JPH03252463A - Durable underwater antifouling agent - Google Patents

Abstract

PURPOSE:To obtain the title underwater antifouling agent gradually eluting for a long period of time an antifouling active ingredient having low toxicity and no accumulation, showing antifouling performances, having stable antifouling performances even variability of water temperature, containing a specific copolymer and a higher aliphatic amine. CONSTITUTION:The objective antifouling agent containing (A) a copolymer which comprises 10-80wt.% polymerizable unsaturated carboxylic acid, 1-25wt.% monomer shown by formula I (R<1> is H or methyl; R<2> is higher aliphatic hydrocarbon; R<3> is H or lower aliphatic hydrocarbon; R<4> is H, aliphatic hydrocarbon, etc.), 5-89wt.% monomer shown by formula II (R<5> is H or methyl; X is residue of 2-4C alkylene oxide containing >=50wt.% ethylene oxide residue; n is 1-100; R<6> is H or 1-5C hydrocarbon) and 0-20wt.% another vinyl based monomer and has 5,000 50,000 average molecular weight and (B) 0.5-1.5mol based on 1 carboxyl group of the copolymer of a higher aliphatic amine shown by formula III (R<5> is higher aliphatic hydrocarbon; R<6> is H or lower aliphatic hydrocarbon; R<7> is H or aliphatic hydrocarbon, etc.).

Description

[Detailed Description of the Invention] [Field of Industrial Application] The present invention provides a sustainable underwater system for preventing sessile organisms, especially underwater sessile organisms, from adhering to fishing nets, ship bottoms, seawater intake channel walls, etc. over a long period of time. Regarding antifouling agents.

[Conventional technology]

In the past, various antifouling agents have been proposed and are actually used to suppress the attachment of fouling organisms to fishing nets, ship bottoms, seawater intake channel walls, etc., in order to prevent them from adhering to surfaces and causing negative effects. .

For example, JP-A-58-120678, JP-A-58-120678,
No. 9-133267 proposes an antifouling agent containing a vehicle containing an effective antifouling ingredient such as an organic tin polymer or cuprous oxide and a specific polymer compound. These antifouling active ingredients are so toxic that they cause marine pollution problems, and they also have the property of accumulating in living organisms. For this reason, especially in the aquaculture industry, there are concerns about the effects on the human body when handling aquacultured organisms for food. On the other hand, the impact on workers who directly handle antifouling agents is also a particular concern.

Therefore, an antifouling agent with low toxicity and no accumulation is desired.

As a low-toxicity antifouling agent, a coating material consisting only of a specific high molecular weight polymer that does not contain the above-mentioned antifouling active ingredient has also been proposed (see Japanese Patent Laid-Open No. 170673/1983). The antifouling effect of this coating material is extremely insufficient during the period when mussels, barnacles, snails, bryozoans, algae, etc. are actively breeding (usually from August to December in the coastal waters of western Japan in the Pacific Ocean). It has the disadvantage that it cannot sufficiently suppress the adhesion of shellfish, etc. In addition, the above-mentioned coating material also has the disadvantage that its antifouling effect does not last for a long period of time (for example, 3 months or more). We have discovered that a specific higher aliphatic amine compound with good properties has an excellent antifouling effect, and have already developed a long-lasting underwater antifouling agent containing this amine compound and a film-forming agent made of a specific copolymer. (Refer to Japanese Patent Application Laid-Open No. 103672/1999).

[Problem to be solved by the invention]

However, the long-lasting underwater antifouling agents just described are still not fully satisfactory in their antifouling effects over a longer period of time (for example, 6 months or more).

During such a long period of time, the temperature of the seawater varies greatly, and accordingly, the degree of elution of the antifouling active ingredient from the antifouling agent also varies greatly, resulting in the magnitude of the antifouling effect. Usually, antifouling agents are prepared so that the elution of antifouling active ingredients increases during the summer when biological activity is active. However, in winter,
This does not mean that sessile organisms are not active at all, and there is a need for an antifouling agent that exhibits similar antifouling effects both in summer and winter.

Therefore, the present invention prevents negative effects on the human body and the environment by using a low-toxicity and non-accumulative agent as the antifouling active ingredient, and also prevents the dissolution of the antifouling active ingredient from changing much depending on the season. The first object of the present invention is to provide a persistent underwater antifouling agent that can stably exhibit an antifouling effect over a long period of time.

