H 5} ) , and the like.

The aralkenyl group of R ² and R ⁴ in the general formula (4) is -Ar-Alke or -Alke-A
r (where Ar represents an aryl group, -Ar represents an arylene group, Alke represents an alkenyl group, and -Alke represents an alkenylene group), for example, styryl (-
C ₆ H ₄ -CH = CH ₂ or -CH = CH-C
₆ H _5), cinnamyl _{(-C 6 H 4 -CH = CH} -CH
₃ or —CH ₂ —CH ＝ CH—C ₆ H ₅ ).

The alkylene group having 1 to 18 carbon atoms of R ³ , R ⁵ and R ⁶ in the general formula (4) includes, for example, methylene, ethylene, trimethylene, propylene, tetramethylene, 3-methyltetramethylene, octamethylene. ,
Examples thereof include linear or branched alkylene groups such as dodecamethylene and octadecamethylene.

Examples of the alkenylene group having 2 to 18 carbon atoms for R ³ , R ⁵ and R ⁶ in the general formula (4) include, for example, vinylene, propenylene, 1-butenylene, 2-butenylene, 3-methyl-1-butenylene , 1-octenylene,
Examples thereof include linear or branched alkenylene groups such as 1-dodecenylene and 1-octadesenylene.

The arylene group of R ³ , R ⁵ and R ⁶ in the general formula (4) includes, for example, o-phenylene, m-
Phenylene, p-phenylene, 1,8-naphthylene,
1,7-naphthylene, 1,6-naphthylene, 1,4-naphthylene, 1,3-naphthylene, 1,2-naphthylene,
Examples thereof include 2,3-naphthylene, 2,6-naphthylene, and 2,7-naphthylene.

The aralkylene group represented by R ³ , R ⁵ and R ⁶ in the general formula (4) is -Ar-Alk- or -Alk
-Ar-(. Wherein Ar refers to an arylene group, Alk refers to an alkylene group) refers to, for example, benzylene _{(-C 6} H 4 -CH ₂ - or _-CH 2 _-C 6 H
₄ -), phenethylene _{(-C 6 H 4 -C 2 H} 5 - or _-C 2 _H5-C 6 H4-) and the like.

The aralkenylene group of R ³ , R ⁵ and R ⁶ in the general formula (4) is -Ar-Alke- or -A
Ike-Ar- (where Ar represents an arylene group;
Ike refers to an alkenylene group. ) Refers to, for example, styrylene _{(-C 6} H 4 -CH = CH- or -CH = C
_H-C 6 H ₄ -), and the like.

