JP2875328B2 - Sustainable underwater antifouling agent - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Application Field] The present invention relates to the use of a fishing net,
The present invention relates to a persistent underwater antifouling agent for preventing the adhering to a ship bottom, a seawater intake channel wall, etc. for a long time.

[Conventional technology]

2. Description of the Related Art Conventionally, various antifouling agents for suppressing the adhesion of attached organisms have been proposed and actually used in order to prevent the attached organisms from adhering to fishing nets, ship bottoms, seawater intake channel walls, and the like, thereby causing adverse effects.

For example, JP-A-58-120678, JP-A-59-1332
No. 67 proposes an antifouling agent containing a vehicle containing an antifouling active ingredient of an organotin polymer or cuprous oxide and a specific polymer compound. These antifouling active ingredients,
It is highly toxic enough to cause marine pollution, and has the property of accumulating in living organisms. For this reason, especially in the aquaculture industry, there is a concern that the human body may be affected when edible cultured organisms are handled. On the other hand, the impact on workers who directly handle antifouling agents is also of particular concern.

Therefore, antifouling agents having low toxicity and no accumulation are desired.

As a low-toxic pollutant, there has been proposed a coating agent comprising only a high-molecular polymer having no antifouling active ingredient (see Japanese Patent Application Laid-Open No. 60-177063). This coating agent has an extremely poor antifouling effect during a remarkable breeding season of mussels, barnacles, scuttles, bryozoans, algae, etc. (usually from August to December in the western Pacific coast of the Pacific Ocean), There is a disadvantage that the attachment of tools and the like cannot be sufficiently suppressed. Further, the coating agent also has a disadvantage that the antifouling effect is not maintained for a long time (for example, three months or more).

Some of the inventors of the present invention have previously found that a specific higher aliphatic amine compound having a low toxicity and a good component dissolving property has an excellent antifouling effect. A persistent underwater antifouling agent comprising a polymer film-forming agent has already been proposed (see JP-A-1-103672).

[Problems to be solved by the invention]

However, the persistent underwater antifouling agent just described has not yet been sufficiently satisfactory with respect to the antifouling effect for a longer period (for example, 6 months or more). In such a long period, the temperature of seawater fluctuates greatly, and accordingly,
The degree of elution of the antifouling active ingredient from the antifouling agent also fluctuates greatly,
The anti-fouling effect is large and small. Usually, an antifouling agent is prepared so that the dissolving property of the antifouling active ingredient is increased in summer when the biological activity is active. However, in winter, attached organisms are not completely inactive, and antifouling agents that exhibit the same antifouling effect in both summer and winter are required.

Therefore, the present invention prevents the adverse effect on the human body and the environment by using a low-toxicity and non-accumulating agent as an antifouling active ingredient, and furthermore, the dissolution of the antifouling active ingredient does not fluctuate much depending on the season, An object of the present invention is to provide a persistent underwater antifouling agent capable of stably exhibiting an antifouling effect over a long period of time.

[Means for solving the problem]

In order to solve the above-mentioned problem, a persistent underwater antifouling agent according to the present invention has a mean molecular weight of 5,000 to 500,000 obtained by polymerizing the following monomers (A), (B) and (C). It contains a polymer. The monomer components for obtaining the copolymer are as follows: monomer (A) 60 to 94% by weight, monomer (B)
1 to 5% by weight and monomer (C) 5 to 39% by weight (provided that the total amount of (A), (B) and (C) is 100% by weight)
It is. ).

(A) general formula (I); (Wherein, in the formula (I), R ¹ is hydrogen or a methyl group, R ² is a saturated or unsaturated higher aliphatic hydrocarbon group, R ³ is a hydrogen or a saturated or unsaturated lower aliphatic hydrocarbon group, R ⁴ is hydrogen, a saturated or unsaturated aliphatic hydrocarbon group, or a saturated or unsaturated lower aliphatic hydrocarbon group substituted with an amino group (provided that the hydrogen of the amino group is a saturated or unsaturated lower aliphatic group) A monomer which may be substituted with a hydrocarbon group.))