[Means for Solving the Problems] In order to solve the above problems, the persistent underwater antifouling agent according to the present invention is produced by polymerizing the following monomers (2), (B), (a and The copolymer has an average molecular weight of 5,000 to 500,000, and a higher aliphatic amine [F] represented by the following general formula (III).

The content ratio of the copolymer and the higher aliphatic amine is 0.000% of the higher aliphatic amine per carboxyl group in the copolymer.
The amount is 5 to 1.5 moles. The monomer components for obtaining the copolymer include 10 to 80% by weight of monomer (2) and monomer (B).
) 1 to 25% by weight, monomer (C55 to 89% by weight and monomer (D) 0 to 20% by weight (However, (A), (8)
, (the total amount of a and (D) is 100% by weight.)
It is.

(A) Polymerizable unsaturated carboxylic acid.

03) General formula (I); R' CH, -^-COO(X), R'' (wherein, in formula (I), R1 is hydrogen or a methyl group,
is 50i based on the total weight of all alkylene oxide residues.
2 carbon atoms containing ethylene oxide residues in an amount of % or more
~4 alkylene oxide residue, n is an integer of 1 to 100, and Rt is hydrogen or a hydrocarbon group having 1 to 5 carbon atoms.

) A monomer represented by

(However, in formula (II), R1 is hydrogen or a methyl group,
R4 is a hydrocarbon group having 1 to 20 carbon atoms. ).

(To) Vinyl monomers other than (A) to (a) above.

(However, in the formula (I [I), R' is a saturated or unsaturated higher aliphatic hydrocarbon group, Ro is hydrogen or a saturated or unsaturated lower aliphatic hydrocarbon group, R7 is hydrogen, a saturated or unsaturated aliphatic hydrocarbon group, or a saturated or unsaturated lower aliphatic hydrocarbon group substituted with an amino group (
However, the hydrogen of the amino group may be substituted with a saturated or unsaturated lower aliphatic hydrocarbon group. ). ) higher aliphatic amines.

As the polymerizable unsaturated carboxylic acid (4), a carboxylic acid having one or more unsaturated bonds between carbon atoms and having 3 to 10 carbon atoms is used, such as acrylic acid, methacrylic acid (hereinafter referred to as "acrylic acid and unsaturated fatty acids such as crotonic acid; unsaturated aromatic monocarboxylic acids such as vinylbenzoic acid; unsaturated acids such as maleic acid, fumaric acid, and itaconic acid. Dicarboxylic acids include α-cyanoacrylic acid and the like, each of which may be used alone or two or more may be used in combination.

Note that these polymerizable unsaturated carboxylic acids may be anhydrides.

The above monomer (R31 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, There are ethylene oxide, propylene oxide, butylene oxide, tetramethylene oxide, etc., but it must contain 50% by weight or more and 100% by weight or less of ethylene oxide residues based on the total weight of the alkylene oxide residue base.Ethylene oxide If the residue is less than 50% by weight, the hydrophobicity of the obtained copolymer becomes large and there is a problem that the elution properties of the antifouling active ingredient tend to fluctuate.The number of repeats n of the alkylene oxide residue X is It is an integer from 1 to 100. When n exceeds 100, there is a problem that copolymerizability with other monomers is poor and it is difficult to obtain the desired copolymer. If the number of carbon atoms is less than 2, the hydrophilicity of the obtained copolymer will be strong and the antifouling active ingredient will be easily eluted. There are problems in that the dissolution of the active ingredient tends to fluctuate, and the monomer is difficult to obtain.The group R2 is hydrogen or a hydrocarbon group having 1 to 5 carbon atoms.The group R is rich in carbon. If the number exceeds 5, the hydrophobicity of the obtained copolymer becomes large, leading to problems such as fluctuations in the elution properties of the antifouling active ingredient and difficulty in obtaining the monomer. Specific examples include hydrogen, alkyl groups such as methyl group, ethyl group, propyl group, butyl group, and amyl group; and fulkenyl groups such as vinyl group, propenyl group, and butenyl group.

The above monomer (a is (meth) represented by general formula (II))
It is an acrylic acid ester. In the formula (I[), the group R' is a hydrocarbon group having 1 to 20 carbon atoms. The number of carbon atoms in the group R4 is 2
If it exceeds 0, the hydrophobicity of the obtained copolymer becomes large and there is a problem that the dissolution properties of the antifouling active ingredient are likely to fluctuate. Specific examples of the group R4 include, for example, a methyl group,
Ethyl group, propyl group, butyl group, amyl group, hexyl group, heptyl group, octyl group, nonyl group, decyl group, undecyl group, dodecyl group, tridecyl group, tetradecyl group, pentadecyl group, hexadecyl group, heptadecyl group, octadecyl group , nonadecyl group, eicosyl group; aralkyl groups such as phenyl group, naphthyl group, octylphenyl group, nonylphenyl group; and cyclic alkyl groups such as cyclohexyl group.

