JPS624758A - Method for preventing deposition of aquatic organism - Google Patents

Abstract

PURPOSE:To effectively a flexible article made of a fiber and to be used underwater, such as a fishing net, from deposition of aquatic organisms, by applying thereto an antifouling agent mainly composed of a copolymer of a triorganotin- contg. monomer and a hydrophilic monomer. CONSTITUTION:A monomer of formula I (wherein R1 is H, methyl; R2, R3, R4 are each a 1-8C alkyl, phenyl), such as tri-n-butyltin methacrylate, and a monomer of formula II (wherein R5, R6, R7 are each H, methyl; R8 is a 1-4C alkyl, acyl; n is 1-30), such as 2-methoxyethyl acrylate, are compolymerized to produce a copolymer contg. a structural unit of formula III and at least 5wt% structural unit of formula IV. An antifouling agent contg. said copolymer and 0-30% nonpolymer antifouling agent (e.g. copper naphthenate) is prepd. and applied to a flexible article made of a fiber and to be used underwater, such as a fishing net, to prevent the deposition of aquatic organisms.

Description

[Detailed Description of the Invention] [Field of Industrial Application] This invention is applicable to various types of flexible underwater fiber inputs such as fishing nets and marine pollution prevention membranes (hereinafter simply referred to as flexible underwater inputs). The present invention relates to a method of preventing adhesion of aquatic organisms by applying an antifouling agent.

[Conventional technology]

Flexible underwater inputs, such as fishing nets such as aquaculture nets and fixed nets that are left in the water, or marine pollution prevention membranes that are deployed in water areas where civil engineering works are being carried out to isolate surrounding water areas from existing hot water areas, are not suitable for long periods of time. During use for a period of time, various aquatic organisms adhere to the product, resulting in various harmful effects.

In other words, if a large amount of plants and animals that live in the water, such as mussels, Fujibo, Serpura, Ulva, and Green Nori, attach to these underwater inputs, they will clog the mesh as they grow, obstructing the flow of seawater, and damaging the aquaculture net. In some cases, the growth of fish is inhibited and fish diseases are likely to be induced. In addition, in the case of fixed nets, as the ocean current resistance increases, this leads to poor net formation, which not only drastically reduces the amount of fish caught (and also significantly shortens the lifespan of the nets). The relative buoyancy of the float being lowered decreases significantly, and the membrane that has been stretched out sinks, resulting in the loss of complete isolation between the existing hot water area and the surrounding water area.As a result, the initial objective of preventing pollution in the surrounding water area is not achieved. There is no suitable method for removing attached aquatic plants and animals.
Since we have no choice but to rely on human power, a great deal of effort is required to remove them.

In order to solve this problem, antifouling agents that prevent aquatic organisms from adhering have been studied, and flexible underwater objects such as fishing nets have been protected by treatment with these agents. These antifouling agents contain organic copper compounds, organic tin compounds, or various inorganic-organic chemicals as active ingredients, and are a type of antifouling agent that prevents aquatic organisms from adhering to them by poisonous components that gradually elute into the water from the treated coating. It is something.

Among these antifouling treatment agents, Japanese Patent Publication No. 40-21426 and Japanese Patent Publication No. 4
It is said that the most suitable is one using an organic tin pendant polymer as shown in Japanese Patent No. 4-9579. This antifouling agent is a homopolymer of a triorganotin-containing monomer obtained by esterifying a triorganotin compound with (meth)acrylic acid, or a copolymer of this and other unsaturated monomers. It is a polymer component.

This type of polymer component is gradually hydrolyzed in slightly alkaline seawater to liberate triorganotin compounds, and carboxyl groups are generated in the polymer. The liberated triorganotin compound functions as an antifouling component and protects against biofouling. On the other hand, the production of carboxyl groups makes the polymer hydrophilic, and as the amount of carboxyl groups in the polymer increases as hydrolysis progresses, the polymer dissolves in seawater.

This kind of polymer is generally called a hydrolyzable polymer, and the antifouling coating formed from this polymer can always expose the active coating surface and maintain a stable sustained release effect of toxic substances over a long period of time. can. Also,
When such a hydrolyzable polymer contains a non-polymeric antifouling agent as another antifouling component, the antifouling effect of the above-mentioned free triorganotin compound can be supplemented, and the film can be dissolved. As a result, the amount of the antifouling component eluted is always almost uniform, and a stable antifouling effect can be maintained.