The carboxyl group-containing compound represented by the general formula (4) includes acetic acid, propionic acid, butyric acid, isobutyric acid, valeric acid, isovaleric acid, pivalic acid, hexanoic acid, heptanoic acid, octanoic acid, pelargonic acid, Decanoic acid, n-undecylenic acid, versatic acid, lauric acid, n-tridecylenic acid, myristic acid, n-pentadecylenic acid, palmitic acid, margaric acid, stearic acid, isostearic acid, monochloroacetic acid, monofluoroacetic acid, hydroxyacetic acid, 3 -Hydroxypropionic acid, glycolic acid, lactic acid, glyceric acid, pyruvic acid, acetoacetic acid, 5-oxovaleric acid, 3-oxovaleric acid, may have a substituent such as 3,5-dioxovaleric acid, Linear or branched saturated aliphatic monocarboxylic acid having 1 to 18 carbon atoms; oxalic acid, malonic acid, succinic acid, Talic acid, methyl succinic acid, adipic acid, α-methyl glutaric acid, pimelic acid, coric acid, azelaic acid, sebacic acid, undecandioic acid, dodecandioic acid, tridecandioic acid, tetradecandioic acid, pentadecandioic acid, hexadecandioic acid Has substituents such as heptadecandioic acid, octadecandioic acid, oxalic acid monoethyl ester, malonic acid monoethyl ester, monochloromalonic acid, monochlorosuccinic acid, tartronic acid, malic acid, tartaric acid, mesooxalic acid, and oxalacetic acid. May be
Linear or branched saturated aliphatic dicarboxylic acids having 2 to 18 carbon atoms and monoesters thereof; acrylic acid, crotonic acid, isocrotonic acid, vinyl acetic acid, methacrylic acid, 2-
Ethyl acrylic acid, 2-n-propyl acrylic acid, 2-
Isopropyl acrylic acid, 2-n-butyl acrylic acid,
2-sec-butylacrylic acid, 2-tert-butylacrylic acid, 2-ethyl-2-butenoic acid, 2-n-propyl-2-butenoic acid, 2-isopropyl-2-butenoic acid, 2-n-butyl -2-butenoic acid, 2-sec-butyl-2-butenoic acid, 2-tert-butyl-2-butenoic acid, 2-pentenoic acid, 2-methyl-2-pentenoic acid, 3
-Methyl-2-pentenoic acid, 4-methyl-2-pentenoic acid, 2-ethyl-2-pentenoic acid, 2-n-propyl-
2-pentenoic acid, 2-isopropyl-2-pentenoic acid,
2-n-butyl-2-pentenoic acid, 2-sec-butyl-2-pentenoic acid, 2-tert-butyl-2-pentenoic acid, 3-pentenoic acid, 4-methyl-3-pentenoic acid,
2-hexenoic acid, 2-methyl-2-hexenoic acid, 2-ethyl-2-hexenoic acid, 2-n-propyl-2-hexenoic acid, 2-isopropyl-2-hexenoic acid, 2-n-butyl-2 -Hexenoic acid, 2-sec-butyl-2-hexenoic acid, 2-tert-butyl-2-hexenoic acid, 3-
Hexenoic acid, 4-hexenoic acid, 5-hexenoic acid, 2-heptenoic acid, 2-methyl-2-heptenoic acid, 2-ethyl-
2-heptenoic acid, 2-n-propyl-2-heptenoic acid,
2-isopropyl-2-heptenoic acid, 2-n-butyl-
2-heptenoic acid, 2-sec-butyl-2-heptenoic acid, 2-tert-butyl-2-heptenoic acid, 3-heptenoic acid, 4-heptenoic acid, 5-heptenoic acid, 6-heptenoic acid, 4-methyl -2-hexenoic acid, 5-methyl-2-
Hexenoic acid, 4,4-dimethyl-2-pentenoic acid, 2,
4-dimethyl-2-pentenoic acid, 2,4-dimethyl-2
-Hexenoic acid, 2,5-dimethyl-2-hexenoic acid,
2,4,4-trimethyl-2-pentenoic acid, 3-methyl-2-butenoic acid, 2,3-dimethyl-2-butenoic acid,
-Methyl-2-pentenoic acid, 2,3-dimethyl-2-pentenoic acid, 3-methyl-2-hexenoic acid, 2,3-dimethyl-2-hexenoic acid, 3,4-dimethyl-2-pentenoic acid, 2,3,4-trimethyl-2-pentenoic acid, 3-
Methyl-2-heptenoic acid, 2,3-dimethyl-2-heptenoic acid, 3,4-dimethyl-2-hexenoic acid, 2,3
4-trimethyl-2-hexenoic acid, 3,5-dimethyl-
2-hexenoic acid, 2,3,5-trimethyl-2-hexenoic acid, 3,4,4-trimethyl-2-pentenoic acid, 2,
3,4,4-tetramethyl-2-pentenoic acid, 7-octenoic acid, 11-dodesenic acid, 15-hexadecenoic acid, 1
7-octadecenoic acid, oleic acid, elaidic acid, 2-
Methyl-3-butenoic acid, 2-methyl-4-pentenoic acid,
2-methyl-5-hexenoic acid, 2-methyl-6-heptenoic acid, 2-methyl-7-octenoic acid, 2-methyl-11
-Dodecenoic acid, 2-methyl-15-hexadecenoic acid, 2
-Methyl-17-octadecenoic acid, 2-oxo-3-butenoic acid, 3-oxo-4-pentenoic acid, 4-oxo-5
-Hexenoic acid, acrylic acid carboxymethyl ester,
2-carboxyethyl acrylate, 3-carboxypropyl acrylate, 4-carboxybutyl acrylate, 5-carboxypentyl acrylate, 6-carboxyhexyl acrylate, 7-carboxyheptyl acrylate, acrylic acid 8-carboxyoctyl ester, acrylic acid 12-carboxydodecyl ester, acrylic acid 18-
A linear or branched unsaturated aliphatic monocarboxylic acid having 2 to 18 carbon atoms, which may have a substituent such as carboxyoctadecyl ester; maleic acid, fumaric acid, itaconic acid, citraconic acid, mesaconic acid, glutacon Acid, hexenedioic acid, brassic acid, monoacryloyloxymethyl oxalate, mono-3-acryloyloxypropyl oxalate, monoacryloyloxymethyl malonate, mono-3-acryloyloxypropyl malonate, etc. A linear or branched unsaturated aliphatic dicarboxylic acid having 2 to 18 carbon atoms and monoesters thereof which may have a substituent; benzoic acid, α-naphthoic acid, β-naphthoic acid, toluic acid, p -Hydroxybenzoic acid, 6-hydroxy-2-naphthoic acid, nitrobenzoic acid, nitronaphtha Lencarboxylic acid, salicylic acid, cresotic acid, anisic acid, vanillic acid, gallic acid, p-benzoylbenzoic acid, 4-vinylbenzoic acid, 4- (1-propenyl) benzoic acid, 4- (i-propenyl) benzoic acid,
4- (1-methyl-1-propenyl) benzoic acid, 4-
(2-methyl-1-propenyl) benzoic acid, 4-vinylphenylacetic acid, 4- (1-propenyl) phenylacetic acid,
Aromatic which may have a substituent such as 4- (i-propenyl) phenylacetic acid, 4- (1-methyl-1-propenyl) phenylacetic acid, 4- (2-methyl-1-propenyl) phenylacetic acid Monocarboxylic acids; aromatic dicarboxylic acids and their monoesters which may have a substituent such as phthalic acid, isophthalic acid, terephthalic acid, naphthalenedicarboxylic acid and p-hydroxyisophthalic acid; phenylacetic acid, phenylpropionic acid 2,4-dichlorophenoxyacetic acid, 2,4,5-trichlorophenoxyacetic acid, p
-Aromatic aliphatic which may have a substituent such as -hydroxyphenylacetic acid, p-hydroxyphenylpropionic acid, o-carboxyphenyl acrylate, m-carboxyphenyl acrylate, p-carboxyphenyl acrylate Mono- or dicarboxylic acids and their monoesters; and rosin. Examples of the alkylene group having 2 to 18 carbon atoms for Y in the general formula (5) include, for example, ethylene, trimethylene, propylene, butylene, n-pentylene, n-hexylene, n-octylene, n-dodecylene, n-octadecylene and the like. An alkylene group is exemplified.

