JPH06122842A - Sustainable underwater antifoulant - Google Patents

Abstract

PURPOSE:To obtain the subject antifoulant capable of preventing, e.g. Hydroides elegans Haswell from sticking, excellent in adhesiveness, useful for fishnets, ship bottoms, seawater intake channels etc., comprising each specific sulfonate group-contg. polymer and higher aliphatic amine compound at specified proportion. CONSTITUTION:This antifoulant comprises (A) a sulfonate group-bearing polymer 2000-600000 in molecular weight and (B) a higher aliphatic amine compound of the formula (R<1> is 12-20C aliphatic hydrocarbon; R<2> is H or 1-6C alkyl; R<3> is H, 1-6C alkyl or 12-20C aliphatic hydrocarbon, etc.) such as dodecylamine at such a proportion as to be 0.8-1.2mol of the component B per one sulfonate group in the component A.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a persistent underwater antifouling agent. In particular, by applying it to fishing nets, ship bottoms, seawater intakes, etc., a sustainable underwater antifouling agent for long-term prevention of adhered organisms, especially in the sea, adhering to fishing nets, ship bottoms, seawater intakes, etc. Regarding

[0002]

2. Description of the Related Art In recent years, aquaculture and fisheries and the construction of marine facilities have become popular, and the habitat of periphyton is expanding. Therefore, the bottom of the ship, underwater structures, aquaculture nets, buoys or stationary nets, etc. are retained in seawater for a long time,
Many adherent organisms such as barnacles, magnolias, and blue mussels attach to them, causing various disorders.

Conventionally, various antifouling agents have been proposed for suppressing the attachment of adherent organisms in order to prevent the adherent organisms from adhering to fishing nets, ship bottoms, seawater intake channels, etc. and causing adverse effects.
It is also used in practice. For example, organotin compounds,
An antifouling agent containing an antifouling active ingredient of a highly toxic compound such as an organic or inorganic copper compound or an organic chlorine compound and a specific acrylic acid polymer has been proposed. However, these antifouling active ingredients are highly toxic enough to cause problems of marine pollution and have the property of accumulating in the living body. For this reason, in the case of handling edible aquatic organisms in the aquaculture industry, in particular, there is a risk that the human body may be affected and that the workers who directly handle the antifouling agent may be affected.

Further, in order to enhance safety, an antifouling agent using a polyisocyanate compound or a metal compound capable of chelating with a carboxyl group instead of the poison has been proposed. However, these highly safe antifouling agents still cannot be said to have sufficient antifouling effects over a long period of time. Therefore, an antifouling agent that is highly safe and has a long-lasting antifouling effect is desired.

The applicant of the present invention has previously found that a specific higher aliphatic amine compound having low toxicity and good biodegradability has an excellent antifouling effect, and the amine compound and a specific carboxyl group have been found. A persistent underwater antifouling agent containing a film-forming agent comprising a contained copolymer (polymer) has already been proposed (JP-A-1-103672, JP-A-3-252462, JP-A-3). (See Japanese Patent No. 252463).

It is also proposed and known that a polymerizable unsaturated monomer having a sulfonic acid group is reacted with a higher aliphatic quaternary ammonium salt and then polymerized to be used as an antifouling agent ( PCT. Published WO9 by J. McCrealey et al.
(See Japanese Patent Publication No. 1/09915).

[0007]

Generally, as an effective antifouling composition, an antifouling active ingredient exhibits a moderate antifouling effect, an antifouling active ingredient is a highly safe compound, and an antifouling effective The component elutes at a constant rate for a long time from the coated surface, that is, the elution amount of the antifouling active ingredient can be adjusted, and after the antifouling active ingredient is eluted, a film forming agent (polymer)
Must not be left in fishing nets, etc.

Of the above-mentioned conventional antifouling agents, those using a highly toxic organic or inorganic metal compound do not satisfy the conditions,
Those using a polyisocyanate compound or a metal compound capable of chelating with a carboxyl group do not satisfy the conditions. Further, those using a polymer obtained by reacting a polymerizable unsaturated monomer having a sulfonic acid group with a higher aliphatic quaternary ammonium salt do not satisfy the condition because they are weakly effective against barnacles and magnolias.

On the other hand, the antifouling agent using a higher aliphatic amine satisfies the conditions and, but the higher aliphatic amine is (1) liquid at room temperature and highly soluble in seawater. (2) Since it has poor compatibility with a polymer (acrylic acid ester or the like) as a coating film forming agent (elution controlling agent), it has a problem that it separates and floats on the coating film surface.