The above monomer (2) is a monomer that is used as necessary to improve the performance of the film formed when the persistent underwater antifouling agent of the present invention is applied to an object. ), (
It is a vinyl monomer other than B) and (C). Specific examples of monomers include unsaturated hydrocarbons such as dodecene, styrene, α-methylstyrene, butadiene, and vinyltoluene; halogenated monomer 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; acrylonitrile and the like.

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

The proportion of monomers (2), (B) and (a) used is based on 100% by weight of the total weight of all these monomers (2), (B) and (a).
A) 10-80% by weight, monomer CBI 1-25% by weight
, monomer (G) 5 to 89% by weight.
2) is used as necessary within a range that does not impede the effects of the present invention, and is used in a proportion of 20% by weight or less of the monomer based on 100% by weight of the total weight of (4) to (D). is preferable. If the proportion of R-mer (2) used is less than the above lower limit, there is a problem that a sufficient content of higher aliphatic amine cannot be obtained, and if it is more than the above upper limit, the It2 film properties are poor and the antifouling This is not preferable because the durability of the effect decreases. If the proportion of monomer 031 used is less than the above lower limit, the hydrophilicity of the copolymer itself to seawater will be poor, the elution of the antifouling active ingredient will be reduced, and a long-term antifouling effect will not be obtained. If the amount is more than the upper limit, the antifouling film will be dissolved in seawater in a short period of time due to the high hydrophilicity, and a long-term antifouling effect will not be obtained, so it will not pass through.

If the proportion of monomer (a) used is less than the above lower limit, film forming properties will be poor, and a long-term antifouling effect will not be obtained due to the inability to impart appropriate hydrophobicity; if it is greater than the above upper limit, hydrophobic Highly sensitive (
Therefore, the elution property of the antifouling film decreases, and a long-term antifouling effect cannot be obtained.

The monomer components consisting of these monomer faces, (B), (0 and (to) used as necessary) are polymerized to obtain a copolymer having an average molecular weight of 5,000 or more and 500,000 or less. If the average molecular weight of the polymer is less than 5,000, there is a problem that the form of the coating agent cannot be maintained in seawater, and if it is larger than 500,000, there is a problem that the antifouling agent has a high viscosity and the workability is significantly inferior.

Such a copolymer is produced, for example, by copolymerizing a monomer component obtained by mixing the above monomers (2) to σ in the above ratio by a known method using a polymerization initiator. . Copolymerization can be carried out by methods such as polymerization in a solvent or bulk polymerization.

Polymerization in a solvent can be carried out either batchwise or continuously, and the solvents used in this case include evaporate, water; methyl alcohol, ethyl alcohol, isopropyl alcohol, butanol, 2-methoxyethanol, 2- Alcohols such as ethoxyethanol; Aromatic hydrocarbons such as benzene, toluene, xylene, ethylbenzene, and methylnaphthalene; Alicyclic hydrocarbons such as cyclohexane; Aliphatic hydrocarbons such as n-hexane; Complex hydrocarbons such as dioxane Cyclic compounds: 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 ab compounds such as butyronitrile, azobisisophthalonitrile, azobisdimethylvaleronitrile, etc. are used. At this time, a promoter such as an amine compound can also be used in combination. The polymerization temperature is appropriately set depending on the solvent and polymerization initiator used, but is usually set within the range of 0 to 120°C. For bulk polymerization, a peroxide such as benzoyl peroxide or lauroyl peroxide is used as a polymerization initiator;
It is carried out using a hydroperoxide such as cumene hydroperoxide; an azo compound such as azobisisobutyronitrile, etc. within a temperature range of 50 to 150°C.

The higher aliphatic amine (2) used in this invention has the general formula (
This is a compound represented by III). Group R' of formula (II)
is a higher aliphatic hydrocarbon group, and may be either saturated or unsaturated. The group R6 is hydrogen or a lower aliphatic hydrocarbon group, and the hydrocarbon group may be either saturated or unsaturated. Group R7 is hydrogen, an aliphatic hydrocarbon group, or a lower aliphatic hydrocarbon group substituted with an amino group (however, the hydrogen of the amine group may be substituted with a lower aliphatic hydrocarbon group). If the group R7 is an aliphatic hydrocarbon group, it may be either lower or higher. The lower or higher aliphatic hydrocarbon groups mentioned herein may be either saturated or unsaturated.