The arylene group for Y in the general formula (5) includes, for example, o-phenylene, m-phenylene, p-
-Phenylene, 1,8-naphthylene, 1,7-naphthylene, 1,6-naphthylene, 1,4-naphthylene, 1,3
-Naphthylene, 1,2-naphthylene, 2,3-naphthylene, 2,6-naphthylene, 2,7-naphthylene and the like.

The aralkylene group represented by Y in the general formula (5) includes, for example, benzylene, phenethylene and the like.

The cycloalkylene group represented by Y in formula (5) preferably has 3 to 10 carbon atoms, and examples thereof include a cyclopropylene group, a cyclobutylene group, a cyclohexylene group, a cyclooctylene group and a cyclodecylene group. No.

As Y in the general formula (5), ethylene, propylene and p-phenylene are preferred.

Examples of the diamine represented by the following general formula (6) in the diphenyl adduct of triphenylboron represented by the general formula (5) include, for example, ethylenediamine, propylenediamine, trimethylenediamine, tetramethylenediamine , 1,3-diaminobutane, 2,3
-Diaminobutane, pentamethylenediamine, 2,4-
C2-C18 alkylenediamines such as diaminopentane, hexamethylenediamine, octamethylenediamine, dodecamethylenediamine, octadecamethylenediamine; phenylenediamines such as m-phenylenediamine and p-phenylenediamine; Arylenediamines such as naphthylenediamines such as diaminonaphthalene and 1,5-diaminonaphthalene; aminobenzylamines such as 3-aminobenzylamine and 4-aminobenzylamine; and 3-aminophenethylamine and 4-aminophenethylamine Aminoaralkylamines such as aminophenethylamines; diaminocycloalkanes such as 1,3-diaminocyclohexane and 1,4-diaminocyclohexane; and the like. Min, p- phenylenediamine are preferable.

The triphenylboron derivative (1) of the present invention
Can be synthesized, for example, by the following method.

Embedded image (In the formula, each symbol is as defined above.)

That is, a diamine adduct of triphenylboron represented by the general formula (5) or a solution thereof is added to a carboxyl group-containing compound represented by the general formula (4) or a solution thereof, and reacted. It is obtained by removing the solvent by distillation under reduced pressure.

Alternatively, a carboxyl group-containing compound represented by the general formula (4) or a solution thereof is added to a diphenyl adduct of triphenylboron represented by the general formula (5) or a solution thereof, and reacted. It is obtained by removing the solvent by distillation under reduced pressure.

In the above method, the carboxyl group-containing compound represented by the general formula (4) and the diphenyl adduct of triphenylboron represented by the general formula (5) are subjected to an equivalent reaction between the carboxyl group and the amino group contained therein. Is fine.

The solvent used in the above-mentioned method is not particularly limited as long as it does not adversely affect the reaction. For example, xylene, toluene, chloroform, methanol, isopropanol, n-butanol, propylene glycol monomethyl ether These may be used alone or in combination of two or more.

The diphenyl adduct of triphenylboron represented by the general formula (5) can be synthesized, for example, by the method shown in the following formula.

Embedded image (In the formula, each symbol is as defined above.)

That is, an aqueous solution of sodium hydroxide adduct of triphenylboron is added to an aqueous solution of the general formula (6):

Embedded image Is obtained by dropping a diamine represented by the formula, washing the precipitated insolubles with water, and drying.

The general formula (2) of the present invention:

Embedded image (Wherein each symbol is as defined above) (hereinafter also referred to as triphenylboron derivative (2)) is a carboxyl group represented by the above general formula (4). Containing compound and general formula (7):

Embedded image (Wherein each symbol has the same meaning as described above), ie, a triphenylboron N-containing heterocyclic adduct represented by the following general formula (8):

Embedded image And an adduct with an N-containing heterocyclic compound substituted with an amino group represented by the formula: The carboxyl group-containing compound represented by the general formula (4) may be the same as the carboxyl group-containing compound in the general formula (1).

The halogen atom of R ¹ in the general formula (2) includes, for example, a chlorine atom, a bromine atom, a fluorine atom and the like. Examples of the alkyl group having 1 to 18 carbon atoms for R ¹ include methyl, ethyl, n-propyl,
Isopropyl, n-butyl, sec-butyl, tert
-Butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, 2-ethylhexyl, n-dodecyl, n-octadecyl and the like straight-chain or branched alkyl groups, among which the number of carbon atoms is 1 to 4 Alkyl groups are preferred. n is preferably 0 or 1. R ¹ is preferably a hydrogen atom or an alkyl group having 1 to 4 carbon atoms.

In the triphenylboron N-containing heterocyclic adduct represented by the general formula (7), the N-containing heterocyclic ring substituted with an amino group represented by the general formula (3) includes: It may be a heterocyclic monocyclic ring or a condensed heterocyclic ring, may be a saturated heterocyclic ring or an unsaturated heterocyclic ring, and may contain a sulfur atom or an oxygen atom, but preferably has a 5- or 6-membered ring or a condensed ring containing the same. Preferably, for example, pyridine ring, pyrimidine ring, pyrrole ring, pyrazole ring, pyrrolidine ring, pyrazoline ring, piperidine ring, piperazine ring,
Pyrazine ring, purine ring, imidazole ring, benzimidazole ring, indole ring, indazole ring, triazole ring, carbazole ring, phenothiazine ring, phenoxazine ring, quinoline ring, etc., among which pyridine ring,
A piperidine ring is preferred.