(B) general formula (II); (Wherein, in the formula (II), R ⁵ is hydrogen or a methyl group, and X is 50% by weight based on the total weight of all the alkylene oxide residues.)
2 to 4 carbon atoms comprising the above ethylene oxide residue
Wherein n is an integer of 1 to 100, and R ⁶ is hydrogen or a hydrocarbon group having 1 to 5 carbon atoms. ) A monomer represented by

(C) general formula (III); (However, in the formula (III), R ⁷ is hydrogen or a methyl group, R ⁸
Is a hydrocarbon group having 1 to 20 carbon atoms. ) A monomer represented by

The monomer (A) is a quaternary ammonium salt of (meth) acrylic acid (acrylic acid and / or methacrylic acid) represented by the general formula (I). However, a normal quaternary ammonium salt forms a monovalent cation by covalently bonding four hydrocarbon groups to an N atom, but the quaternary ammonium salt used here is an N atom X
(X = 1 to 3) hydrogen and (4-x) hydrocarbon groups (where x is 1 or 2 and 1
One hydrocarbon group may be substituted with an amino group) to form a monovalent cation. The groups R ² , R ³ and R ⁴ covalently bonded to the N atom are as follows.

The group R ² is a higher aliphatic hydrocarbon group, and may be either saturated or unsaturated.

The group R ³ is hydrogen or a lower aliphatic hydrocarbon group, and the hydrocarbon group may be either saturated or unsaturated.

The group R ⁴ is hydrogen, an aliphatic hydrocarbon group, or a lower aliphatic hydrocarbon group substituted with an amino group (however, the hydrogen of the amino group may be substituted with a lower aliphatic hydrocarbon). There, when group R ⁴ is an aliphatic hydrocarbon group may be either lower or higher of the. The lower or higher aliphatic hydrocarbon groups mentioned here may be either saturated or unsaturated.

If the groups R ² , R ³ and R ⁴ are other than the above-mentioned groups, a good antifouling effect cannot be obtained.

Examples of the lower aliphatic hydrocarbon group include a methyl group, an ethyl group, a propyl group, a butyl group, a saturated hydrocarbon group such as a pentyl group and a hexyl group; an ethenyl group, a propenyl group, a butenyl group, an ethynyl group and a propynyl group. And unsaturated hydrocarbon groups.

Examples of the higher aliphatic hydrocarbon group include an aliphatic hydrocarbon group having 12 to 20 carbon atoms.

When both groups R ² and R ⁴ are higher aliphatic hydrocarbon groups, they may be the same or different. When both groups R ³ and R ⁴ are lower aliphatic hydrocarbon groups, they may be the same or different.

The monomer (A) is a neutralized salt of (meth) acrylic acid and a higher aliphatic amine represented by the following general formula (IV).
As described above, when a higher aliphatic amine is formed with a monomer and a neutralized salt before polymerization, it is more stable and stable with the resin substrate than when a copolymer and a neutralized salt are formed after polymerization. Will be combined.

General formula (IV); (However, in the formula (IV), R ² , R ³ and R ⁴ are the same as those in the formula (I).) In this neutralization reaction, for example, a higher aliphatic amine is placed in a predetermined amount of a container. The usual practice is to add an equimolar amount of (meth) acrylic acid with sufficient stirring to form a neutralized salt.