[Problem that the invention seeks to solve]

However, in conventional hydrolyzable polymers such as those mentioned above, the hydrolyzability of the coating is determined by the amount of triorganotin ester contained in the polymer, and unless this content is quite high, for example, triorganotin-containing monomers are present in the monomer composition. If the content of the polymer was not 50% by weight or more, it did not have hydrolyzability, had no sustained release effect, and had extremely poor antifouling properties. However, polymers using such a large amount of triorganotin-containing monomers are expensive because the triorganotin compound is very expensive. Further, from the viewpoint of environmental hygiene, it is preferable that the triorganotin-containing monomer be as small as possible.

Therefore, in order to impart hydrolyzability to the film without being greatly influenced by the amount of triorganotin ester, free carboxyl groups and hydroxyl groups were introduced into the above polymer, but these hydrophilic groups There is a problem in that it reacts with other pendant tin esters in the polymer or reacts with other antifouling components, causing a crosslinking reaction in the container and gelling, making it unusable. In addition, there have been attempts to improve the hydrolyzability of the polymer by partially using relatively hydrophilic monomers such as methyl acrylate and ethyl acrylate as monomers when obtaining the above polymer, but none of them have been satisfactory. I don't see it.

On the other hand, in the case of flexible underwater objects that have been treated with a hydrolyzable polymer for antifouling, although the polymer that makes up the film gradually dissolves, the film becomes hard over time after being placed in water, making the objects more flexible. It has the disadvantage of gradually losing its elasticity and causing what is called "stiffness." In particular, it is necessary to repeatedly treat the materials put into the water to maintain their antifouling performance, and as a result, the polymer film gradually becomes laminated, so the above-mentioned "stiffness" cannot be avoided. .

[Means for solving problems]

As a result of intensive studies in order to solve the above problems, the inventor has developed an antifouling polymer using a hydrolyzable copolymer obtained by copolymerizing a specific hydrophilic monomer with the triorganotin-containing monomer. If the flexible underwater charge is treated with a treatment agent, it is possible to form a treatment film with a high antifouling effect that exhibits good hydrolyzability even if the amount of triorganotin ester in the polymer is reduced; The present invention was made based on the knowledge that a coated substance placed in water retains its original flexibility well for a long period of time after being placed in water, and does not become "stiff" as in the past.

That is, this invention provides: a) the following formula; [wherein, R is a hydrogen atom or a methyl group, R2+R,
R, is an alkyl group having 1 to 8 carbon atoms or a phenyl group] and b) the following formula; The other is a hydrogen atom or a methyl group, R8 is an alkyl group or acyl group having 1 to 4 carbon atoms, and n is a real number of 1 to 30.] , an antifouling agent containing a polymer component in which the total weight of the above-mentioned structural units in the copolymer is at least 5% by weight, and further comprising 0 to 30% by weight of a non-polymeric antifouling agent. , relates to a method for preventing adhesion of underwater organisms, which is characterized in that the method is applied to a flexible underwater object.

[Structure and operation of the invention]

In the specific polymer component of the antifouling treatment agent of the present invention, the ester group in the structural unit a included as an essential structural unit is hydrolyzed in seawater to liberate a triorganotin compound that functions as an antifouling component. However, carboxyl groups are generated in the polymer component. Here, the above polymer component contains a structural unit S as another essential structural unit, and this has an alkylene oxide group as a hydrophilic side chain, making the coating highly hydrophilic. The above hydrolysis occurs more easily, and the solubility in seawater due to the generated carboxyl group is effectively increased.

Therefore, the ratio of the structural unit a in the polymer component is at least higher than that of the conventional polymer components, and this property allows an active coating surface to appear at all times. Therefore, good results can also be obtained in terms of antifouling properties. In other words, even if the amount of the structural unit a having an expensive trioliorganotin ester group is reduced, there is an advantage that high hydrolyzability and solubility as well as excellent antifouling properties can be obtained.