In the triphenylboron N-containing heterocyclic adduct represented by the general formula (7), the N-containing heterocyclic group substituted by an amino group represented by the general formula (8) includes, for example, 3-amino Pyridine, 4-aminopyridine, 4-aminopyrimidine, 5-aminopyrimidine, 3-aminopyrazole, 4-aminopyrazole, 4-aminoimidazole, 4-aminoindazole, 5-aminoindazole, 4-aminoindole, 5-amino Indole, 4
-Aminobenzimidazole, 3-aminopyrrolidine,
3-aminopiperidine, 4-aminopiperidine, 3-aminoquinoline, 5-aminoquinoline, 1-aminopiperazine, aminopyrazine, 2-aminopurine, 3-aminopyrrole, 3-aminopyrazoline, 3-amino-1,
2,4-triazole, 4-amino-1,2,4-triazole, 4-aminocarbazole, 4-aminophenitidine, 4-aminophenoxazine and the like, among which 4-aminopyridine, 4-aminopiperidine Is preferred.

The triphenylboron derivative (2) of the present invention
Can be synthesized, for example, by the following method.

Embedded image (In the formula, each symbol is as defined above.)

That is, the N-containing heterocyclic adduct of triphenylboron represented by the general formula (7) or a solution thereof is added dropwise to the carboxyl group-containing compound represented by the general formula (4) or a solution thereof to react. And then the solvent is removed by distillation under reduced pressure.

In the above method, the solvent used is not particularly limited as long as it does not adversely affect the reaction, and examples thereof include xylene, toluene, chloroform, methanol, isopropanol, n-butanol,
Examples thereof include propylene glycol monomethyl ether and the like, and these may be used alone or as a mixture of two or more.

The N-containing heterocyclic adduct of triphenylboron represented by the general formula (7) can be synthesized, for example, by the method shown in the following formula.

Embedded image (In the formula, each symbol is as defined above.)

That is, an N-containing heterocycle substituted with an amino group represented by the general formula (8) is added to an aqueous solution of sodium hydroxide adduct of triphenylboron, and the precipitated insoluble material is washed with water and dried. It is obtained by doing.

The triphenylboron derivative (1) of the present invention
And (2) can be prepared as antifouling agents such as fishing net antifouling agents and underwater antifouling paints (for example, ship bottom paints) by a usual method, for example, the following method.

A. Fishing net antifouling agent The fishing net antifouling agent of the present invention has low toxicity and high safety, and is a long-term intestinal animal such as hydro insects and oberia; shellfish such as barnacles, mussels, oysters, and serplas; It exhibits an excellent anti-adhesion effect on tubal polychaetes such as yak Kansashi and squid, and other aquatic fouling organisms.

The antifouling agent for fishing nets of the present invention is prepared by dispersing or dissolving the triphenylboron derivative (1) or (2) in an organic solvent. In the fishing net antifouling agent of the present invention, the content of the triphenylboron derivative (1) or (2) can be arbitrarily changed depending on the application environment, but is preferably 1 to 25% by weight, more preferably 2 to 10% by weight. %. If the content is less than 1% by weight, the effect of preventing adhesion to aquatic fouling organisms is insufficient, and if the content exceeds 25% by weight, the effect of preventing adhesion to aquatic fouling organisms corresponding to the increased amount cannot be obtained.

Examples of the organic solvent used in the antifouling agent for fishing nets of the present invention include aromatic compound-based organic solvents, ketone compound-based organic solvents, and aliphatic compound-based organic solvents. Examples include xylene, toluene, pseudocumene, diethylbenzene, triethylbenzene, mesitylene, solvent naphtha, butanol, isopropanol, methyl isobutyl ketone, hexane, propylene glycol monomethyl ether, and the like. These solvents may be used alone or in combination of two or more.

If necessary, acrylic resin, synthetic rubber, rosin resin, silicone resin, polybutene resin,
Various resins such as a chlorinated rubber resin, a vinyl chloride resin, an alkyd resin, a coumarone resin, an ethylene-vinyl acetate resin, and an epoxy resin may be blended. These resins may be used alone or in combination of two or more. When the triphenylboron derivative (1) or (2) in the present invention is used as an antifouling agent for fishing nets, the polymer alone exhibits an excellent effect of preventing adhesion to aquatic fouling organisms. By blending the antifouling component and the like, a more excellent adhesion preventing effect can be exhibited.

Examples of the silicone oil used in the fishing net antifouling agent of the present invention include dimethyl silicone oil, methyl hydrogen silicone oil, (higher) fatty acid-modified silicone oil, alkyl-modified silicone oil, amino-modified silicone oil, and epoxy-modified silicone oil. Examples thereof include silicone oil, polyether-modified silicone oil, and methylphenyl silicone oil. Among them, polyether-modified silicone oil and (higher) fatty acid-modified silicone oil are preferable. These may be used alone or in combination of two or more. The content of these silicone oils can be arbitrarily changed depending on the application environment, but is preferably 0.1 to 50% by weight, more preferably 0.5 to 25% by weight in the fishing net antifouling agent. If the content is less than 0.1% by weight, the combined effect cannot be expected, while if it exceeds 50% by weight, the physical properties of the coating film are undesirably reduced.