Specific examples of the higher aliphatic amine represented by the above formula (IV) include, for example, dodecylamine, octadecylamine, tetradecylamine, hexadecylamine, oleylamine, myristoleylamine, palmitoleylamine, tallowalkylamine, coconut Primary amines such as alkylamines; di (dodecyl) amine, di (octadecyl) amine, di (oleyl) amine, di (tallowalkyl) amine, di (cocoalkyl) amine, dodecyltetradecylamine, dodecylhexadecylamine, Dodecyloctadecylamine, tetradecylhexadecylamine, tetradecyloctadecylamine, hexadecyloctadecylamine, dodecyloleylamine, dodecylmethylamine, oleylethylamine, hexadecylmethylamine, octadecyl Secondary amines such as methylamine, tallowalkylmethylamine, cocoalkylamine, hexadecylbutylamine, and cocoalkylpropylamine; dodecyldimethylamine, hexadecyldimethylamine, octadecyldimethylamine, tetradecyldimethylamine, tallowalkyldimethylamine, Coconut alkyldimethylamine, didodecylmethylamine, dioctadecylmethylamine, di-tallow alkylmethylamine,
Di (cocoalkyl) methylamine, dodecyltetradecylmethylamine, dodecylhexadecylmethylamine,
Dodecyloctadecylmethylamine, tetradecylhexadecylmethylamine, tetradecyloctadecylmethylamine, hexadecyloctadecylmethylamine, dodecylmethylpropylamine, hexadecylmethylethylamine, tallowalkylethylpropylamine, tallowalkyldiethylamine, tallowalkyldipropylamine, Tertiary amines such as tallowalkyldibutylamine, tallowalkylmethylhexylamine, cocoalkyldipentylamine, and cocoalkyldihexylamine; dodecyl trimethylenediamine, hexadecyltrimethylenediamine, octadecyltrimethylenediamine, tallowalkyltrimethylenediamine, coconut Alkyl trimethine diamine, tallow alkyl methylene diamine, coco alkyl ethylene diamine , N- tallow-alkyl -N'- dimethyl trimethylene diamine, N- coconut alkyl -N'-
And diamines such as dibutyltrimethylenediamine. Among these amines, “coconut alkyl (·
..) amine "and" tallow alkyl (...) amine "are the groups in the above formula (IV) wherein the amine is produced from coconut oil or coconut fat, tallow, etc. by known means.
R ² and / or R ⁴ having a saturated or unsaturated aliphatic hydrocarbon group having 12 to 20 carbon atoms means a mixture of amines (mixed alkylamine) occupying a major component thereof. As the higher aliphatic amine, any one of the compounds represented by the formula (IV) may be used alone, or two or more of them may be used in combination.

As the monomer (A), in the compound represented by the above formula (I), the group R ¹ is a hydrogen or methyl group, and the group R ² is a group having 12 carbon atoms.
20 saturated or unsaturated aliphatic hydrocarbon group, group R ³ is hydrogen or an alkyl group having 1 to 6 carbon atoms, groups R ⁴ are hydrogen, an alkyl group having 1 to 6 carbon atoms, of 12 to 20 carbon atoms A saturated or unsaturated aliphatic hydrocarbon group or an alkyl group having 1 to 6 carbon atoms substituted with an amino group (provided that hydrogen of the amino group may be substituted with an alkyl group having 1 to 6 carbon atoms) ) Is preferably used. This is because such compounds are easily available industrially at relatively low cost.

The monomer (B) is a (meth) acrylic ester containing an alkylene oxide residue X having 2 to 4 carbon atoms in its structure. Specific examples of the alkylene oxide residue X include, for example, ethylene oxide, propylene oxide, butylene oxide, tetramethylene oxide, and the like. However, the total weight of the alkylene oxide residue is 50% by weight or more and 100% by weight or less. Must contain the ethylene oxide residue of If the ethylene oxide residue content is less than 50% by weight, there is a problem that the hydrophobicity of the obtained copolymer becomes large and the dissolution of the antifouling active ingredient tends to fluctuate. The repeating number n of the alkylene oxide residue X is an integer of 1 to 100. When n exceeds 100, there is a problem that the copolymerizability with other monomers becomes poor and it is difficult to obtain a desired copolymer. Further, when the number of carbon atoms of the alkylene oxide residue X is less than 2, the hydrophilicity of the obtained copolymer becomes strong and the antifouling active ingredient is easily eluted. There is a problem that the hydrophobicity becomes large and the dissolution of the antifouling active ingredient fluctuates easily, and the monomer becomes difficult to obtain. The group R ⁶ is hydrogen or a hydrocarbon group having 1 to 5 carbon atoms. When the number of carbon atoms in the group R ⁶ exceeds 5, the obtained copolymer has high hydrophobicity, and the dissolution of the antifouling active ingredient tends to fluctuate, or the monomer is difficult to obtain. is there. Group R ⁶
Specific examples include hydrogen, an alkyl group such as a methyl group, an ethyl group, a propyl group, a butyl group, and an amine group; and an alkenyl group such as a vinyl group, a propenyl group, and a butenyl group.