Moreover, in the above polymer component, the structural unit a
The hydrolyzability and solubility of the film can be improved by changing the ratio of the structural unit C and the structural unit S, or by adding a relatively hydrophobic structural unit C as an optional component to these structural units, or by changing the ratio. It can be changed freely, and furthermore, even if this polymer component is combined with an appropriate non-polymeric antifouling agent, the problem of gelation of the paint does not occur, so the above combination can further enhance the antifouling effect. After all, it has the characteristic that hydrolyzability, solubility, and antifouling effect can be adjusted very easily.

Furthermore, since this polymer component has an alkylene oxide group as a structural unit molecule side chain,
As a result of this molecular structure, the polymer itself is easily plasticized, and as a result, it has the characteristic of providing an antifouling film that provides excellent flexibility to the materials put into the water, and this flexibility does not deteriorate significantly over time after being put into the water. have. Common copolymerizable monomers used to impart flexibility to polymer films are extremely hydrophobic, and the use of such monomers significantly impairs the hydrophilicity of the polymer, resulting in a complete loss of hydrolyzability and solubility. I end up. On the other hand, according to the polymer component according to the present invention, the structural unit greatly helps maintain flexibility, and as mentioned above, it also gives good results in imparting hydrophilicity, so that the hydrolyzability of the film and It becomes possible to freely adjust solubility and flexibility.

In this invention, the above-mentioned polymer component that exhibits such an effect is obtained by copolymerizing, for example, the following monomer A for forming the structural unit a and the following Bjili monomer for forming the structural unit A. Alternatively, it can be obtained by copolymerizing the above-mentioned A and Boi monomers together with other unsaturated monomers (hereinafter referred to as C monomers) that can be copolymerized with them. The polymer component obtained using the above C monomer contains a structural unit C corresponding to the C monomer as well as structural units a and b.

A) R.

HC=CCOSn　Ra HRIOR3 B) HR5ORb R.

(In both formulas, R1 to R8 and n are all as described above) Examples of the above A monomer include tri-n-butyltin methacrylate, tri-n-butyltin acrylate, tricyclohexyltin methacrylate, Cyclohexyltin acrylate, triphenyltin methacrylate, triphenyltin acrylate, tripropyltin methacrylate, tripropyltin acrylate, triisopropyltin methacrylate, triisopropyltin acrylate, tri5ee-butyltin methacrylate, tri5eC-butyltin acrylate, triethyltin Methacrylate, triethyltin acrylate, diethylbutyltin methacrylate, diethylbutyltin acrylate, diethylamyltin methacrylate, diethylamyltin acrylate, cyamylmethyltin methacrylate, cyamylmethyltin acrylate, propylbutylamyltin methacrylate, propylbutylamyltin acrylate, diethylphenyltin methacrylate , diethylphenyltin acrylate,
Examples include ethyldiphenyltin methacrylate, ethyldiphenyltin acrylate, n-octyldiphenyltin methacrylate, n-octyldiphenyltin acrylate, diethyloctyltin methacrylate, and diethyloctyltin acrylate.

These A monomers are produced by reacting acrylic acid or methacrylic acid with triorganotin hydroxide or bis(triorganotin) oxide.
Alternatively, it can be obtained by reacting an alkali metal salt of these acids with triorganotin halide.

The above B monomer is preferably one in which R6 is a methyl group, ethyl group or acyl group, and specific examples thereof include 2-methoxyethyl methacrylate, 2-methoxyethyl acrylate, 2-methoxypropyl Methacrylate, 2-methoxypropyl acrylate, methoxytriethylene glycol methacrylate, methoxytriethylene glycol acrylate, methoxytetraethylene glycol methacrylate, methoxytetraethylene glycol acrylate, ethoxytripropylene glycol methacrylate, ethoxytripropylene glycol acrylate, ethoxyhexaethylene glycol methacrylate, Examples include ethoxyhexaethylene glycol acrylate, acetoxydiethylene glycol methacrylate, acetoxydiethylene glycol acrylate, acetoxy nonaethylene glycol methacrylate, acetoxy nonaethylene glycol acrylate, methoxytricosaethylene glycol methacrylate, and methoxytricosaethylene glycol acrylate. Furthermore, among these monomers, Rh in the formula
, R7 are both hydrogen atoms.