Known antifouling components used in the fishing net antifouling agent of the present invention include, for example, 1,3-dicyanotetrachlorobenzene, 2- (thiocyanomethylthio) benzothiazole, bis (2-pyridylthio-1-). Oxide) zinc, bis (2-pyridylthio-1-oxide) copper, 2-
Tertiary butylamino-4-cyclopropylamino-6-
Methylthio-1,3,5-triazine, cuprous oxide, copper thiocyanate (CuSCN), N, N-dimethyldichlorophenylurea, 4,5-dichloro-2-n-octyl-
3-isothiazolone, N- (fluorodichloromethylthio) phthalimide, 2,3,5,6-tetrachloro-4
-(Methylsulfonyl) pyridine, 2,4,5,6-tetrachloroisophthalonitrile, dimethyldithiocarbamate zinc salt, bis (dimethyldithiocarbamoyl) zinc ethylenebisdithiocarbamate, pyridine-triphenylboron, triphenylboron-alkyl (C3-C30) amine (e.g., triphenylboron-n
-Octadecylamine, triphenylboron-n-hexadecylamine, triphenylboron-n-octylamine, etc.), triphenylboron-rosinamine, rodane copper, copper hydroxide, copper naphthenate, manganese ethylene bisdithiocarbamate, zinc Ethylenebisdithiocarbamate, N, N'-dimethyl-N'-phenyl- (N
-Fluorodichloromethylthio) sulfide, 3-iodo-2-propynylbutylcarbamate, diiodomethylparatolylsulfane, 2- (4-thiazolyl)-
Examples include benzimidazole and other non-tin antifouling compounds.

Further, the general formula (9):

Embedded image (In the formula, R ⁷ is the same or different and represents an alkyl group having 1 to 4 carbon atoms.) Tetraalkylthiuram disulfides represented by the formula: Examples of the alkyl group having 1 to 4 carbon atoms of R ⁷ in the general formula (9) include straight-chain or branched-chain groups such as a methyl group, an ethyl group, an n-propyl group, an isopropyl group, and a butyl group. Among them, an ethyl group and a butyl group are preferred.

Specific examples of the tetraalkylthiuram disulfide represented by the general formula (9) include tetramethylthiuram sulfide, tetraethylthiuram disulfide, tetraisopropylthiuram disulfide, and tetra-ethylthiuram disulfide. n-butylthiuram disulfide and the like.

Further, the general formula (10):

Embedded image (Wherein, R ⁸ represents a hydrogen atom, 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,
Indicates an alkyl-substituted benzyl group or a halogen-substituted benzyl group. )), And 2,3-dichloromaleimides.

Examples of the alkyl group represented by R ⁸ in the general formula (10) include a methyl group, an ethyl group, an isopropyl group, an n-butyl group, a tert-butyl group, an octyl group,
Examples thereof include a linear or branched one having 1 to 18 carbon atoms such as a dodecyl group, a tetradecyl group, a hexadecyl group, and an octadecyl group. Examples of the halogen-substituted alkyl group include a dichloromethyl group, a dichloroethyl group, and a trichloroethyl group. Examples of the cycloalkyl group include a cyclohexyl group. Examples of the alkyl-substituted phenyl group include a dimethylphenyl group, a diethylphenyl group, a trimethylphenyl group, and a methylethylphenyl group. Examples of the halogen-substituted phenyl group include a dichlorophenyl group. Examples of the alkyl-substituted benzyl group include a methylbenzyl group, a dimethylbenzyl group, a diethylbenzyl group, and an α-methylbenzyl group. Examples of the halogen-substituted benzyl group include a chlorobenzyl group and a dichlorobenzyl group. R ⁶ is preferably an ethyl group, a butyl group, a diethylphenyl group, a methylethylphenyl group, or a benzyl group.

Specific examples of the 2,3-dichloromaleimide represented by the general formula (10) include, for example, 2,3-dichloro-N-ethylmaleimide and 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- Benzyl maleimide, 2,3-dichloro-N- (2-chlorobenzyl) maleimide, 2,3-dichloro-N- (4-chlorobenzyl) maleimide, 2,3-dichloro-N- (2-methylbenzyl) maleimide , 2,3-dichloro-N- (2,
4-dimethylbenzyl) maleimide, 2,3-dichloro-N- (3,4-dimethylbenzyl) maleimide,
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
-(2,6-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 and the like.

Among the above known antifouling components, bis (2
-Pyridylthio-1-oxide) zinc, bis (2-pyridylthio-1-oxide) copper, 2-tert-butylamino-4-cyclopropylamino-6-methylthio-1,
3,5-triazine, cuprous oxide, copper thiocyanate (Cu
SCN), N, N-dimethyldichlorophenylurea,
4,5-dichloro-2-n-octyl-3-isothiazolone, N- (fluorodichloromethylthio) phthalimide, 2,3,5,6-tetrachloro-4- (methylsulfonyl) pyridine, 2,4,5 6-tetrachloroisophthalonitrile, dimethyldithiocarbamate zinc salt,
Bis (dimethyldithiocarbamoyl) zinc ethylenebisdithiocarbamate, pyridine-triphenylboron, triphenylboron-alkyl (C3-30)
Amines (e.g., triphenylboron-n-octadecylamine, triphenylboron-n-hexadecylamine, triphenylboron-n-octylamine, etc.), triphenylboron-rosinamine, rodan copper, and tetraethylthiuram disulfide; preferable.