The monomer (C) is a (meth) acrylate represented by the general formula (III). (III) In the formula, the group R ⁸ is a hydrocarbon group having 1 to 20 carbon atoms. If the number of carbon atoms of the radicals R ⁸ exceeds 20, there is a problem that the hydrophobicity of the resulting copolymer is liable to occur fluctuation of the dissolution of the large next antifouling effective component. Specific examples of the group R ⁸ include, for example, a methyl group, an ethyl group, a propyl group, a butyl group, an amyl group, a hexyl group,
Heptyl group, octyl group, nonyl group, decyl group, undecyl group, dodecyl group, tridecyl group, tetradecyl group,
Alkyl groups such as pentadecyl group, hexadecyl group, heptadecyl group, octadecyl group, nonadecyl group and eicosyl group; aralkyl groups such as phenyl group, naphthyl group, octylphenyl group and nonylphenyl group; and cyclic alkyl groups such as cyclohexyl group .

The copolymer used in the present invention may contain the above-mentioned (A) or (A) as necessary for adjusting the performance of a film formed by applying the persistent underwater antifouling agent of the present invention to an object.
It may be made using a vinyl monomer (D) other than (B) and (C). Specific examples of the monomer (D) include, for example, (meth) acrylic acid, crotonic acid, vinylbenzoic acid, α-cyanoacrylic acid, maleic acid, fumaric acid,
Unsaturated carboxylic acids such as itaconic acid (which may be anhydrides); unsaturated hydrocarbons such as dodecene, styrene, α-methylstyrene, butadiene and vinyltoluene; halogenated unsaturated hydrocarbons such as vinyl chloride and vinylidene chloride;
Vinyl esters such as vinyl acetate and vinyl butyrate;
Vinyl ethers such as methyl vinyl ether, octyl vinyl ether and dodecyl vinyl ether; and acrylonitrile.

As the monomers (A) to (D), one compound may be used alone, or two or more compounds may be used in combination.

The proportion of the monomers (A), (B) and (C) used is 60 to 94% by weight of the monomer (A), The amount is 1 to 5% by weight and the monomer (C) is 5 to 39% by weight. In addition, monomer (D)
Is used as needed as long as the effect of the present invention is not impaired. The monomer (D) is used in an amount of 10% by weight or less based on 100% by weight of the total weight of (A) to (D). Is preferred. When the proportion of the monomer (A) is less than the above lower limit, there is a problem that a sufficient content of higher aliphatic amine cannot be obtained. It is not preferable because the persistence of the effect is reduced. When the usage ratio of the monomer (B) is less than the above lower limit, the hydrophilicity of the copolymer itself in seawater is inferior, and the dissolution of the antifouling active ingredient is reduced, so that a long-term antifouling effect cannot be obtained. If it is more than the above upper limit, the hydrophilicity is too high and the antifouling film dissolves in seawater in a short period of time, so that a long-term antifouling effect cannot be obtained, which is not suitable. When the use ratio of the monomer (C) is less than the above lower limit, the film-forming properties are poor, and a proper hydrophobicity cannot be imparted, so that a long-term antifouling effect cannot be obtained. The hydrophobicity is increased, and the dissolving property of the antifouling film is reduced, so that a long-term antifouling effect cannot be obtained.

A monomer component comprising these monomers (A), (B), (C) and optionally (D) is polymerized to form a copolymer having an average molecular weight of 5,000 or more and 500,000 or less. Get.
If the average molecular weight of the copolymer is less than 5,000, there is a problem that the form of the coating agent cannot be maintained in seawater. If the average molecular weight is more than 500,000, the antifouling agent has a high viscosity and the workability is extremely poor.