Moreover, as the above-mentioned C monomer, as shown in the following specific example, an unsaturated monomer that does not contain a carboxyl group or a hydroxyl group in the molecule is usually used. Examples of this include methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, propyl acrylate, propyl methacrylate, butyl acrylate, butyl methacrylate, isobutyl acrylate, isobutyl methacrylate, 2-ethylhexyl acrylate, cyclohexyl acrylate, cyclohexyl Acrylic compounds such as methacrylate, phenyl acrylate, acrylamide, and acrylonitrile; vinyl compounds such as vinyl chloride, vinyl butyrad, vinyl acetate, vinylidene chloride, vinyl propionate, and vinyl butyl ether; butadiene; and ethylene, styrene, and α-methylstyrene. There are vinyl hydrocarbons such as

In addition, if the C81 body contains carboxyl groups and hydroxyl groups in its molecule, these groups may react with other pendant tin esters in the polymer, or copper compounds may be used as non-polymer antifouling agents in antifouling agents. When a metal-based antifouling agent such as , tributyltin compound, or triphenyltin compound is included, the antifouling agent and the carboxyl group or hydroxyl group contained in the polymer component easily react at room temperature, resulting in crosslinking in the container. This is not preferable because it may cause a reaction and cause gelation, making it unusable.

Copolymerization of these monomers is mainly carried out by solution polymerization, but emulsion polymerization or other addition polymerization methods may also be employed. In the case of solution polymerization, solvents such as xylene, toluene, propatool, isopropanol, butanol, isobutanol, butyl acetate, ethyl acetate, and ethylene glycol monoethyl ether can be used alone or in combination as a reaction solvent. A chain transfer agent such as dodecyl mercaptan may also be used to control the degree of polymerization.

The polymer component in the antifouling treatment agent of the present invention uses the unsaturated acid for synthesizing this monomer, that is, acrylic acid or methacrylic acid, instead of the AJILii form in the above copolymerization method. After copolymerizing the acid with the B monomer or the B monomer and the C monomer, the acid residue in the resulting copolymer and triorganotin hydroxide, bis(triorganotin) oxide, or triorganotin hydroxide It can also be obtained by reacting with tin halide. That is, after performing a necessary copolymerization reaction, a triorganotin ester group may be introduced into the copolymer molecule to form the structural unit a.

The polymer component according to the present invention obtained by these methods is a copolymer consisting of the structural unit a and the structural unit (hereinafter referred to as a two-component copolymer), or a copolymer consisting of the structural unit a and the structural unit C (hereinafter referred to as a ternary copolymer).

In both of these valve polymers, the total weight of the structural units in the copolymer must be at least 5% by weight, and particularly preferably 10% by weight or more. When the amount is less than 5% by weight, it becomes difficult to adjust the hydrolyzability and flexibility as the object of this invention. Moreover, each structural unit a, b.

As for the proportion of C, the total weight of structural unit a is in the range of 0.1 to 45% by weight, the total weight of structural unit A is in the range of 5 to 99.9% by weight, and the total weight of structural unit C is in the range of 5 to 99.9% by weight. The total weight is preferably in the range of 0 to 80% by weight.

Among these, in the case of a two-component copolymer, it is desirable that the total weight of the structural unit a is 0.1 to 45% by weight, and the total weight of the structural unit I is 99.9 to 55% by weight. Here, if even a small amount of structural unit a is not included, satisfactory hydrolyzability will not be imparted to the film, and conversely, if it is too large, the expensive triorganotin compound will be wasted, which is economically undesirable. Furthermore, the amount of triorganotin compounds liberated by hydrolysis increases, which is unfavorable from an environmental health perspective.

In addition, in the case of a ternary copolymer, the total weight of structural unit a is 0.1 to 45% by weight, and the total weight of structural unit S and structural unit C is 99.9 to 55% by weight. Of which, the total weight of structural unit C is 5 to 90% by weight, and the total weight of structural unit C is 5% by weight.
It is desirable that the amount is in the range of 80% by weight. The same applies to the structural unit a, and if the content of the structural unit is less than 5% by weight, it becomes difficult to adjust the hydrolyzability and flexibility as described above. Constituent unit C has the function of adjusting the physical properties of the film and preventing excessive wear of the film, but if its proportion is too large, the hydrophilicity of the copolymer decreases, and this decrease in hydrophilicity causes Trio Jl / Hydrolysis of the tin ester group is difficult to occur (there is a risk that the hydrolyzability of the coating may be impaired).

