JPH0121805B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to an antifouling agent containing as an active ingredient a tri-organotin-containing copolymer having an N-coordinated tri-organotin-containing repeating unit in the polymer main chain. The bottom of a ship; fishing nets such as aquaculture nets and fixed nets; or general underwater structures, etc.
Contaminant organisms such as brown algae and other seaweed, barnacles, celluloids, oysters, sea squirts, and bryozoans adhere to the surface, causing various types of damage. In other words, when these polluting organisms adhere to the bottom of a ship, they increase the frictional resistance between the ship's hull and the seawater, reducing ship speed and increasing fuel consumption. In addition, when contaminated organisms adhere to fishing nets, they clog the nets, obstructing the flow of seawater, causing poor growth of farmed fish, and reducing the amount of fish caught.In some cases, fishing nets with increased resistance due to attached organisms may be washed away by ocean currents This will result in a situation where the In order to suppress such damage, various antifouling agents and paints are applied to the sea or to the surfaces of substrates exposed to water.Today, in particular, antifouling paints are applied to the bottoms of large tankers to prevent long-term contamination. Preventing the adhesion of organisms is considered important from the viewpoint of economic efficiency and resource conservation. To prevent the attachment of contaminant organisms, tri-organotin compounds such as tributyltin compounds (oxides, chlorides, fluorides) and triphenyltin compounds (hydroxides, chlorides,
Fluoride) has been used, but since these are highly toxic antifouling agents that are dispersed or dissolved, they cause problems such as rash during paint manufacturing and application, and their antifouling performance is poor at the initial stage. Since it elutes into seawater and it is difficult to control the elution, long-term antifouling cannot be obtained. So now we have improved this and put it in the molecule.
A triorganotin-containing polymer type antifouling agent having COOSnR ₃ (R is an alkyl group or a phenyl group) has been used, but it has the following drawbacks. That is,
First, these polymer-type antifouling agents thicken and gel during storage. For example, triphenyltin-containing polymers are particularly prone to this phenomenon, and in severe cases gelation occurs during the polymerization process during production, making it difficult to obtain stable polymers. In addition, tributyltin-containing polymers and copper compounds, such as cuprous oxide, are used in combination with ship bottom paints for long-term antifouling purposes, but in this case, the thickening and gelation of the paint during storage is further promoted, making it unusable. occurs. In order to prevent thickening and gelation during storage, methods have been adopted such as adding a stabilizer and separating the polymer component and copper compound component and mixing them immediately before forming the paint, but these methods are essential It's not a solution. Yet another drawback is the difficulty in producing triphenyltin-containing polymers that are particularly effective against algae. As a result of conducting research from a new perspective, the present inventors found that if a completely new triorganotin-containing copolymer containing an N-coordinated triorganotin compound in the molecule was used as an antifouling component, the above drawbacks would be eliminated. Furthermore, they have discovered that an antifouling agent that exhibits various excellent effects can be obtained, and have arrived at the present invention. That is, in the present invention, (a) the following general formulas [a], [b] and [c] are present in the main chain of the polymer.

【formula】

【formula】

[Formula] [In the formula, R is the same or different alkyl group, cycloalkyl group, aryl group, or aralkyl group having 1 to 8 carbon atoms, and X is a group -NCS, a group-
NCO, the group -N ₃ or the group -CN, R ¹ and R ² are independently selected from hydrogen atoms, methyl groups, ethyl groups and halogen atoms, p is an integer from 1 to 4, Y
is an alkylene group, phenylene group, or group having 1 to 12 carbon atoms.

[Formula] Group

[Formula] Group

[Formula] Group -O-Z- or group -S-Z- (wherein Z is an alkylene group or group having 2 to 12 carbon atoms

[Formula] (m: an integer of 1 to 8), A and B may or may not be bonded to each other, (i) When A and B are not bonded to each other; A and B are hydrogen atoms , alkyl groups having 1 to 18 carbon atoms, cycloalkyl groups, aryl groups, aralkyl groups, hydroxyalkyl groups or alkoxyalkyl groups having 2 to 12 carbon atoms, and groups.