Such a copolymer is produced, for example, by copolymerizing a monomer component obtained by mixing the above-mentioned monomers (A) to (D) in the above-mentioned ratio by a known method using a polymerization initiator. Is done. The copolymerization can be performed by a method such as polymerization in a solvent or bulk polymerization. The polymerization in a solvent can be carried out batchwise or continuously, and the solvent used in this case is, for example, water; methyl alcohol, ethyl alcohol, isopropyl alcohol, butanol,
Alcohols such as -methoxyethanol and 2-ethoxyethanol; aromatic hydrocarbons such as benzene, toluene, xylene, ethylbenzene and methylnaphthalene; alicyclic hydrocarbons such as cyclohexane; aliphatic hydrocarbons such as n-hexane. Heterocyclic compounds such as dioxane; esters such as ethyl acetate and butyl acetate; ketones such as acetone and methyl ethyl ketone. Examples of the polymerization initiator include persulfates such as ammonium persulfate and sodium persulfate; peroxides such as benzoyl peroxide, t-butyl peroxide and lauroyl peroxide; hydroperoxides such as cumene hydroperoxide; Aliphatic azo compounds such as butyronitrile, azobisisophthalonitrile, and azobisdimethylvaleronitrile are used. At this time, an accelerator such as an amine compound may be used in combination. The polymerization temperature is appropriately set depending on the solvent and the polymerization initiator used, but is usually set in the range of 0 to 120 ° C. The bulk polymerization uses a peroxide such as benzoyl peroxide or lauroyl peroxide as a polymerization initiator; a hydroperoxide such as cumene hydroperoxide; an azo compound such as azobisisobutyronitrile; Done within.

The persistent antifouling agent in water of the present invention is usually prepared in the form of a solution by dissolving the copolymer thus obtained in a suitable solvent. As the solvent, for example, methanol, ethanol, xylene, toluene, kerosene, methyl isobutyl ketone, butyl acetate, dimethylformamide, naphtha, methyl cellosolve and the like are used, and various other solvents used in the field of paints are also used. It can be used and may contain water. Solid content concentration 20-50% by weight
It is preferable to set the degree to such a degree in terms of film formability, film strength, and the like. The solution prepared in this manner is easy to dissolve and handle at the time of the coating operation, avoids extra adhesion, and enables cost reduction.

As described above, the underwater antifouling agent of the present invention can be used as it is by dissolving it in an appropriate solvent. However, the antifouling paint is mixed with a vehicle, a pigment, a plasticizer, a surfactant, a solvent or a diluent, and the like. It is also possible to prepare In this case, it is appropriate to use the underwater antifouling agent in an amount of 10 to 60% by weight based on the whole paint. The vehicle, pigment, plasticizer, surfactant, solvent, diluent, and the like are not particularly limited as long as they can be used in a paint, and can be used as appropriate.

The persistent underwater antifouling agent of the present invention is applied by using an appropriate coating method such as immersion, brush coating, spraying, or the like according to an object, dried at room temperature or by heating, and baked if necessary. A film is formed on the surface of the object. The formed film shows good adhesion to the object and continues to adhere without dropping off in the natural sea for more than 12 months. In the meantime, the attachment of attached organisms is prevented.

As the target, fixed nets, fishing nets such as aquaculture nets,
There are various structures in a cooling water system using seawater, various underwater structures such as bridges, and the like, such as a ship bottom, a seawater intake channel wall, and the like.

[Action]

The copolymer having an average molecular weight of 5,000 to 500,000 obtained by polymerizing the above specific monomers (A), (B), (C) and optionally (D) at the above specific ratio is A (meth) acrylic acid containing a (meth) acrylic acid salt of a higher aliphatic amine as a low-toxic antifouling active ingredient as a monomer component and containing an alkylene oxide residue X in a specific ratio. Has a certain proportion of esters. For this reason, the higher aliphatic amine is firmly and stably bonded to the resin base, and the higher aliphatic amine is eluted into water gradually over a long period of time. It is stable without receiving it.

〔Example〕

Hereinafter, specific examples and comparative examples of the present invention will be described, but the present invention is not limited to the following examples.

Example 1 In a flask equipped with a thermometer, a stirrer, two dropping funnels, a gas inlet tube and a reflux condenser, 45 g of xylene, 7.5 g of 2-ethoxyethanol, 7.5 g of isopropyl alcohol,
60.5 g of acrylic acid dodecylamine salt, 2.8 g of 2-hydroxyethyl acrylate, 22.6 g of methyl methacrylate and 14.5 g of 2-ethylhexyl acrylate were charged,
The atmosphere in the flask was replaced with nitrogen while stirring, and the flask was
Heated to ° C. Thereafter, while maintaining the same temperature under a stream of nitrogen, the liquid in the flask was charged with 90 g of xylene, 15 g of 2-ethoxyethanol, 15 g of isopropyl alcohol, dodecylamine acrylate from one of the two dropping funnels. 60.5 g, 2-hydroxyethyl acrylate 2.8 g, methyl methacrylate 22.6 g and 2-ethylhexyl acrylate 14.1 g of a monomer mixed solution
Over a period of 0 minutes, the polymerization initiator solution comprising 13.7 g of xylene, 2.3 g of 2-ethoxyethanol, 2.3 g of isopropyl alcohol and 1.7 g of azobisdimethylvaleronitrile was simultaneously dropped from the other dropping funnel over 180 minutes. . After dropping, heat the inside of the flask to 90 ° C.
Maintained for 60 minutes to complete the polymerization. The solution of the obtained copolymer had a solid content of 50% by weight, and the average molecular weight of the obtained copolymer was 125,000 as a result of GPC (gel permeation chromatography) analysis using polystyrene as a standard.