It goes without saying that in order to set the proportions of structural units a, b, and c as above, A, in the copolymerization reaction,
The amounts of B and C monomers to be used may be determined in proportions according to each of the above units. Also, A! When using the unsaturated acid without a triorganotin ester group instead of the li form,
The copolymerization ratio of this unsaturated acid and the B and C monomers may be set in accordance with each of the above units.

The molecular weight of the polymer component according to the present invention configured in this way is such that the average molecular weight (weight average) is 3,000 to 3,000.
It is preferably about 200.00Q, more preferably in the range of 5.000 to 100,000.

The polymer component used in this invention has excellent antifouling properties by itself, and therefore does not necessarily require any other antifouling agent. Further, as the gist of the present invention, using other antifouling agents may be economically disadvantageous in some cases and cannot be said to be preferable in terms of environmental hygiene. However, other non-polymeric antifouling agents may be used if necessary.

As such a non-polymeric antifouling agent, it is preferable to use one that dissolves in the polymer component or solvent as much as possible.
Specific examples of such antifouling agents, which preferably do not impair the flexibility of the flexible underwater charge after coating drying, include copper oleate, copper naphthenate, tributyltin chloride, triphenyltin. Common antifouling agents include fluoride, tributyltin oxide, triphenyltin hydroxide, triphenyltin oxide, triphenyltin dimethyldithiocarbamate, triazine compounds, and organic sulfur compounds.

The blending amount of these non-polymer antifouling agents is 0 to 0 in the antifouling treatment agent.
The amount may be appropriately determined within the range of 30% by weight depending on the antifouling property of the polymer component. For example, when the content of the structural unit a of the polymer component is very small, such as less than 10% by weight, 1 to 30% by weight, preferably 1 to 10% by weight of the antifouling treatment agent may be necessary to supplement the antifouling effect. Can be used in weight%.

Of course, even if the content of the structural unit a is as high as 10% by weight or more, it can be used within the above range if necessary.

The antifouling treatment agent of the present invention contains the above-mentioned polymer component as a main component, and contains the above-mentioned non-polymer antifouling agent in an amount of 0 to 30% by weight depending on the properties of the polymer component. However, in addition to these components, dyes are usually used for coloring, and various additives and solvents can be included.

Examples of dyes include azo, anthraquinone, indigo, triphenylmethane, pyrazolone, stilbene, diphenylmethane, xanthine, alizarin, acridine, quinoneimine, thiazole, methine, sulfur dyes, and nitro dyes. Dyes, nitroso dyes, etc. Incidentally, a pigment may be used, but if it is not dissolved in the antifouling treatment agent, it generally does not have a good effect on the flexibility of the coating, so even if it is used, it is desirable to use it in a small amount.

In addition, various additives include plasticizers such as dioctyl phthalate, diphenyl phthalate, tributyl phosphate, tricresyl phosphate, and chlorinated paraffin, as well as paint additives such as thickeners, dispersants, wetting agents, and anti-sagging agents. Can be used. If these various additives are used in too large a quantity, they may adversely affect the hydrolyzability and solubility and impair the antifouling effect, so it is better to use as little as possible. Further, as the solvent, the same solvents as those used in solution polymerization to obtain the above-mentioned polymer components can be used.

The antifouling treatment agent used in the present invention is prepared by charging the above-mentioned components into a dispersing machine, stirring and mixing them, and then removing aggregates or foreign matter by filtration. At this time, if the dye used as the coloring agent is soluble in the polymer and solvent, first dissolve the dye in the solvent using a disilver, etc., add the polymer solution and other ingredients to this, and mix and stir thoroughly. Just do it. On the other hand, when using a small amount of non-polymer antifouling agents or pigments that are insoluble in polymers or solvents, add these ingredients to some of the polymer solution using an attritor or the like (to a particle size of 30 μm or less).
After dispersion, the remaining polymer solution and other ingredients such as solvents and additives are preferably added.

