JP3368541B2 - Persistent underwater antifouling agent - Google Patents

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 for preventing adherent organisms, particularly adherent organisms in the sea, from adhering to fishing nets, ship bottoms, seawater intake channels, etc. for a long period of time. More specifically, the present invention relates to a persistent underwater antifouling agent that can be applied to fishing nets, ship bottoms, seawater intake channels, etc. to maintain the elution of highly safe antifouling active ingredients for a long period of time.

[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 adhering organisms such as barnacles, magnolias, and blue mussels are attached, causing various disorders.

Conventionally, various antifouling agents have been proposed and are actually used in order to prevent adverse effects of adhered organisms on fishing nets, ship bottoms, seawater intake channels, etc. For example, JP-B-50-8730, JP-B-54-37008, JP-A-55-92774, JP-A-58-120678, and JP-A-59-
In Japanese Patent No. 133267 and Japanese Patent Publication No. 1-54388, an antifouling agent containing an antifouling active ingredient such as an organic tin compound, an organic or inorganic copper compound or an organic chlorine compound, and a specific acrylic acid polymer is disclosed. 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.

In order to enhance safety, antifouling agents using polyisocyanate compounds or metal compounds capable of chelating with a carboxyl group instead of the above-mentioned poisons are disclosed, for example, in Japanese Patent Publication No. 53-21883 and Japanese Patent Publication No. 53-21885. It has been proposed in the publication. However, these highly safe antifouling agents still cannot be said to have sufficient antifouling effects over a long period of time.

Therefore, there is a demand for an antifouling agent that is highly safe and has a long-lasting antifouling effect. 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 this amine compound and a specific carboxyl group-containing copolymer A persistent underwater antifouling agent containing a film-forming agent composed of a polymer (polymer) has already been proposed (JP-A-1-103672, JP-A-3-252462).
(See Japanese Patent Laid-Open No. H3-252463).

Further, it is proposed and known that a polymerizable unsaturated monomer having a sulfonic acid group is reacted with a higher aliphatic quaternary ammonium salt, and then the polymerized compound is used as an antifouling agent ( International Patent Application Publication No. 91/09915
(See the official gazette).

[0007]

Generally, as an effective antifouling composition, an antifouling active ingredient has a moderate antifouling effect, and the antifouling active ingredient is a compound highly safe for humans and seafood. That the antifouling active ingredient elutes at a constant rate for a long time from the surface to which it has been applied, that is, the elution amount of the antifouling active ingredient can be adjusted.
It is necessary to satisfy the conditions such as not remaining in fishing nets.

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 reaction polymer of a polymerizable unsaturated monomer having a sulfonic acid group and a higher aliphatic quaternary ammonium salt do not satisfy the conditions 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 the ocean for a long time by applying it 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 this is mainly because the carboxyl group in the copolymer reacts with the hardness component of seawater.

Therefore, it is an object of the present invention to provide a composition useful as a persistent antifouling agent in water satisfying the above conditions (1) to (4).

[0013]

SUMMARY OF THE INVENTION The inventors of the present invention have
As a result of various studies on a polymer obtained by polymerizing a reaction product of a polymerizable unsaturated monomer having a sulfonic acid group and a higher aliphatic amine, a fishing net etc. coated with this specific polymer has a long period of time. The present invention has been completed by confirming that the antifouling effect is continuously maintained for a long time and that no polymer remains on the fishing net or the like after a certain period.

Thus, according to the present invention, the polymerizable unsaturated monomer having a sulfonic acid group and the general formula (I):

[0015]

[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 of 6]
Another polymerizable unsaturated monomer (b) which is capable of polymerizing the reaction product (a) with at least one species or copolymerizable with the reaction product (a).
And a polymer having an average molecular weight of 3000 to 400,000 obtained by polymerizing

The polymerizable unsaturated monomer having a sulfonic acid group used in the present invention may be an unsaturated compound having a sulfonic acid group, such as styrenesulfonic acid,
2-acrylamido-2-methylpropanesulfonic acid,
2-methacrylamido-2-methylpropanesulfonic acid, vinylsulfonic acid, methallylsulfonic acid, allylsulfonic acid, propenylsulfonic acid, 2-methacryloyloxyethylsulfonic acid, 3-methacryloyloxy-
2-hydroxypropyl sulfonic acid etc. are mentioned.