After the polymerization was completed, the content of the flask was cooled, and then 126.3 g of xylene was added, followed by stirring for 2 hours. Thus, a solution of the antifouling agent A in water was obtained.

-Examples 2 to 12 and Comparative Examples 1 to 6 In Example 1, polymerization was carried out in exactly the same manner as in Example 1, except that the components shown in Table 1 were used in the proportions shown in the same table. Underwater antifouling agents BR were obtained.

The underwater antifouling agents A to L are persistent underwater antifouling agents according to the present invention, and the underwater antifouling agents MR are comparative underwater antifouling agents.

Table 1 also shows the average molecular weight of the obtained copolymer.

In Table 1, the symbols of the amine species in the column of monomer species (A) are A1; dodecylamine A2; octadecylamine A3; di (dodecyl) amine A4; di (octadecyl) amine A5; N, N-dimethyldodecylamine A6. N, N-dimethyloctadecylamine A7; N-dodecyltrimethylenediamine A8; N-octadecyltrimethylenediamine A9; tallowalkylamine (tallowalkyl; having 12 to 20 carbon atoms)
A10; N-methylethyldodecylamine A11; triethylamine, AA salt; Acrylic acid amine salt MAA salt; Methacrylic acid amine salt MAA; Methacrylic acid . Symbols in the column of monomer species (B) are as follows: a; 2-hydroxyethyl acrylate b; methoxy PEG (9) acrylate c; methoxy PPG (3) -PEG (9) methacrylate d; n-propoxy PEG (25) acrylate e; Methoxy PEG (23) methacrylate (however, PEG indicates polyethylene glycol, PPG indicates polypropylene glycol, and the number in parentheses indicates the number of moles added). Symbols in columns (C) and (D) of monomer species are as follows: MA; methyl acrylate BA; butyl acrylate 2EHA; 2-ethylhexyl acrylate DA; dodecyl acrylate SA; stearyl acrylate MMA; methyl methacrylate TBMA; t-butyl methacrylate DMA; dodecyl Methacrylate St; represents styrene.

The following antifouling performance evaluation tests were performed using the underwater antifouling agents A to R obtained in Examples and Comparative Examples.

Antifouling performance evaluation test method As a test net, a polyethylene farming net (10
0, 5 sections, 40 cm × 60 cm, 60 g) were used.

After immersing the test net in each underwater antifouling agent, it was air-dried for 3 days. In this case, the adhesion amount of the underwater antifouling agent calculated from the weight difference before and after immersion was controlled as follows. That is, the amount of the structural portion of the monomer (A) contained in the underwater antifouling agent attached to the test net was adjusted to 8.5 to 9.5% by weight based on the weight of the net.

A test net with an underwater antifouling agent was hung on a raft off Tokushima Prefecture at a depth of 1.0 to 1.5 m below the sea surface, and the antifouling efficacy was periodically evaluated.

The antifouling effect is based on the area of the test net (40cm x 60cm)
Evaluation was based on the ratio of the area occupied by the attached organisms. Table 2 shows the evaluation results. The immersion time differs greatly between the low water temperature period and the high water temperature period since the species and amount of attached organisms differ greatly.
Start immersion on the same sample on the day and August 1,
Fluctuations in dissolution due to seawater temperature were also confirmed.