Therefore, the above-mentioned Japanese Patent Laid-Open No. 1-110367.
No. 2, JP-A-3-252462, JP-A-3-
The persistent underwater antifouling agent containing a higher aliphatic amine described in Japanese Patent No. 252463 is also an active ingredient of the underwater antifouling agent when it is immersed in seawater for a long period of time by being applied to a fishing net, a ship bottom, a seawater intake channel, or the like. The elution amount of a certain higher aliphatic amine compound could be adjusted to some extent, but it was not sufficient, and the elution amount immediately after immersion became large, and the elution amount tended to decrease with the passage of time. For this reason, the antifouling effect is maintained for a considerable period in a sea area with a small amount of attached organisms, but a long term (for example, 6
The antifouling effect of 10 months) was not yet satisfactory.

It is considered that this is because the polycarboxylic acid type copolymer has a weak ability to fix the amine compound.
Further, with the passage of time, the copolymer becomes insoluble and remains as a coating film on a fishing net or the like.When the antifouling agent is applied again, the adhesion with the remaining coating film is poor and the antifouling agent peels off. It also had the problem of being easy.

It is considered that the cause of the insolubility of the copolymer is mainly that the carboxyl group in the copolymer reacts with the hardness component of seawater. Therefore, the present invention is based on the above conditions
It is an object to provide a persistent underwater antifouling agent that satisfies all of the above.

[0013]

SUMMARY OF THE INVENTION The inventors of the present invention have
A fishing net etc. coated with a salt of a polymer having a sulfonic acid group and a higher aliphatic amine compound has a long-lasting antifouling effect, and after a certain period of time, no polymer remains in the fishing net etc. I confirmed and completed this invention.
Thus, according to the present invention, a polymer having a sulfonic acid group having a molecular weight of 2000 to 600,000 and a compound represented by the general formula (I):

[0014]

[Chemical 2] (In the formula, R ¹ represents a saturated or unsaturated aliphatic hydrocarbon group having 12 to 20 carbon atoms, and R ² represents a hydrogen atom or 1 carbon atom.
R ³ is substituted with a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, a saturated or unsaturated aliphatic hydrocarbon group having 12 to 20 carbon atoms, or an alkyl group having 1 to 6 carbon atoms. 1 to 1 carbon atoms substituted with an optionally substituted amino group
6 represents an alkyl group. And a higher aliphatic amine compound represented by the formula (1) is contained in the polymer in a proportion of 0.8 to 1.2 mol of the higher aliphatic amine compound per sulfonic acid group in the polymer. To be done.

In the present invention, specific examples of the higher aliphatic amine compound represented by the general formula (I) include dodecylamine, tetradecylamine, hexadecylamine, octadecylamine, oleylamine, tallow alkylamine, and coconut alkyl. Primary amines such as amines; di (dodecyl) amine, di (octadecyl) amine, di (oleyl) amine, di (tallow alkyl) amine, di (coconut alkyl) amine, dodecyl octadecylamine, dodecylmethylamine, dodecylethylamine, Secondary amines such as hexadecylbutylamine, hexadecylmethylamine, octadecylmethylamine, tallow alkylmethylamine, hardened tallow alkylmethylamine, coconut alkylmethylamine; dodecyldimethylamine, hexadecyldimethylamine, Kuta decyl dimethyl amine, coconut alkyl dimethylamine, beef tallow alkyl dimethyl amine,
Hardened tallow alkyldimethylamine, didodecylmethylamine, dioctadecylmethylamine, dodecylhexadecylmethylamine, tallow alkyldiethylamine, coconut alkyldihexylamine and other tertiary amines; dodecylethylenediamine, hexadecylethylenediamine, octadecylethylenediamine, oleylethylenediamine, N-monosubstituted ethylenediamine such as beef tallow alkylethylenediamine; dodecyltrimethylenediamine, hexadecyltrimethylenediamine, octadecyltrimethylenediamine, oleyltrimethylenediamine, palm alkyltrimethylenediamine, tallowalkyltrimethylenediamine, hardened tallowalkyltrimethylenediamine And the like, such as N-monosubstituted trimethylenediamine.