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

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

The higher aliphatic hydrocarbon group has 12 to 20 carbon atoms.
Examples include aliphatic hydrocarbon groups.

In addition, when both groups R5 and R7 are higher aliphatic hydrocarbon groups, they may be the same or different from each other.

Furthermore, when both groups R- and R7 are lower aliphatic hydrocarbon groups, they may be the same or different from each other.

Specific examples of the higher aliphatic amine represented by the above formula (I [ , primary amines such as coconut alkylamine; di(dodecyl)amine, di(octadecyl)amine, di(oleyl)amine, di(tallow alkyl)amine, di(cocoalkyl)amine, dodecyltetradecylamine, dodecylhexadecyl Amine, dodecyloctadecylamine, tetradecylhexadecylamine, tetradecyloctadecylamine, hexadecyloctadecylamine, dodecyloleylamine, dodecylmethylamine, oleylethylamine, hexadecylmethylamine, octadecylmethylamine, tallow alkylmethylamine, coconut alkylmethylamine , hexadecylbutylamine, coconut alkylpropylamine, etc.
dodecyldimethylamine, hexadecyldimethylamine, octadecyldimethylamine, tetradecyldimethylamine, tallow furkyldimethylamine, coconut alkyldimethylamine, didodecylmethylamine, dioctadecylmethylamine, ditallow alkylmethylamine, di( Cocoalkyl) methylamine, dodecyltetradecylmethylamine, dodecylhexadecylmethylamine, dodecyloctadecylmethylamine, tetradecylhexadecylmethylamine, tetradecyloctadecylmethylamine, hexadecyloctadecylmethylamine, dodecylmethylpropylamine, hexadecylmethylamine Tertiary amines such as thylamine, tallow alkyl ethylpropylamine, tallow alkyl diethylamine, tallow alkyl dipropylamine, tallow alkyl dibutylamine, tallow alkylmethylhexylamine, coconut alkyl dibentylamine, coconut alkyl dihexylamine; dodecyl trimethylene diamine , hexadecyl trimethylene diamine, octadecyl trimethylene diamine, tallow alkyl trimethylene diamine, coconut alkyl trimethylene diamine, beef tallow alkyl methylene diamine, coconut alkyl ethylene diamine, N-tallow alkyl-N'-dimethyl trimethylene diamine, N-coco alkyl-N ′−
Examples include diamines such as dibutyltrimethylenediamine. Among these amines, “coconut alkyl (・
...) amine" and "tallow alkyl (...) amine" mean that the amine is a group R5 and/or A mixture of amines in which the main component is a saturated or unsaturated aliphatic hydrocarbon group in which R7 has 12 to 20 carbon atoms (mixed alkylamine)
It means that. As higher aliphatic amine 0,
Any one of the compounds represented by formula (II[) may be used alone, or two or more may be used in combination.

Higher aliphatic amines (2) are those represented by the above formula (II[), in which the group R' is a saturated or unsaturated aliphatic hydrocarbon group having 12 to 20 carbon atoms, and the group R6 is hydrogen or a carbon number 1-6 alkyl group, group Rte is hydrogen, carbon number 1-6
an alkyl group having 12 to 20 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 substituted with an amino group (provided that the hydrogen of the amino group has 1 to 6 carbon atoms) It is preferable to use a compound which is optionally substituted with an alkyl group. This is because such compounds are easily available industrially at relatively low cost.

The above copolymer and the above higher aliphatic amine (E) are mixed. This mixing can be carried out by adding the higher aliphatic amine to a solution dissolved using an appropriate solvent and stirring the mixture. The solution temperature at this time is approximately 20 to 60
C., and the stirring time is suitably about 0.5 to 2 hours. The ratio of the copolymer to the higher aliphatic amine must be set such that the amount of the higher aliphatic amine is 0.5 to 1.5 moles per carboxyl group in the copolymer. If the amount of higher aliphatic amine is higher than this, the density of the film-forming components in the antifouling film that is formed is low, so the film strength is weak and the film is easily eluted or destroyed, resulting in a long-term antifouling effect. There is a problem that if the higher aliphatic amine content is low, the antifouling effect will not be effectively exhibited. Examples of solvents used include methanol, ethanol, xylene, toluene, kerosene, methyl isobutyl ketone, butyl acetate, dimethyl formamide, naphtha, and methyl cellosolve, but there are also various solvents used in the paint field. It can be used and may also contain water.