[Formula] (wherein R ³ represents an alkyl group or aryl group having 1 to 18 carbon atoms), (ii) when A and B are bonded to each other;
and B represent a 5- to 6-membered hetero ring formed together with the nitrogen atom of formula [a] or [b] or a condensed ring thereof;

[Formula] represents a 5- to 6-membered heterocycle or a fused ring thereof, each of which is bonded to the carbon atom to which R ¹ is bonded by a ring member other than the nitrogen atom. (b) an acrylic compound, a vinyl compound having a functional group, a vinyl hydrocarbon compound, a triorganotin salt of a polymerizable unsaturated carboxylic acid, and a polymerizable unsaturated dicarboxylic acid or anhydride thereof; This is an antifouling agent characterized by containing as an antifouling component a triorganotin-containing copolymer containing a comonomer repeating unit derived from at least one comonomer selected from the group consisting of: In the above formula [a] or [b], A and B
are bonded to each other, i.e., the groups

[Formula] includes, for example, the following groups;

【formula】

【formula】

【formula】

【formula】

【formula】

【formula】

【formula】

【formula】

【formula】

【formula】

【formula】

[Formula] (where R' is a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, an aryl group, or an aralkyl group,
R'' represents an alkylene group having 2 to 3 carbon atoms, a cyclohexylene group, or a phenylene group, and q represents an integer of 1 to 5.

As [formula] For example, the following groups;

【formula】

【formula】 【formula】

【formula】

Examples include [Formula]. N represented by the above general formula [a], [b] or [c] in the polymer main chain used in the present invention
A tri-organotin-containing copolymer containing a coordinated tri-organotin-containing repeating unit (hereinafter referred to as the tri-organotin-containing copolymer of the present invention) is usually obtained as follows.
That is, the following formula [a], [b] or [c]