Among these amines, "coconut alkyl ...
"Amine", "beef tallow alkyl ... amine,""hardened beef tallow alkyl ..." Amine is a straight chain having 12 to 20 carbon atoms, which is produced by known means from coconut oil, coconut fat, beef tallow, or the like. It means that it is a mixture of amines (branched alkylamines) in which branched saturated or unsaturated aliphatic hydrocarbon groups occupy the main components, and higher aliphatic amines are represented by the general formula (I). Any one of these compounds may be used alone, or two or more of them may be used in combination.

The polymer having a sulfonic acid group used in the present invention is capable of polymerizing the polymerizable unsaturated monomer (a) having a sulfonic acid group or copolymerizing with the monomer (a). Is a polymer having an average molecular weight of 3,000 to 400,000 obtained by polymerization with another polymerizable unsaturated monomer (b), and as the polymerizable unsaturated monomer (a) having a sulfonic acid group, Any aromatic or aliphatic compound having at least one sulfonic acid group and an unsaturated bond in one monomer may be used, for example, 1) styrene-based styrenesulfonic acid, 2) (meth) acrylamide-based 2 -Acrylamido-2-methylpropanesulfonic acid,
2-methacrylamido-2-methylpropanesulfonic acid, 3) vinyl-based vinylsulfonic acid, methallylsulfonic acid, allylsulfonic acid, propenylsulfonic acid, 4) (meth) acryloyloxy-based 2-acryloyloxyethylsulfonic acid, 3 -Acryloyloxyethyl sulfonic acid-2-hydroxypropyl sulfonic acid, 2-methacryloyloxyethyl sulfonic acid, 3-methacryloyloxy-2-hydroxypropyl sulfonic acid and the like.

Further, for the other polymerizable unsaturated monomer (b) copolymerizable with the polymerizable unsaturated monomer (a) having a sulfonic acid group, the persistent underwater antifouling agent of the present invention is targeted. It is a monomer used as necessary for adjusting the performance of a film formed by being applied to an object, of which the proportion of the monomer (b) used is the same as that of the monomer (a). If necessary, a range of 0 to 70% by weight is used with respect to 100% by weight of the total weight of the monomer (b). Specific examples thereof include methyl methacrylate, ethyl methacrylate, ter.
t-butyl methacrylate, 2-ethylhexyl methacrylate, lauryl methacrylate, stearyl
Acrylic ester-based unsaturated monomers such as methacrylate, ethyl acrylate, butyl acrylate, 2-ethylhexyl acrylate, lauryl acrylate, stearyl acrylate, and cyclohexyl acrylate; 2-hydroxyethyl acrylate, 2
-Hydroxypropyl acrylate, diethylene glycol monoacrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl methacrylate and other hydroxy lower alkyl (meth) acrylates; Others (meth) acrylic acid, crotonic acid, vinylbenzoic acid, α-cyanoacrylic acid , Hydrophilic unsaturated monomers such as maleic acid, fumaric acid and itaconic acid; styrene,
Examples include α-methylstyrene, butadiene, vinyltoluene, vinyl chloride, vinylidene chloride, vinyl acetate, vinyl butyrate, methyl vinyl ether, octyl vinyl ether, acrylonitrile and methacrylonitrile, which may be used alone or in combination of 2 or more. You may use a compound together.

The sulfonic acid group-containing polymer used in the present invention preferably has an average molecular weight of 2000 or more and 600,000 or less. If it is less than 2,000, there is a problem that the form of the coating agent cannot be maintained in seawater, and if it is more than 600,000, there is a problem that the antifouling agent has a high viscosity and the workability is extremely poor.

The polymer having a sulfonic acid group in the present invention can be obtained by a known method using the above monomers and a polymerization initiator, such as polymerization in a solution or bulk polymerization. As the solvent used at that time, water; alcohols such as methyl alcohol, ethyl alcohol, butanol, ethylene glycol monoethyl ether, propylene glycol monoethyl ether, etc .; aromatic hydrocarbons such as toluene, xylene, ethylbenzene, methylnaphthalene, etc. Alicyclic such as cyclohexane; aliphatic hydrocarbons such as n-hexane; ethers such as dioxane; esters such as ethyl acetate, butyl acetate; ketones such as acetone, methyl ethyl ketone, methyl isoamyl ketone, etc. .

Examples of the polymerization initiator include persulfates such as ammonium persulfate and sodium persulfate; peroxides such as benzoyl peroxide, t-butyl peroxide, lauroyl peroxide; hydroperoxides such as cumene hydroperoxide; azo. Aliphatic azo compounds such as bisisobutyronitrile, azobisisophthalonitrile and azobisdimethylvaleronitrile are used.