The above antifouling components may be used alone,
Also, two or more kinds may be used in combination. The weight ratio of the above-mentioned known antifouling component to the triphenylboron derivative (1) or (2) of the present invention can be arbitrarily changed depending on the application environment, but is preferably 1:50 to 50: 1. More preferably 1:25 to 25: 1, still more preferably 1:10 to
The range is 10: 1.

The elution modifier used in the fishing net antifouling agent of the present invention includes a compound represented by the following general formula (11):

Embedded image (Wherein R ⁹ is the same or different and each has 1 to 2 carbon atoms)
It represents 0 alkyl groups, and r represents an integer of 2 to 10. )).

In the general formula (11), as the alkyl group having 1 to 20 carbon atoms represented by R ⁹ , an ethyl group, a propyl group, a tert-butyl group, a tert-amyl group,
A straight or branched chain having 2 to 19 carbon atoms such as a tert-nonyl group, a tert-dodecyl group and a nonadecyl group is preferred. r is preferably 3 to 8.

Specific examples of the dialkyl polysulfides represented by the general formula (11) include, for example, diethyl pentasulfide, dipropyl tetrasulfide, ditertiary butyl disulfide, and ditertiary butyl disulfide. Tertiary butyl tetrasulfide, ditertiary amyl tetrasulfide, ditertiary nonyl pentasulfide, ditertiary octyl pentasulfide, ditertiary dodecyl pentasulfide, dino Nadecyl tetrasulfide and the like.

Further, polybutene having an average molecular weight of 200 to 1,000, paraffins, vaseline, glycerin, polyhydric alcohols, and fatty acid esters can also be used as the dissolution controlling agent.

Examples of polybutene having an average molecular weight of 200 to 1,000 include, for example, LV-5, manufactured by Nippon Oil Co., Ltd.
LV-10, LV-25, LV-50, LV-100,
HV-15, HV-35, HV-50, HV-100,
HV-300 and the like. As paraffins,
For example, liquid paraffin, paraffin wax, chlorinated paraffin and the like can be mentioned. Examples of petrolatum include white petrolatum, yellow petrolatum, and the like. Examples of polyhydric alcohols include (poly) ethylene glycol, (poly) propylene glycol, and the like.

Among the above-mentioned elution modifiers, di-tertiary nonyl pentasulfide, di-tertiary octyl pentasulfide, polybutene, liquid paraffin, white petrolatum,
Yellow petrolatum, polyethylene glycol and polypropylene glycol are preferred.

The above-mentioned dissolution controlling agents may be used alone or in combination of two or more. The content of the above-mentioned elution modifier can be arbitrarily changed depending on the application environment, but is preferably 1 to 30% by weight, more preferably 3 to 20% by weight in the fishing net antifouling agent. The content is 1% by weight
When the amount is less than 30%, the combined effect cannot be expected. On the contrary, when the amount exceeds 30% by weight, the properties of the coating film are deteriorated, which is not preferable.

B. Underwater antifouling paint The underwater antifouling paint of the present invention has low toxicity and high safety, and for a long period of time, worms such as hydro insects and oberia; shellfish such as barnacles, mussels, oysters, and serplas; It exhibits an excellent anti-adhesion effect on tubal polychaetes such as yak Kansashi and squid, and other aquatic fouling organisms.

The underwater antifouling paint of the present invention is prepared by mixing the triphenylboron derivative (1) or (2) with a water-soluble resin or a water-insoluble resin and mixing and dispersing the mixture using a paint conditioner, a homomixer or the like. Prepared.
Other components commonly used in paints, solvents (xylene, methyl isobutyl ketone, n-butanol, butyl acetate, etc.), pigments (silver, titanium oxide, zinc oxide, etc.), plasticizers, fillers (talc, finely divided silica, etc.) ), An additive such as a curing accelerator can be blended as required.

The content of the triphenylboron derivative (1) or (2) in the underwater antifouling paint of the present invention can be arbitrarily changed depending on the application environment, but is preferably 1% by weight or less.
It is 50% by weight, more preferably 2% to 20% by weight. If the content is less than 1% by weight, the effect of preventing adhesion to aquatic fouling organisms is insufficient, and if it exceeds 50% by weight, the effect of preventing adhesion to aquatic fouling organisms corresponding to the increased amount cannot be obtained.

When the triphenylboron derivative (1) or (2) in the present invention is used as an underwater antifouling paint, the polymer alone exhibits an excellent effect of preventing adhesion to aquatic fouling organisms. By blending an agent and a known antifouling component, a more excellent adhesion preventing effect can be exhibited. Examples of the silicone oil, the dissolution controlling agent, and the known antifouling component include those described in the description of the fishing net antifouling agent. Further, if necessary, various resins as described in the description of the fishing net antifouling agent may be blended.

The content of the silicone oil can be arbitrarily changed depending on the application environment, but is preferably 0.1 to 50% by weight, more preferably 0.5 to 2% by weight in the underwater antifouling paint.
5% by weight. If the content is less than 0.1% by weight, the combined effect cannot be expected, and if it exceeds 50% by weight, the properties of the coating film deteriorate, which is not preferable.