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, palm alkylamine. Primary amines such as; di (dodecyl) amine, di (octadecyl) amine, di (oleyl) amine, di (tallow alkyl) amine, di (coconut alkyl) amine, dodecyl octadecylamine, dodecylmethylamine, dodecylethylamine, hexa Secondary amines such as decylbutylamine, hexadecylmethylamine, octadecylmethylamine, tallow alkylmethylamine, hardened tallow alkylmethylamine, coconut alkylmethylamine; dodecyldimethylamine, hexadecyldimethylamine, octa Tertiary such as tadecyldimethylamine, coconut alkyldimethylamine, tallow alkyldimethylamine, hardened tallow alkyldimethylamine, didodecylmethylamine, dioctadecylmethylamine, dodecylhexadecylmethylamine, tallowalkyldiethylamine, cocoalkyldihexylamine. Amine; N-monosubstituted ethylenediamine such as dodecylethylenediamine, hexadecylethylenediamine, octadecylethylenediamine, oleylethylenediamine, tallow alkylethylenediamine; and dodecyltrimethylenediamine,
Examples thereof include N-monosubstituted trimethylenediamine such as hexadecyltrimethylenediamine, octadecyltrimethylenediamine, oleyltrimethylenediamine, cocoalkyltrimethylenediamine, tallow alkyltrimethylenediamine, and hardened tallowalkyltrimethylenediamine.

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 or coconut fat, beef tallow, etc. A branched or branched saturated or unsaturated aliphatic hydrocarbon group is a mixture of amines whose main component is a higher aliphatic amine, and is a compound represented by the formula (I). Any one of these is used alone, or two or more are used together.

Among these higher aliphatic amines represented by the general formula (I), tertiary amines in which R ¹ is an alkyl group having 12 to 20 carbon atoms and R ² and R ³ are methyl groups are more preferable. It is preferable because a good antifouling effect is exhibited. In the present invention, the other polymerizable unsaturated monomer (b) copolymerizable with the reaction product (a) of the polymerizable unsaturated monomer having a sulfonic acid group and the higher aliphatic amine is used in the present invention. A water-soluble underwater antifouling agent is a monomer that is used as necessary to adjust the performance of a film formed by applying it to an object, and is a monomer copolymerizable with the polymer (a). If there is no particular limitation.
Specific examples of the monomer (b) include methyl methacrylate, ethyl methacrylate, tert-butyl methacrylate, 2-ethylhexyl methacrylate, lauryl methacrylate, stearyl methacrylate, ethyl acrylate, butyl acrylate, 2-ethylhexyl acrylate, lauryl acrylate, stearyl acrylate. , Acrylic ester unsaturated monomers such as cyclohexyl acrylate; 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, diethylene glycol monoacrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl methacrylate, etc. ) Acrylate, etc .; Others (meth) acrylic acid, crotonic acid, vinylbenzoic acid, α-sia Acrylic acid, maleic acid, fumaric acid, hydrophilic unsaturated monomers such as itaconic acid, and the like; styrene,
Examples include α-methylstyrene, butadiene, vinyltoluene, vinyl chloride, vinylidene chloride, vinyl acetate, vinyl butyrate, methyl vinyl ether, octyl vinyl ether, acrylonitrile and methacrylonitrile.

As the reaction product (a) and the monomer (b), one compound may be used alone,
Two or more compounds may be used in combination. The reaction between the polymerizable unsaturated monomer having a sulfonic acid group and the higher aliphatic amine is carried out by adding 0.8 mol to 1 mol of the higher aliphatic amine to 1 mol of the polymerizable unsaturated monomer having a sulfonic acid group. It is preferable to react and polymerize in the range of 0.2 mol, preferably 0.9 to 1.1 mol. Polymerization becomes difficult when the amount of amine is large, while antifouling effect becomes weak when the amount is small, which is not preferable. The reaction product produced by this reaction is a neutralized salt of a polymerizable unsaturated monomer having a sulfonic acid group and a higher aliphatic amine. The polymer of the present invention can be obtained by polymerizing the reaction product as it is, or by polymerizing it after extraction and purification.

As described above, the higher aliphatic amine is more firmly bonded to the resin substrate when the neutralized salt with the monomer is formed before the polymerization, than when the neutralized salt of the polymer is formed after the polymerization. , Will become a stable bond. The ratio of the monomer (b) used is
Total weight of reactant (a) and monomer (b) 100% by weight
On the other hand, it is optionally used in the range of 0 to 70% by weight. If the amount of the monomer (b) exceeds 70% by weight, the content of the higher aliphatic amine, which is an active ingredient in the antifouling agent, decreases and the antifouling effect becomes weak, which is not preferable.