The polymerization temperature is appropriately set depending on the solvent used and the polymerization initiator, but is usually set in the range of 0 to 120 ° C, preferably 60 to 80 ° C. The reaction time varies depending on the molecular weight of the target polymer, but is usually 2 to 8 hours, 3
~ 7 hours is preferred.

By mixing the polymer having a sulfonic acid group thus obtained with the above-mentioned higher aliphatic amine compound, the persistent underwater antifouling agent of the present invention can be obtained.
This mixing can be performed by adding a higher aliphatic amine to a solution dissolved using a suitable solvent and mixing and stirring. At this time, the solution temperature is about 10 to 80 ° C., preferably 20 to 70 ° C., and the stirring time is 0.5 to 3 hours, preferably 1 to 2 hours.
The ratio of the polymer to the higher aliphatic amine is such that the higher aliphatic amine is 0.5 to 1.5 mol, preferably 0.8 to 1.2 mol, per one sulfonic acid group in the polymer. Must be set. If the amount of higher aliphatic amine is higher than this, the density of the film-forming components in the antifouling film formed is low, so the film strength is weak and the film is easily eluted or destroyed, resulting in a long-term antifouling effect. If the amount of the higher aliphatic amine is small, the antifouling effect is not exhibited, which is not preferable.

The solvent is usually a solvent such as methyl alcohol, ethyl alcohol, xylene, toluene, cyclohexanone, kerosene, methyl isobutyl ketone, butyl acetate, dimethylformamide, naphtha, ethylene glycol monoethyl ether and propylene glycol monoethyl ether. In addition to these, various solvents used in the field of paints can be used, and some water may be contained.

The persistent underwater antifouling agent of the present invention is usually a mixture of the thus-obtained polymer having a sulfonic acid group and a higher aliphatic amine compound for improving the coating workability. Dissolve it in a suitable solvent to prepare a solution. When used as an antifouling agent for fishing nets, it is necessary to make the mixture of a polymer having a sulfonic acid group and a higher aliphatic amine compound to have a solid content concentration of about 15 to 60% by weight. It is preferable in terms of film properties and film strength. To improve the adhesion to the net and the stiffness of the net, dioctyl phthalate, dioctyl adipate, tricresyl phosphate, trioctyl phosphate, polybutene, etc. may be added. .

When used in an antifouling paint, a mixture of a polymer having a sulfonic acid group and a higher aliphatic amine compound is blended in a solid content of about 20 to 80% by weight and dissolved in a suitable solvent to prepare a pigment, An antifouling paint is prepared by adding a plasticizer, a surfactant, a coating film adjusting vehicle and the like. Examples of the pigment include talc, white titanium, yellow lead, navy blue, red iron oxide, phthalocyanine blue and the like. As the plasticizer, dioctyl phthalate, dioctyl adipate, tricresyl phosphate,
Trioctyl phosphate and the like can be mentioned. Examples of vehicles for adjusting the coating strength include rosin, boil oil, chlorinated rubber, polybutene, vinyl chloride resin, acrylic resin, epoxy resin and the like.

Further, the persistent underwater antifouling agent of the present invention may optionally contain copper powder, cuprous oxide, copper rhodanide, copper naphthenate, copper oleate, dimethyldithiocarbamate, tetraethylthiuram disulfide, zinc pyrithione,
4,5-dichloro-2-n-octyl-isothiazolin-3-one, 5-chloro-2-n-octyl-isothiazolin-3-one, 2,3-dichloro-N- (2 ', 6'-
Diethylphenyl) maleimide, 2,3-dichloro-N
-(2'-ethyl-6'-methylphenyl) maleimide, 2
-A known antifouling active ingredient such as thiocyanomethylthiobenzothiazole and tetrachloroisophthalonitrile may be appropriately used in combination.

The persistent underwater antifouling agent of the present invention is useful for various seawater structures, fishing nets, ship bottoms, and seawater intake channels, and is preferably applied by dipping, brushing, spraying or the like. The antifouling agent of the present invention thus applied to the antifouling object forms an antifouling film by drying and exhibits a long-term antifouling effect.

[0029]

EXAMPLES Specific examples and comparative examples of the present invention will be shown below, but the present invention is not limited to the following examples.