In this invention, the above-mentioned antifouling treatment agent is applied to a flexible underwater object to form an antifouling coating of a desired thickness on the surface thereof. The above-mentioned flexible underwater objects are objects made of various fibers such as flexible fishing nets, marine pollution prevention membranes, synthetic resin fibers, organic fibers such as natural fibers, and inorganic fibers, which are put into the water and ready for use. Anything provided is included.

The above-mentioned underwater input materials treated in this way have a treated film that exhibits good hydrolyzability and antifouling properties, which prevents aquatic organisms from adhering to the surface of the input materials, and also makes the treated film flexible and stable over time. Because almost no physical deterioration is observed, the flexibility of the fiber object is not impaired, especially when the coating becomes laminated due to repeated processing.In other words, the original flexibility is maintained without the "stiffness" that occurs in the past. Maintains well over a long period of time.

〔Effect of the invention〕

As described above, in this invention, by using a hydrolyzable polymer containing a specific structural unit as the antifouling agent, the triorganotin ester content has at least good hydrolyzability. It is possible to form an antifouling film that easily dissolves in water, and this film has good results in maintaining flexibility due to the above-mentioned structural units. According to the method of the present invention, which coats the water, it is possible to obtain a great antifouling effect that can prevent the attachment of aquatic organisms, and
It has the advantage that it does not suffer from the "stiffness" that occurs in the conventional treatment film, and therefore is easier to handle, is less harmful to environmental hygiene, and can significantly reduce treatment costs.

〔Example〕

Next, examples of the present invention will be described in more detail. In addition, the following Examples 1 to 10 and Comparative Examples 1 to 3
The copolymer solutions A-G and H,I used in the above were obtained by the following production examples A-G and H,I.

Production example A: Put 100g of toluene in a flask with a stirrer and heat to 90°C.
It was heated to triphenyltin acrylate) 20g, methoxytetraethylene glycol methacrylate 100g
, butyl acrylate 40g/methyl methacrylate 4
A mixture of 0g and 4g of benzoyl peroxide,
The mixture was added dropwise to the above toluene over 2 hours while stirring.

After that, it was kept at 90°C for 3 hours, cooled, and toluene 9
6 g was added to obtain copolymer solution A.

The solid content concentration of this solution A is 50% by weight, and the viscosity (20°C)
is 5.0 voids, and the weight average molecular weight of the copolymer is 50.
It was 000.

Production Example B 84 g of xylene was placed in a flask equipped with a stirrer and heated to 90°C. 40 g of tripropyltin methacrylate, 100 g of methoxydiethylene glycol acrylate),
Butyl acrylate 30g, ethyl acrylate 30g
A mixed solution of 4 g of azobisisobutyronitrile and azobisisobutyronitrile was added dropwise to the above xylene over 2 hours with stirring. After that, it was held at 90°C for 30 minutes, then heated to 110°C and held at this temperature for 2 hours. 112g xylene after cooling
was added to obtain copolymer solution B.

The solid content concentration of this solution B is 50% by weight, and the viscosity (20°C)
is 9. O voids, the weight average molecular weight of the copolymer is 68
,000.

Production example C: Put 120g of xylene in a flask with a stirrer and
Warmed to ℃. tributyltin methacrylate 80g, methoxydiethylene glycol methacrylate 50g, methyl methacrylate 30g, butyl methacrylate 40g
A mixed solution of 4 g of g and t-butylperoxybenzony) was added dropwise to the above xylene over 2.5 hours with stirring, and then maintained at 125° C. for 3 hours. After cooling, 76 g of toluene was added to obtain copolymer solution C.

The solid content concentration of this solution C is 50% by weight, and the viscosity (20°C)
is 2.5 voids, and the weight average molecular weight of the copolymer is 30,
It was 000.

Example of production: 70 g of xylene and 30 g of butanol in a flask with a stirrer.
g and heated to 90°C. A mixed solution of 10 g of tributyltin methacrylate, 140 g of ethoxytripropylene glycol methacrylate, 50 g of methyl methacrylate, and 4 g of benzoyl peroxide was added dropwise to the above mixed solvent of xylene and butanol over 2 hours with stirring, and then for 3 hours. It was maintained at 90°C. After cooling, 96 g of xylene was added to obtain a copolymer solution.