The average molecular weight of the polymer obtained by polymerization is 3
It is preferably 000 or more and 400,000 or less. If it is less than 3000, there is a problem that the form of the coating agent cannot be maintained in seawater, and if it is more than 400,000, there is a problem that the antifouling agent has a high viscosity and the workability is remarkably poor. The polymer in the present invention can be polymerized by a known method using 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 and butanol; ethers such as ethylene glycol monoethyl ether, propylene glycol monoethyl ether and dioxane; toluene, xylene, ethylbenzene, methylnaphthalene, etc. Aromatic hydrocarbons; aliphatic and alicyclic hydrocarbons such as n-hexane and cyclohexane; esters such as ethyl acetate and butyl acetate; ketones such as acetone, methyl ethyl ketone and methyl isoamyl ketone.

As the polymerization initiator, persulfates such as ammonium persulfate and sodium persulfate; peroxides such as benzoyl peroxide, t-butyl peroxide and 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 persistent underwater antifouling agent of the present invention is usually prepared in the form of a solution by dissolving the polymer thus obtained in a suitable solvent for improving the coating workability. Examples of the solvent include methyl alcohol, ethyl alcohol, xylene, toluene, cyclohexanone, kerosene, methyl isobutyl ketone, butyl acetate, dimethylformamide, naphtha, ethylene glycol monoethyl ether, propylene glycol monoethyl ether, and the like. Also, various solvents used in the field of paints can be used, and some water may be contained.

When used as an antifouling agent for fishing nets, the polymer has a solid content of 10 to 60% by weight, preferably 20 to 60% by weight.
Antifouling property, film forming property, and
It is preferable in terms of film strength and the like, and in order to improve the adhesion to the net, the stiffness of the net, etc., dioctyl phthalate, dioctyl adipate, tricresyl phosphate, trioctyl phosphate, polybutene, etc. may be blended.

When applied to a fishing net, a conventional method such as a dipping method is used. When using for antifouling paint,
The polymer has a solid content of 20 to 80% by weight, preferably 3
About 0 to 60% by weight is mixed and dissolved in an appropriate solvent to prepare a pigment,
An antifouling paint is prepared by adding a plasticizer, a surfactant, a coating film adjusting vehicle and the like. As the pigment, talc, titanium white,
Examples include yellow lead, navy blue, red iron oxide, and phthalocyanine blue. Examples of the plasticizer include dioctyl phthalate, dioctyl adipate, tricresyl phosphate, trioctyl phosphate and the like. 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.

When applied as an antifouling paint, a usual method such as brush coating, roller method or spray method is used. 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,
Known antifouling active ingredients such as 4,5-dichloro-2-n-octyl-4-isothiazolin-3-one, 2-thiocyanomethylthiobenzothiazole and tetrachloroisophthalonitrile can be appropriately used in combination.

[0028]

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. Reference Example 1 [Synthesis of reaction product (a-1) of 2-acrylamido-2-methylpropanesulfonic acid and N, N-dimethyloctadecylamine] Sulfonic acid group-containing polymerizable unsaturated monomer and higher aliphatic amine The reaction of was carried out using a flask equipped with a thermometer, a stirrer and a reflux condenser. That is, xylene 10 in the flask
0 g, 2-acrylamido-2-methylpropanesulfonic acid 0.2 mol, tert-butylcatechol 0.001
While adding 0.2 mol of N, N-dimethyloctadecylamine with stirring, the mixture was gradually added dropwise while keeping the internal temperature at 60 ° C or lower, and after stirring for 1 hour, stirring was continued for 2-acrylamido-2-methylpropane. A reaction product (a-1) of sulfonic acid and N, N dimethyloctadecylamine was obtained.

Reference Example 2 [Reaction product of p-styrenesulfonic acid and N, N-dimethylhexadecylamine (a-2)]
Synthesis] The reaction between the sulfonate group-containing polymerizable unsaturated monomer and the higher aliphatic amine was carried out using a flask equipped with a thermometer, a stirrer, and a reflux condenser. That is, 50 g of ethanol and 0.2 mol of N, N-dimethylhexadecylamine were added to the flask and 0.2 mol of hydrochloric acid was gradually added dropwise at room temperature with stirring. After completion of the addition, 0 of p-styrenesulfonic acid sodium was added. What melt | dissolved 0.2 mol in 200 g of pure water was dripped gradually, and after stirring for 30 minutes, it left for 1 hour. The obtained precipitate was filtered, washed with pure water and then dissolved in xylene to obtain a reaction product (a-2) of p-styrenesulfonic acid and N, N-dimethylhexadecylamine.