The weight ratio of the known antifouling component to the triphenylboron derivative (1) or (2) of the present invention can be arbitrarily changed depending on the application environment, but is preferably 1:50.
To 50: 1, more preferably 1:25 to 25: 1, even more preferably 1:10 to 10: 1.

The content of the dissolution controlling agent can be arbitrarily changed depending on the application environment, but is preferably 1 to 30% by weight, more preferably 3 to 20% by weight in the underwater antifouling paint. If the content is less than 1% by weight, the combined effect cannot be expected, and if it exceeds 30% by weight, the properties of the coating film deteriorate, which is not preferable.

The present invention will be described in detail below with reference to examples and comparative examples, but the present invention is not limited to these examples. Example 1 <Synthesis of triphenylboron adduct> An aqueous sodium hydroxide adduct of triphenylboron (manufactured by Tokyo Chemical Industry Co., Ltd.) ; 9% aqueous solution), and stirring was started. Ethylenediamine at room temperature (Tosoh Corporation)
4.81 g is gradually dropped from the dropping funnel. After the addition, the mixture was stirred at the same temperature for 5 hours. The precipitate was collected by filtration, washed with water, and dried to obtain 21.64 g of a white powdery substance. The obtained compound was analyzed by elemental analysis and IR (infrared) spectrum. As a result, it was confirmed that the compound was the target product, triphenylboron-ethylenediamine adduct (triphenylboron adduct A). Melting point 157.8-1
59.8 ° C. Examples 2 to 4 Synthesis was performed in the same manner as in Example 1 to obtain triphenylboron adducts BD. They are shown in Table 1 together with the triphenylboron adduct A. The unit of each number in Table 1 is g.

[Table 1] Example 5 <Synthesis of triphenylboron derivative> 3 equipped with a mechanical stirrer, a cooling pipe, and a thermometer
In a 00 mL four-necked flask, 28.3 g of oleic acid,
Xylene / propylene glycol monoethyl ether =
100 g of an 80/20 mixed solvent was charged, and stirring was started. At room temperature, 30.2 g of the triphenylboron-ethylenediamine adduct (triphenylboron adduct A) synthesized in Example 1 was charged. After stirring at the same temperature for 2 hours,
The solvent was removed by distillation under reduced pressure, and the residue was dried under reduced pressure to obtain 56.7 g of a yellow-orange wax (triphenylboron derivative A). As a result of analysis by IR (infrared) spectrum, it was confirmed that it was a target substance. FIG. 1 shows the IR (infrared) spectrum of this derivative. Examples 6 to 15 Using the triphenylboron adduct, the carboxyl group-containing compound, and the solvent shown in Table 2, synthesis was performed in the same manner as in Example 5, and triphenylboron derivatives BK were obtained. The unit of each number in Table 2 is g unless otherwise specified.
It is.

[Table 2] Examples 16 to 29 and Comparative Examples 1 to 3 <Examples of Formulation of Fishing Net Antifouling Agent> Using the triphenylboron derivatives A to obtained in Examples 5 to 15, the fishing net antifouling agent of the present invention (Examples 16 to 29) 29) was prepared according to the formulation shown in Table 3. Similarly, Comparative Examples 1 to
3 fishing net antifouling agents were prepared. The unit of each number in Table 3 is% by weight.

[Table 3] Examples 30 to 44 and Comparative Examples 4 to 7 <Examples of Formulation of Ship Bottom Paint> Triphenylboron Derivatives A to K Obtained in Examples 5 to 15
Was used to prepare ship bottom paints of the present invention (Examples 30 to 44) according to the formulations shown in Table 4. Similarly, Comparative Examples 4 to
7 Bottom paints were prepared. The unit of each number in Table 4 is% by weight.

[Table 4] <Fishing net antifouling agent effect test> The fishing net antifouling agents of Examples 16 to 29 and Comparative Examples 1 to 3 of the present invention were each applied to a polyethylene knotless net (6 sections, 400 denier / 60 lines) by dip coating. After air-drying, it was set in a metal frame. These test nets were immersed about 1.5 m below the sea surface off Sukumo City, Kochi Prefecture, and the state of fouling of the test nets due to the attachment of aquatic fouling organisms was observed. The fouling status of the net was evaluated according to the criteria shown below, and the results are shown in Table 5.

[Table 5] No treatment: Evaluation criteria for the soiling status of a polyethylene knotless net not treated with a fishnet antifouling agent Evaluation A: Soiled area of fishnet 0%. No aquatic fouling organisms attached. Evaluation B: Soiled area of fishing net 0 to 10%. Although aquatic fouling organisms are slightly attached, they are practically acceptable. Evaluation C: 10 to 50% of the fouled area of the fishing net. Aquatic fouling organisms are often attached and can no longer be used as fishing nets. Evaluation D: Fouling area of fishing net is 50% or more. Extremely large amount of aquatic fouling organisms attached. A large number of aquatic fouling organisms such as barnacles and kansane kanashi adhered to Comparative Examples 1 to 3 and the untreated net after one to two months. On the other hand, in Examples 16 to 29,
For at least 4 months, no attachment of shellfish, tubal polychaete and other aquatic fouling organisms was found on the submerged nets. <Ship bottom paint effect test> The bottom paints of Examples 30 to 44 of the present invention and Comparative Examples 4 to 7 were applied to both sides of a 50 x 100 x 2 mm hard vinyl chloride plate so as to obtain a dry coating film of about 100 microns. did. After air-drying for one day, these test plates were immersed about 1.5 m below the sea surface off Sukumo City, Kochi Prefecture, and the test plates were observed for contamination by aquatic organisms. The contamination status of the net was evaluated according to the criteria shown below, and the results are shown in Table 6.