The persistent underwater antifouling agent of the present invention is usually dissolved in a suitable solvent and used in the form of a solution. As the solvent, for example, the solvent used for mixing the above-mentioned copolymer and higher aliphatic amine (2) can be used. It is preferable to adjust the solid content concentration to about 20 to 50% by weight in terms of film formability, film strength, etc. The solution prepared in this way is easy to handle during coating operations, avoids excessive adhesion, and reduces costs.

As described above, the underwater antifouling agent of the present invention can be used as it is after being dissolved in a suitable solvent, but it can also be used as an antifouling paint by being blended with a vehicle, pigment, plasticizer, surfactant, solvent or diluent, etc. 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 entire paint. The vehicle, pigment, plasticizer, surfactant, solvent, diluent, etc. are not particularly limited as long as they can be used in paints and can be used as appropriate.

The persistent underwater antifouling agent of this invention can be immersed or
It is applied using an appropriate coating method such as brushing or spraying, dried at room temperature or by heating, and baked if necessary to form a film on the surface of the object. The formed film shows good adhesion to the object and continues to adhere to the object for more than 12 months without falling off, even in the natural sea. and,
During this time, it prevents the attachment of sessile organisms.

Examples of the objects include fishing nets such as fixed nets and aquaculture nets, ship bottoms, walls of seawater intake channels, and various underwater structures such as various structures in cooling water systems that use seawater and bridges.

[For production]

The average molecular weight obtained by polymerizing the above-mentioned specific monomers (2), (a and fD) at the above-mentioned specific ratios: 5000-
By using the 500,000 copolymer and the above-mentioned specific higher aliphatic amine in the above-mentioned specific ratio, the (meth)acrylic acid ester containing the alkylene oxide residue X in the specific ratio can be produced in a specific ratio. By using the above copolymer and the higher aliphatic amine (5) in a specific ratio, the higher aliphatic amine, which is a low-toxicity antifouling active ingredient, gradually dissolves into water over a long period of time. It happened, and
This dissolution property is not affected by fluctuations in water temperature and is stable.

〔Example〕

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

Example 1 - A flask equipped with a thermometer, a stirrer, two dropping funnels, a gas inlet tube, and a reflux condenser was charged with 22.8 g of xylene and 53.2 g of 2-methoxyethanol, and the inside of the flask was heated while stirring. Direct nitrogen exchange and 80% under nitrogen flow
heated to ℃. Then, while maintaining the temperature under a nitrogen stream, 21.0 g of xylene, 49.0 g of 2-methoxyethanol, and 50 g of acrylic acid were added to the liquid in the flask from one of the two dropping funnels. .0 g, 2
- A monomer mixed solution consisting of 10.0 g of hydroxyethyl acrylate, 80.0 g of methyl methacrylate, and 60.0 g of 2-ethylhexyl acrylate was added dropwise over 60 minutes, and at the same time 15.0 g of xylene was added from the other dropping funnel. g, 2-methoxyethanol 35. A polymerization initiator solution consisting of Og and 4.0 g of azobisdimethylvaleronitrile was added dropwise over 120 minutes. After the dropwise addition was completed, the same temperature was further maintained for 60 minutes to complete the polymerization. The obtained copolymer solution had a solid content of 50% by weight, and the average molecular weight of the obtained copolymer was 5 as a result of GPC (gel permeation chromatography) analysis using polystyrene as a standard.
．． After the polymerization was completed, the temperature of the contents of the flask was cooled to 60°C, and then 680.4 g of xylene and 339.6 g of octadecyltrimethylenediamine were added and stirred for 2 hours. This provided a solution for the underwater antifouling agent.

Examples 2 to 12 and Comparative Examples 1 to 7 - In Example 1, polymerization was carried out in exactly the same manner as in Example 1, except that each component shown in Table 1 was used in the proportions shown in the same table, Underwater antifouling agent B-3 was obtained.

Note that the underwater antifouling agent A-L is a persistent underwater antifouling agent according to the present invention, and the underwater antifouling agent M-3 is a comparative underwater antifouling agent.

Table 1 shows the average molecular weight of the obtained copolymer, and
The number of moles of higher aliphatic amine per carboxyl group in the copolymer is also shown.