Example 1 [Polymerization of Reactant (a-1)] Polymerization of the reaction product (a-1) of 2-acrylamido-2-methylpropanesulfonic acid and N, N dimethyloctadecylamine was carried out using a thermometer, It was carried out using a flask equipped with a stirrer, a dropping funnel, a gas introduction tube and a reflux condenser. Reference example 1
200 g of a xylene solution of the reaction product (a-1) obtained in (1) was charged, the inside of the flask was replaced with nitrogen while stirring, and the mixture was heated to 80 ° C. under a nitrogen stream to obtain azobisisobutyronitrile (AI
BN) 0.16 g was added and while maintaining the same temperature, 5
The stirring was continued for a while to obtain a polymer A which is an example of the present invention. The average molecular weight of the obtained polymer A was 85,000 as a result of GPC (gel permeation chromatography) analysis using polystyrene as a standard.

Examples 2 to 12 and Comparative Examples 1 to 6 [Polymerization of reaction product (a) of polymerizable unsaturated monomer having various sulfonic acid groups and various higher aliphatic amines or reaction product (a)] Other polymerizable unsaturated monomer (b) copolymerizable with the reactant
Polymerization with] In the same manner as in Reference Examples 1 and 2 and Example 1, a reaction product (a) of a polymerizable unsaturated monomer having various ratios of various sulfonic acid groups and various higher aliphatic amines, or Reactant (a) and other polymerizable unsaturated monomer (b) copolymerizable with the reactant
Polymer B which is an example of this invention having various molecular weights of
~ L was obtained.

Polymers M to R as comparative examples were also obtained. The results are shown in Table 1.

[0033]

[Table 1] In Table 1, the abbreviations in the columns of the monomers used for polymer production are as follows. [Higher aliphatic amine compound name] DMODA --- N, N-dimethyloctadecylamine DDA --- didodecylamine HDA --- hexadecylamine TTMDA --- beef tallow Alkyl trimethylene diamine DMHDA ··· N, N-dimethylhexadecylamine DMA ··· dodecylmethylamine DDMBA ··· dodecyldimethylbenzylammonium chloride DTMAB ··· dodecyltrimethyl Ammonium bromide DA ··· Dodecylamine [sulfonic acid group-containing monomer] AMPS ··· 2-acrylamido-2-methylpropanesulfonic acid STS ··· styrenesulfonic acid MS ·· .... Methallyl sulfonic acid MES Royloxyethylsulfonic acid [other polymerizable unsaturated monomer] EHA ··· 2-ethylhexyl acrylate MMA ··· methyl methacrylate BA ··· butyl acrylate AA ·・ ・ ・ ・ ・ Acrylic acid ST ・ ・ ・ ・ ・ Styrene HEA ・ ・ ・ ・ ・ 2-Hydroxyethyl acrylate EHMA ・ ・ ・ ・ ・ 2-Ethylhexyl methacrylate MAA ・ ・ ・ ・ ・ BMA methacrylate ... Butyl Methacrylate Preparation Examples 1 to 18 A plasticizer and a solvent were added to the above-mentioned polymers A to R (the mixing ratio is% by weight) to obtain an antifouling agent for fishing nets.

The results are shown in Table 2. In Table 2, Formulation Nos. 1 to 12 are formulation examples of the present invention, Formulation Nos. 13 to 18
Is a comparative example.

[0035]

[Table 2] Formulation Examples 19 to 31 Pigments, plasticizers, solvents and the like were blended with the polymers obtained in the above Polymerization Examples (blending ratio was wt%) to obtain antifouling paints.
The results are shown in Table 3. Formulation numbers 19 to 2 in Table 3
7 is a formulation example of the present invention, and formulation numbers 28 to 31 are comparative examples.