The solid concentration of this solution is 50% by weight, and the viscosity (20°C)
is 4.9 poise, and the weight average molecular weight of the copolymer is 44,
It was 000.

Production example E: 80 g of xylene and 80 g of butanol in a flask with a stirrer
g and heated to 100°C. 14g methacrylic acid
, methoxynonaethylene glyco-minor methacrylate 60
A mixed solution of 40 g of methyl methacrylate, 40 g of butyl acrylate, and 4 g of benzoyl peroxide was added dropwise to the above mixed solvent of xylene and butanol over 2 hours with stirring, and then held at 100° C. for 3 hours. The mixture was cooled to 60° C., 48 g of bis(tributyltin) oxide and 36 g of xylene were added, and the mixture was maintained at 60° C. for 1 hour. Thereafter, the temperature was raised, and the reaction product water that azeotropically distilled under reduced pressure and reflux conditions was removed by decantation. When it was confirmed that 0.35 g of produced water had been distilled out, which was the amount of continuous production, heating was stopped and copolymer solution E was obtained by cooling.

This solution E has a solid content concentration of 50% by weight and a viscosity (20°C
) is 2.8 poise, and the weight average molecular weight of the copolymer is 36
,000. In addition, the obtained copolymer was found to have -COO3n (
It was confirmed that an absorption attributed to C=0 of Bu) 3 groups (Bu: = butyl group) was generated, and based on this absorption, the above tributyltin ester group was quantified, and the theoretical amount of the above was determined. base was generated.

Production Example F Put 90g of butyl acetate into a flask with a stirrer and
It was warmed to ℃ and brought to reflux. A mixture of 60 g of triphenyltin methacrylate, 140 g of methoxyethyl methacrylate, and 8 g of t-butylperoxy-2-ethyl hexaate was added to the above butyl acetate with stirring for 2.5 g.
The mixture was added dropwise over a period of time, and then maintained at 126° C. for 2.5 hours while refluxing. After cooling, 106 g of butyl acetate was added to obtain a copolymer solution F.

The solid content concentration of this solution F is 50% by weight, and the viscosity (20°C)
is 2.0 voids, and the weight average molecular weight of the copolymer is 26.
It was 000.

Production example G: Put 100g of toluene into a flask with a stirrer and heat to 90°C.
It was heated to Diethyl amyltin methacrylate 30g1
Acetoxydiethylene glycol methacrylate 120
A mixture of 50 g of methyl methacrylate, 20 g of ethyl acrylate, and 4 g of benzoyl peroxide was added dropwise to the above toluene over 2 hours with stirring. After sowing, hold at 90℃ for 3 hours, and after cooling, add 96g of toluene.
was added to obtain copolymer solution G.

The solid content concentration of this solution G is 50% by weight, and the viscosity (20°C)
is 3.0 voids, and the weight average molecular weight of the copolymer is 39,
It was 000.

Production example H: Put 100g of xylene in a flask with a stirrer and heat to 90°C.
It was heated to 140g of tripropyltin methacrylate,
20g ethyl acrylate, 40g methyl methacrylate
A mixture of 3 g and 4 g of t-butyl peroxy 2-ethyl hexaate was added to the above xylene with stirring.
It dripped in time. Thereafter, the temperature was maintained at 90° C. for 2 hours, and after cooling, 96 g of xylene was added to obtain a copolymer solution H.

This solution I (solid content concentration is 50% by weight, viscosity (20℃
) is 5.2 poise, and the weight average molecular weight of the copolymer is 52
．． It was OOO.

Production example■ Put 100g of toluene in a flask with a stirrer and heat to 90℃.
It was heated to A mixture of 60 g of tributyltin methacrylate, 0 g of ethyl acrylate, 80 g of butyl acrylate, and 4 g of benzoyl peroxide was added dropwise to the above toluene over 2 hours with stirring. After that 9
The mixture was kept at 0° C. for 3 hours, and after cooling, 96 g of toluene was added to obtain a copolymer solution I.

The solid content concentration of this solution I is 50% by weight, and the viscosity (20°C)
has a void of 3.1, and the weight average molecular weight of the copolymer is 38.
It was 000.

Examples 1 to 10 Using copolymer solutions A to G, ten types of antifouling agents according to the present invention were prepared according to the formulations shown in Table 1 below. The numbers in Table 1 represent weight %.