In Table 1, the symbols in the monomer type (A) column represent AA; acrylic acid MAA; methacrylic acid MLA; maleic acid. The symbols in the monomer type (B) column are a; 2-hydroxyethyl acrylate b; methoxy PEG (9) acrylate C; methoxy PPG (3) -PEG (9
) methacrylate den-propoxy PEG (25) acrylate C; methoxy PEG (23) methacrylate (however, PE
G represents polyethylene glycol, PPG represents polypropylene glycol, and the number in parentheses represents the number of moles added. ) is shown. Monomer type (0@ and the symbol in the (D) column is M
A; Methyl acrylate BA; Butyl acrylate-1.2EHA; 2-ethylhexyl acrylate 1) A; Dodecyl acrylate SA; Stearyl acrylate MMA; Methyl methacrylate TBMA; t-Butyl methacrylate DMA; Dodecyl methacrylate St-styrene. The symbols in the type column of higher aliphatic amines are A-tododecylamine 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; tallow alkylamine (tallow alkyl; saturated or unsaturated aliphatic hydrocarbon group having 12 to 20 carbon atoms) AIO; N-methylethyldodecylamine All;) ethylamine Kt Cow; potassium carbonate represents.

The following antifouling performance evaluation test was conducted using the underwater antifouling agents A to S obtained in Examples and Comparative Examples.

1--1 As a test net, a polyethylene aquaculture cage circumferential line (I0
0 pieces, 5 sections, 40 cm x 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 amount of attached underwater antifouling agent calculated from the weight difference before and after immersion was controlled as follows. That is, the amount of higher aliphatic amine contained in the underwater antifouling agent attached to the test net was set to 8.0 to 9.0% by weight based on the amount of M in the same line.

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

The antifouling effect was evaluated by the ratio of the area occupied by attached organisms to the area of the test net (40 cm x 60 cm). The evaluation results are shown in Table 2. The immersion period is important because the species and amount of attached organisms differ greatly between the low water temperature period and the high water temperature period.
Dipping was started on April 1st and August 1st with the same samples, and changes in dissolution properties due to seawater temperature, etc. were also confirmed.

However, its antifouling performance is stable.

Claims (1)

[Scope of Claims] 1 10 to 80% by weight of the following monomer (A), monomer (
B) 1 to 25% by weight, monomer (C) 5 to 89% by weight, and monomer (D) 0 to 20% by weight (however, (A), (B)
), (C) and (D) is 100% by weight. ) A copolymer having an average molecular weight of 5,000 to 500,000 obtained by polymerizing a monomer component consisting of A persistent underwater antifouling agent containing an amine in a proportion of 0.5 to 1.5 moles. (A) Polymerizable unsaturated carboxylic acid. (B) General formula (I); ▲There are mathematical formulas, chemical formulas, tables, etc.▼ (However, in formula (I), R^1 is hydrogen or methyl group, and X is based on the total weight of all alkylene oxide residues. 5
An alkylene oxide residue having 2 to 4 carbon atoms containing 0% by weight or more of ethylene oxide residue, n being an integer of 1 to 100, and R^2 being hydrogen or a hydrocarbon group having 1 to 5 carbon atoms. ) is a monomer represented by (C) General formula (II); ▲There are mathematical formulas, chemical formulas, tables, etc.▼ (However, in formula (II), R^3 is hydrogen or a methyl group,
R^4 is a hydrocarbon group having 1 to 20 carbon atoms. ) is a monomer represented by (D) Vinyl monomers other than the above (A) to (C). (E) General formula (III); ▲Mathematical formulas, chemical formulas, tables, etc.▼ (However, in formula (III), R^5 is a saturated or unsaturated higher aliphatic hydrocarbon group, R^6 is hydrogen or A saturated or unsaturated lower aliphatic hydrocarbon group, R^7 is hydrogen, a saturated or unsaturated aliphatic hydrocarbon group, or a saturated or unsaturated lower aliphatic hydrocarbon group substituted with an amino group (but , the hydrogen of the amino group may be substituted with a saturated or unsaturated lower aliphatic hydrocarbon group. ) A higher aliphatic amine represented by 2 In the formula (III), R^5 is a saturated or unsaturated aliphatic hydrocarbon group having 12 to 20 carbon atoms, R^6 is hydrogen or an alkyl group having 1 to 6 carbon atoms, and R^7 is hydrogen or carbon Numbers 1-6
an alkyl group having 12 to 20 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 substituted with an amino group (provided that the hydrogen of the amino group has 1 to 6 carbon atoms) The persistent underwater antifouling agent according to claim 1, which is optionally substituted with an alkyl group.