Examples 1 to 5 Polymerization of a polymer having a sulfonic acid group was carried out using a flask equipped with a thermometer, a stirrer, a dropping funnel, a gas introduction tube and a reflux condenser.

80 g of 2-acrylamido-2-methylpropanesulfonic acid and 80 g of ethyl alcohol were charged,
The inside of the flask was replaced with nitrogen while stirring, and the mixture was stirred under a nitrogen stream for 7
Azobisisobutyronitrile (AIB
1.6 g of N) was added and stirring was continued for 5 hours while maintaining the same temperature to obtain a polymer A '. In this polymer A ', N,
Add 114.8 g of N-dimethyloctadecylamine and add 2
After stirring for an hour, an antifouling agent A in water was obtained. Obtained polymer A '
The average molecular weight of GPC was 55,000 as a result of GPC (gel permeation chromatography) analysis using polystyrene as a standard. Polymers B'to E'and an underwater antifouling agent B to B'in the same manner except that the components shown in Table 1 were used in the proportions shown in the same table.
I got E.

Examples 6 and 7 Polymerization of polymers having sodium sulfonate groups was carried out using a flask equipped with a thermometer, a stirrer, a dropping funnel, a gas introduction tube and a reflux condenser. 36.8 g of sodium p-styrene sulfonate, ethylhexyl acrylate 63.
Charge 2 g and xylene 100 g, replace the inside of the flask with nitrogen while stirring, heat to 70 ° C. under a nitrogen stream, add 1.6 g of azobisisobutyronitrile (AIBN) and maintain the same temperature, Polymer G'was obtained by continuing stirring for an hour.

After completion of the polymerization, 85.0 g of a 10% hydrochloric acid solution in a small excess over the equimolar amount of sodium in the polymer was added to 30
After changing to a sulfonic acid group with stirring for 1 minute, the lower aqueous layer portion was removed. Hexadecylamine 4 was added to this polymer.
3.0 g was added and stirred for 2 hours to obtain an underwater antifouling agent G. The average molecular weight of the obtained polymer G ′ was 120,000 as a result of GPC (gel permeation chromatography) analysis using polystyrene as a standard. A polymer F ′ and an underwater antifouling agent F were obtained in the same manner except that the components shown in Table 1 were used in the proportions shown in the same table.

Example 8, Comparative Examples 1 and 2 8-methacryloyloxyethyl sulfonic acid 81.7
g, methyl methacrylate 5 g, butyl acrylate 10
g, styrene 2 g, and 2-ethylhexyl methacrylate 1.3 g were charged, the inside of the flask was replaced with nitrogen while stirring, and the mixture was heated to 70 ° C. under a nitrogen stream, and 1.6 g of azobisisobutyronitrile (AIBN) was added. While maintaining the same temperature, stirring was continued for 5 hours to obtain a polymer H '. N, N-dimethyloctadecylamine 7 was added to this polymer H '.
4.1 g was added and stirred for 2 hours to obtain an antifouling agent A in water.
The average molecular weight of the obtained polymer A ′ was 50,000 as a result of GPC (gel permeation chromatography) analysis using polystyrene as a standard. Further, a polymer I ′ as a comparative example,
J'and the underwater antifouling agents I and J were obtained. The results are shown in Table 1 (blending ratio is% by weight).

[Table 1] In Table 1, the abbreviations in the columns of the monomers used for polymer production are as follows. [Sulfonic acid group-containing monomer] AMPS: 2-acrylamido-2-methylpropanesulfonic acid STS: styrenesulfonic acid MES: 2-methacryloyloxyethylsulfonic acid [polymerizable unsaturated monomer] AA: acrylic acid BA: Butyl acrylate EA: Ethyl acrylate ST: Styrene EHA: 2-Ethylhexyl acrylate MMA: Methyl methacrylate EHMA: 2-Ethylhexyl methacrylate [Higher aliphatic amine compound] DMODA: N, N-Dimethyl-octadecylamine DDA: Di Dodecylamine DMHDA: N, N-dimethyl-hexadecylamine HDA: Hexadecylamine TTMDA: Tallow alkyl trimethylenediamine

(Formulation Examples 1 to 7 as antifouling agents for fishing nets) A plasticizer and a solvent were added to the underwater antifouling agents obtained in the above Examples and Comparative Examples (the mixing ratio is% by weight), An antifouling agent for fishing net was obtained. The results are shown in Table 2 (formulation number 1 in Table 2).
5 are examples of the present invention, and formulation numbers 6 and 7 are comparative examples).