Next, this antifouling treatment agent was applied to a marine pollution prevention membrane made of polyester synthetic fiber (trade name 5PS-300, manufactured by Taiyo Kogyo Co., Ltd.) cut into a size of 70 cm x 50 cm, and a polyester film with a size of 70 cI11 x 50 CII+. Each coating was applied to ethylene fiber aquaculture fishing nets using the dipping method.
After sufficient drying, an antifouling coating was formed on the membrane and net.

Comparative Examples 1 to 3 Using copolymer solutions H and I, three types of antifouling agents for comparison were applied in the same manner as Examples 1 to 10 with the formulation shown in Table 1 below. Using this treatment agent, antifouling coatings were formed on marine pollution prevention membranes and aquaculture fishing nets in the same manner as in Examples 1 to 10.

The marine pollution prevention membrane and aquaculture fishing net formed with the antifouling coating by the methods of Examples 1 to 10 and Comparative Examples 1 to 3 above were evaluated for the antifouling effect and flexibility over time by the following method. We investigated changes in

■) Antifouling effect test A marine pollution prevention film with an antifouling coating and a fishing net for aquaculture were attached to an iron frame for immersion, and these were submerged 1.5 m below the water surface in Yura Bay, Sumoto City, Hyogo Prefecture. immersed in.

After a predetermined period of time, the adhesion status of marine organisms was observed with the naked eye and evaluated as follows. The results were as shown in Table 2 below.

◎... Total adhesion of marine life (None O... Less than 10% of the total area is covered by marine life △... More than 10% and less than 20% of the total area is covered by marine life ×・・・Marine organisms are attached to 20% or more and less than 50% of the total area × × ・・Marine organisms are attached to 50% or more of the total area ■) Same as in the case of flexibility test and antifouling effect test The material was immersed in seawater, and changes in flexibility after immersion for a predetermined period of time were examined by touch and evaluated as follows.

0...The flexibility is almost unchanged compared to the untreated one.Δ...The flexibility is slightly lower than the untreated one.×...The flexibility is less than the untreated one. As is clear from the above test results, it is difficult for marine pollution prevention membranes and aquaculture fishing nets that have been antifouled using conventional antifouling agents to maintain their flexibility. Moreover, when the amount of triorganotin ester in the polymer component is small (Comparative Examples 2 and 3), the antifouling effect deteriorates, whereas the antifouling agent of this invention can maintain flexibility and It can be seen that the antifouling effect is large regardless of the amount of triorganotin ester in the polymer component.

Claims (3)

[Claims] (1)a) The following formula; ▲There are mathematical formulas, chemical formulas, tables, etc.▼ [In the formula, R_1 is a hydrogen atom or a methyl group, R_2, R
_3, R_4 are alkyl groups or phenyl groups having 1 to 8 carbon atoms] and b) the following formula; ▲ Numerical formulas, chemical formulas, tables, etc. , R_6R_
7 is a hydrogen atom and the other is a hydrogen atom or a methyl group, R_8 is an alkyl group or acyl group having 1 to 4 carbon atoms, n is a real number from 1 to 30] A copolymer containing as a structural unit, the above-mentioned structural unit b occupying in this copolymer
An antifouling treatment agent containing a polymer component having a total weight of at least 5% by weight and further comprising 0 to 30% by weight of a non-polymeric antifouling agent is applied to the flexible fibrous underwater input. A method for preventing adhesion of aquatic organisms, characterized by: (2) A copolymer in which the polymer component is composed of structural unit a and structural unit b, in which the total weight of structural unit a in the copolymer is 0.1 to 45% by weight, and the total weight of structural unit b is The method for preventing the adhesion of aquatic organisms according to claim (1), which uses an antifouling treatment agent having a weight of 99.9 to 55% by weight. (3) A copolymer in which the polymer component is composed of structural unit a, structural unit b, and structural unit c other than these, and the total weight of structural unit a in this copolymer is 0.1 to 45% by weight. %, the total weight of structural unit b and structural unit c is 99.
9 to 55% by weight (of which the total weight of structural unit b is 5 to 9%)
0% by weight, and the total weight of the structural unit c is in the range of 5 to 80% by weight).