As shown in Table 2, the underwater antifouling agents A to L of the examples are:
Although it shows antifouling effect even 12 months after the start of immersion,
The underwater antifouling agents M to R of the comparative examples have considerably reduced the antifouling effect 3 to 6 months after the start of immersion, and have no antifouling effect at 12 months. In addition, after the start of immersion in the examples, 6
The antifouling effect for three months is equal to or better than the antifouling effect for three months after the start of immersion in the comparative example. Even when the immersion start times are different, the antifouling effect of the example is more stable than that of the comparative example, and is far superior.

In addition, the underwater antifouling agents A to L of the examples, when used as a fishing net antifouling agent, penetrate into fishing nets, good drainage becomes good, and when used as an antifouling paint, there is no liquid dripping and the elongation is good. Excellent coating workability.

〔The invention's effect〕

The persistent underwater antifouling agent according to the present invention is as described above, and gradually dissolves an antifouling active ingredient having a low toxicity and no accumulation over a long period of time to exhibit antifouling performance. Therefore, even if the water temperature fluctuates, its antifouling performance is stable.

──────────────────────────────────────────────────の Continued on the front page (51) Int.Cl. ⁶ Identification symbol FI C09D 133/02 C09D 133/02 155/00 155/00 // (C08F 220/06 220: 28 220: 12 220: 20) ( 72) Inventor Kenji Rakuya 14-1, Chidori-cho, Kawasaki-ku, Kawasaki-shi, Kanagawa Prefecture Inside the Kawasaki Research Laboratory, Nippon Shokubai Chemical Industry Co., Ltd. (72) Inventor Yusuke Shioda 14-1, Chidori-cho, Kawasaki-ku, Kawasaki-shi, Kanagawa Japan (56) References JP-A-62-39672 (JP, A) JP-A-60-217277 (JP, A) JP-A-60-177063 (JP, A) JP-A 62-39673 (JP, A) JP-A-1-103672 (JP, A) (58) Fields investigated (Int. Cl. ⁶ , DB name) C08F 220/20-220/28 C08F 290/06 C08F 20/02-20 / 28 C09D 5 / 14,133 / 02,155 / 00 A01N 33 / 04,37 / 06

Claims (2)

(57) [Claims] (1) 60 to 94% by weight of a monomer (A), 1 to 5% by weight of a monomer (B) and 5 to 39% by weight of a monomer (C) described below.
(However, the total amount of the above (A), (B) and (C) is
100% by weight. A) a persistent underwater antifouling agent comprising a copolymer having an average molecular weight of 5,000 to 500,000, obtained by polymerizing the monomer component comprising (A) general formula (I); (Wherein, in the formula (I), R ¹ is hydrogen or a methyl group, R ² is a saturated or unsaturated higher aliphatic hydrocarbon group, R ³ is a hydrogen or a saturated or unsaturated lower aliphatic hydrocarbon group, R ⁴ is hydrogen, a saturated or unsaturated aliphatic hydrocarbon group, or a saturated or unsaturated lower aliphatic hydrocarbon group substituted with an amino group (provided that the hydrogen of the amino group is a saturated or unsaturated lower aliphatic group) A monomer which may be substituted with a hydrocarbon group.)) (B) general formula (II); (Wherein, in the formula (II), R ⁵ is hydrogen or a methyl group, and X is 50% by weight based on the total weight of all the alkylene oxide residues.)
2 to 4 carbon atoms comprising the above ethylene oxide residue
Wherein n is an integer of 1 to 100, and R ⁶ is hydrogen or a hydrocarbon group having 1 to 5 carbon atoms. ) A monomer represented by (C) general formula (III); (However, in the formula (III), R ⁷ is hydrogen or a methyl group, R ⁸
Is a hydrocarbon group having 1 to 20 carbon atoms. ) A monomer represented by 2. In the formula (I), R ¹ is hydrogen or a methyl group, R ²
Is a saturated or unsaturated aliphatic hydrocarbon group having 12 to 20 carbon atoms, R ³ is hydrogen or an alkyl group having 1 to 6 carbon atoms, R ⁴ is hydrogen, an alkyl group having 1 to 6 carbon atoms, A saturated or unsaturated aliphatic hydrocarbon group of 20 or an alkyl group having 1 to 6 carbon atoms substituted with an amino group (provided that hydrogen of the amino group is substituted with an alkyl group having 1 to 6 carbon atoms) The persistent underwater antifouling agent according to claim 1, wherein