[0036]

[Table 2]

(Formulation Examples 8 to 14 as Antifouling Paint) The underwater antifouling agent obtained in the above Examples and Comparative Examples is mixed with a pigment, a plasticizer, a solvent and the like (the mixing ratio is% by weight). , Got antifouling paint. The results are shown in Table 3 (in Table 3, formulation Nos. 8 to 12 are examples of the present invention, and formulation Nos. 13 and 14 are comparative examples).

[0038]

[Table 3]

Test Example 1 [Test for confirming antifouling performance of fishing net antifouling agent] A test net made of polyethylene (100 pieces, 4 sections, 40 pieces)
(cm × 60 cm) using a net for aquaculture. The test nets were immersed in the various fishing net antifouling agents of the formulation numbers 1 to 7 obtained by the above formulation examples, the antifouling agents were attached to the nets, and the nets were air dried for 3 days. In this case, the amount of antifouling agent attached should be approximately 2 with
It was set to 0%. Then, from May, it was hung at a depth of 1.0 to 1.5 m below the sea level from the raft in the gravel bay of Mie Prefecture, and the antifouling effect against magpie staghorn and other attached organisms was observed after 3 months and 6 months. The test results are shown in Table 4. That is, in Table 4, the weight (wet weight) of the organisms attached to the net and the degree of attachment of the attached organisms are shown.

[0040]

[Table 4] +++, ++, +,-in the table indicate the degree of adhesion of mussels and the like. ++++: Remarkably adhered and cannot be used for aquaculture. ++: It adheres and cannot be used for aquaculture. +: Slightly adhered, it can be sufficiently used for aquaculture. -: No adhesion.

Test Example 2 [Confirmation test for evaluation of antifouling performance as antifouling paint] A hard vinyl chloride plate of 7 cm x 20 cm was used as a test plate. The various antifouling paints of formulation numbers 8 to 14 obtained in the above formulation examples were applied twice so that the application amount was about 2.0 kg / m ² . Then, for one year from May, it is hung from the raft at a depth of 1.5 to 2.0 m below the sea level in the gravel bay of Mie prefecture, and the antifouling effect against maggots and other adherent organisms is shown after 6 months and 12 months.
Observed after a month. The test results are shown in Table 5. That is, in Table 5, the weight of attached organisms (wet weight) and the composition ratio (%) of attached organisms are shown.

[0042]

[Table 5]

[0043]

INDUSTRIAL APPLICABILITY The persistent underwater antifouling agent of the present invention is useful as an antifouling agent for various seawater structures, and an appropriate coating method such as dipping, brushing or spraying is used depending on the object. Then, it is dried at room temperature or by heating, and baked if necessary to form a film on the surface of the object. The formed film exhibits good adhesion to an object, adheres in the natural sea without dropping for 12 months or longer, and gradually elutes in seawater. And, in the meantime, it prevents the adherent organisms, especially the maggots, from adhering. Since the coating film does not remain, the adhesion of the coating film formed on the object is good when recoating after elution. The objects include fixed nets, fishing nets such as aquaculture nets, ship bottoms, seawater intake channel walls, various structures in a cooling water system using seawater, and various underwater structures such as bridges.

Claims (2)

[Claims] 1. A polymer having a sulfonic acid group having a molecular weight of 2000 to 600,000 and a compound represented by the general formula (I): (In the formula, R ¹ represents a saturated or unsaturated aliphatic hydrocarbon group having 12 to 20 carbon atoms, and R ² represents a hydrogen atom or 1 carbon atom.
R ³ is substituted with a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, a saturated or unsaturated aliphatic hydrocarbon group having 12 to 20 carbon atoms, or an alkyl group having 1 to 6 carbon atoms. 1 to 1 carbon atoms substituted with an optionally substituted amino group
A higher aliphatic amine compound represented by the formula (6 represents an alkyl group of 6) is contained at a ratio of 0.8 to 1.2 mol of the higher aliphatic amine compound per one sulfonic acid group in the polymer. A persistent underwater antifouling agent. 2. The higher aliphatic amine compound of the general formula (I), wherein R ¹ is an alkyl group having 12 to 20 carbon atoms and R ^{2 is}
The persistent underwater antifouling agent according to claim 1, wherein R ³ and R ³ are methyl groups.