[Table 6] No treatment: Evaluation criteria of the soiling status of the hard vinyl chloride plate test plate not treated with the ship bottom antifouling paint Evaluation A: Stained area of the test plate 0%. No aquatic fouling organisms attached. Evaluation B: Stained area of test plate 0 to 10%. Although aquatic fouling organisms are slightly attached, they are practically acceptable. Evaluation C: Stained area of test plate 10 to 50%. Attached to aquatic fouling organisms, not used as ship bottom paint. Evaluation D: The stained area of the test plate was 50% or more. Extremely large amount of aquatic fouling organisms attached. After 1 month to 4 months, many aquatic fouling organisms including barnacles and kansane kanashi adhered to Comparative Examples 4 to 7 and the untreated plate. On the other hand, in Examples 30 to 44,
No attachment of shellfish, tubal polychaete and other aquatic fouling organisms was observed on the test plate that had been immersed for 6 months.

As is apparent from the above description, the triphenylboron derivative (1) or (2) of the present invention is a coelenterate such as a hydroid or an oberia; a shellfish such as a barnacle, a mussel, an oyster, or a serpla. Tubal polychaetes such as kansane kansashi, human kansetsu, yakko kansashi, and squid moss; and extremely low adhesion of other aquatic fouling organisms, exhibiting an excellent anti-adhesion effect, and further containing other paint resins and antifouling components. Has good miscibility and little adverse effect on the environment. Therefore, the antifouling agent containing the triphenylboron derivative (for example, a fishing net antifouling agent or an underwater antifouling paint such as a ship bottom antifouling paint)
It will be very useful.

[Brief description of the drawings]

FIG. 1 shows an IR (infrared) spectrum of the triphenylboron derivative obtained in Example 5. [IR measurement conditions] Apparatus: Specru manufactured by PERKIN-ELMER
m One measurement method: KBr tablet method

──────────────────────────────────────────────────の Continuation of the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) C09D 201/00 C09D 201/00 (72) Inventor Masanori Furuhara 955, Kotoyoshi, Yoshitomi-cho, Yoshitomi-gun, Fukuoka F-term in the Research & Development Division, Wealth Fine Chemicals Co., Ltd. F-term (reference)

Claims (8)

[Claims] 1. General formula (1): Or, the general formula (2): [In the formula, p and q are not simultaneously 0 and each represent 0 or 1. When p = 0 and q = 1, X is an alkyl group having 1 to 18 carbon atoms, and 2 to 18 carbon atoms. Alkenyl group, aryl group, aralkyl group, aralkenyl group,-
CH (= O) groups, -C (= O) -R ² group, -C (= O)
-OR ^{2 group,} -R 3 ^{-O-R 4 group,} -R 3 -C (= O)
-R indicates ^four, when p = 1 and q = 1, X is an alkylene group having 1 to 18 carbon atoms, an alkenylene group having 2 to 18 carbon atoms, an arylene group, aralkylene group, Ararukeniren group, -R ⁵ —OR ⁶ — group, —R ⁵ —C (＝ O) —R
⁶ represents a ⁶ -group, Y represents an alkylene group having 2 to 18 carbon atoms, an arylene group, an aralkylene group or a cycloalkylene group, and n R ^{1 s} are the same or different and are each a halogen atom or a carbon atom having 1 to 18 carbon atoms. Represents an alkyl group represented by
² represents an alkyl group having 1 to 18 carbon atoms, an alkenyl group having 2 to 18 carbon atoms, an aryl group, an aralkyl group, and an aralkenyl group, wherein R ³ , R ⁵ , and R ⁶ are the same or different, Alkylene group of 1 to 18, carbon number of 2 to 18
Represents an alkenylene group, an arylene group, an aralkylene group, or an arkenenylene group, wherein R ⁴ is a hydrogen atom,
8 represents an alkyl group, an alkenyl group having 2 to 18 carbon atoms, an aryl group, an aralkyl group, and an aralkenyl group;
And represents an integer of from 1 to 3, and represented by the general formula (3): The group represented by represents an N-containing heterocyclic ring substituted with an amino group. ] The triphenylboron derivative represented by these. 2. The triphenylboron derivative according to claim 1, wherein the carboxyl group-containing compound in the general formulas (1) and (2) is rosin. 3. A composition containing the triphenylboron derivative according to claim 1 or 2. 4. The composition according to claim 3, further comprising at least one selected from the group consisting of a silicone oil, an elution modifier and a known antifouling component. 5. An antifouling agent containing the triphenylboron derivative according to claim 1. 6. The antifouling agent according to claim 5, further comprising at least one selected from the group consisting of a silicone oil, an elution control agent, and a known antifouling component. 7. The antifouling agent according to claim 5, which is used for antifouling of fishing nets. 8. The anti-fouling paint for underwater use according to claim 5 or 6.
The antifouling agent according to the above.