[0036]

[Table 3] Test Example 1 [Confirmation test for evaluation of antifouling performance of fishing net antifouling agent] As a test net, polyethylene (100, 4 sections, 40
(cm × 60 cm) using a net for aquaculture. Formulation number 1
The test net was immersed in the various anti-fouling agents for fishing nets obtained in 18, the antifouling agent was attached to the nets, and the nets were air-dried for 3 days. In this case, the adhesion amount of the antifouling agent was set to about 20% with respect to the weight of the net. Then, during the three months from May to July, it was hung at a depth of 1.0 to 1.5 m below the sea level from the raft in Isaura Bay, Mie Prefecture, and the antifouling effect against maggots and other attached organisms was measured after three months. 6
Observed after a month. 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.

[0037]

[Table 4] +++, ++, +,-in the table indicate the degree of adhesion of mussels and the like. ++++: Remarkably adhered. ++: Attached and cannot be used for aquaculture. +: Slightly adhered, it can be sufficiently used for aquaculture.

-: No adhesion. [Discussion of Table 4] As shown in Table 4, in Formulation Nos. 1 to 12 prepared from the polymer which is an example of the present invention, the antifouling effect is maintained for a long time, particularly 6 months. It can be seen from the observation of the subsequent adhesion state that a good antifouling effect is exhibited regardless of the type of the target adherent organisms. In comparison with these, a polymer obtained by polymerizing a reaction product of a quaternary ammonium salt and a polymerizable unsaturated monomer having a sulfonic acid group (the polymer described in International Patent Application Publication No. 91/09915). (Preparation Nos. 13 and 14) or a polymer preparation obtained by polymerizing a reaction product of a higher aliphatic amine and a polymerizable unsaturated monomer having no sulfonic acid group (Formulation Nos. 15 to 15). In 18), when the state of adhesion after 6 months is examined, it can be seen that especially Kasengakuenshi, barnacles and bryozoa are markedly adhered and cannot be used for a long period of time.

Test Example 2 [Confirmation Test for Evaluation of Antifouling Performance as Antifouling Paint] A hard vinyl chloride plate of 7 cm × 20 cm was used as a test plate. The various antifouling paints obtained in Formulation Nos. 19 to 31 were applied twice so that the applied amount was about 2.0 kg / m ² . Then, for one year from May, it was hung in the sea of Miso Prefecture from the raft to a depth of 1.5 to 2.0 m below the sea level, and the antifouling effect against maggots and other attached organisms was measured 6 months and 12 months later. I observed. The test results are shown in Table 5. That is,
Table 5 shows the weight of attached organisms (wet weight) and the percentage of attached organisms (%).

[0040]

[Table 5] [Discussion of Table 5] As shown in Table 5, in Formulation Nos. 19 to 27 prepared from the polymer which is an example of the present invention, the antifouling effect is maintained for a long time, particularly 12
Observing the adhesion state after a month, it can be seen that regardless of the kind of the target adherent organisms, the adhered area of the adherent organism amount is 10% or less, which shows a good antifouling effect. In comparison with these, a polymer obtained by polymerizing a reaction product of a quaternary ammonium salt and a polymerizable unsaturated monomer containing a sulfonic acid group (the polymer described in the above-mentioned International Application Publication No. 91/09915). (Preparation Nos. 28 and 29) or a polymer preparation obtained by polymerizing a reaction product of a higher aliphatic amine and a polymerizable unsaturated monomer having no sulfonic acid group (Preparation Nos. 30 and 30). In 31), when the state of adhesion after 12 months is examined, it can be seen that especially Kazan harlequin, barnacles and bryophytes are remarkably adhered and cannot be used for a long period of time.

[0041]

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 attachment of attached organisms. 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.

─────────────────────────────────────────────────── ─── Continuation of front page (56) References JP-A-3-252463 (JP, A) JP-A-3-252462 (JP, A) JP-A-5-504365 (JP, A) (58) Field (Int.Cl. ⁷ , DB name) A01N 33/12 101 A01N 61/00 D A01N 33/04 A01N 41/04 Z A01N 41/06 C09D 5/14 C09D 5/16

Claims (2)

(57) [Claims] 1. A polymerizable unsaturated monomer having a sulfonic acid group 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
6 represents an alkyl group of 6]
Another polymerizable unsaturated monomer (b) which is capable of polymerizing the reaction product (a) with at least one species or copolymerizable with the reaction product (a).
A continuous underwater antifouling agent containing a polymer having an average molecular weight of 3,000 to 400,000 obtained by polymerizing. 2. In the general formula (I), R ¹ has 12 to 2 carbon atoms.
The persistent underwater antifouling agent according to claim 1, which is an alkyl group of 0 and R ² and R ³ are methyl groups.