【formula】 【formula】

[Formula] (In the formula, R ¹ , R ² , P, Y, A, B and groups

The general formula R 3 is a copolymer obtained by copolymerizing an unsaturated compound having a nitrogen atom in the molecule represented by [Formula] (has the same meaning as above) and another polymerizable unsaturated compound ( _comonomer ). It is obtained by directly reacting with a triorganotin compound represented by SnX (wherein R and X have the same meanings as above). The unsaturated compound having a nitrogen atom in the molecule represented by the above formula [a] used to obtain the triorganotin-containing copolymer of the present invention is N-
Examples include vinylamine, N-vinylamide, N-vinylimide and the like. Examples of N-vinylamine include N-vinylethylamine, N-vinyl n-butylamine, N-vinyl n-dodecylamine, N-vinylcyclohexylamine, N-vinyldimethylamine, N-vinyldiethylamine,
N-vinylmethylphenylamine, N-vinylphenylamine, N-vinylphenyl β-naphthylamine, N-vinyl p-tolyl α-naphthylamine, N-vinylpyrrole, N-vinylindole, N-vinyl α-methylindole, N-vinylcarbazole, N-vinyl-1,2,3,4-
Tetrahydrocarbazole, N-vinylphenothiazine, N-vinylnaphthophenothiazine, N-
Vinylmorpholine, N-vinylpiperidine, N-
Examples of the N-vinylamide include vinylphenoxazine, N-vinylpyrrolidine, etc.
Vinyl acetamide, N-vinyl N-methylacetamide, N-vinylacetanilide, N-vinyl N-methylbenzamide, N-vinylpyrrolidone, N-vinyl 3-methylpyrrolidone, N-vinyl 5-methylpyrrolidone, N-vinyl 5 - Phenylpyrrolidone, N-vinyl 3-benzylpyrrolidone, etc.;
-Vinyl succinimide, N-vinylglutarimide, N-vinyl diglycolimide, N-
Examples include vinyl phthalimide and N-vinyltetrahydrophthalimide. Examples of the unsaturated compound having a nitrogen atom in the molecule represented by the above formula [b] include aminoolefin, aminostyrene, olefinamide, aminoacrylate, aminomethacrylate, aminovinyl ether, aminovinyl sulfide, and the like. Examples of aminoolefins include allylamine, allylmethylamine, allyldimethylamine, allylethylamine, allyldiethylamine, methallylamine, methallylmethylamine, methallylethylamine, methallylmethylethylamine, methallylphenylethylamine, 1-
ethylamino-3-butene, 1-dimethylamino-4-pentene, 1-diethylamino-4-pentene, 12-dodecenylamine, allyldibenzylamine, allylethylphenylamine, N-allylmorpholine, N-methallylmorpholine, N-allylpyrrole, N-allylindole, N-methallylpiperidine, N-methallylpyrrolidine, N-
Methallylpyrrolidone, N-allylcarbazole,
Examples of aminostyrene include N-allylaniline, N-allylN-methylaniline, etc.
-Aminostyrene, m-aminostyrene, p-aminostyrene, p-dimethylaminostyrene, p
-diethylaminostyrene, o-vinylbenzylamine, p-N,N-dimethylaminomethylstyrene, N-(o-vinylbenzyl)pyrrolidine,
N-(p-vinylbenzyl)morpholine, N-
(o-vinylbenzyl)piperidine, N-(o-
Examples of olefinamides include acrylamide, methacrylamide, N-methylacrylamide, N,N-dimethylacrylamide, N-ethylacrylamide,
N,N-diethylacrylamide, N,N-dimethylmethacrylamide, N,N-diethylmethacrylamide, N-ethyl N-phenylacrylamide, N-methylolacrylamide, N-octylacrylamide, N-methoxymethylacrylamide, N- 2,2-dimethylpropoxymethylacrylamide, N,N-diethanolacrylamide, N,N-diethanolmethacrylamide, diacetone acrylamide, N-methylacrylanilide, acryloylmorpholine, methacryloylpiperidine, acryloylpyrrolidine, methacryloylmorpholine, acryloyl indole, acryloyl Examples of the aminoacrylate or aminomethacrylate include carbazole, methacryloyltetrahydrocarbazole, N-methylaminoethyl acrylate, N-ethylaminoethyl acrylate, N,
N-dimethylaminoethyl acrylate, N,N
- Diethylaminoethyl acrylate, N-methylaminoethyl methacrylate, N,N-dimethylaminoethyl methacrylate, N-ethylaminoethyl methacrylate, N,N-diethylaminoethyl methacrylate, N,N-dimethylaminopropyl methacrylate, N-t-butyl Aminoethyl acrylate, N,N-diethylaminohexyl methacrylate, N-methoxymethylaminoethyl acrylate, N-ethoxyethylaminoethyl methacrylate, N-methyl N-phenylaminoethyl methacrylate, p-N,N-
Diethylaminobenzyl methacrylate, o-
N,N-dimethylaminophenethyl methacrylate, β-morpholinoethyl methacrylate, γ-
Morpholinopropyl acrylate, β-pyrrolidylethyl methacrylate, β-carbazolylethyl acrylate, etc., and amino vinyl ethers include, for example, N,N-dimethylaminoethyl vinyl ether, N,N-diethylaminoethyl vinyl ether, 3-aminopropyl vinyl ether, 5-aminopentyl vinyl ether, 8-aminooctyl vinyl ether, 10-aminodecyl vinyl ether, 2-aminobutyl vinyl ether, N-t-butylaminoethyl vinyl ether, N-methylaminoethyl vinyl ether, N
-2-ethylhexylaminoethyl vinyl ether, (N-β-hydroxyethyl N-methyl)aminoethyl vinyl ether, N,N-dihydroxyethylaminoethyl vinyl ether, N,N-
Diphenylaminoethyl vinyl ether, β-pyrrolidylethyl vinyl ether, β-morpholinoethyl vinyl ether, β-piperidinoethyl vinyl ether, γ-morpholinopropyl vinyl ether, β-carbazolylethyl vinyl ether, etc. are aminovinyl sulfides. For example, aminoethyl vinyl sulfide, N,N-
Dimethylaminoethyl vinyl sulfide, 5-
Examples include aminopentyl vinyl sulfide, N-ethyl N-phenylaminopropyl vinyl sulfide, and N,N-diethylaminoethyl vinyl sulfide. Further, as the unsaturated compound having a nitrogen atom in the molecule represented by the above formula [c], for example, 2
- Vinylpyridine, 3-vinylpyridine, 4-vinylpyridine, 2-vinyl-4-methylpyridine, 4-vinyl-2-methylpyridine, 2-vinylpiperidine, 4-vinylpiperidine, 4-vinyl-2-methylpiperidine , 2-vinylpyrrolidine, 3-vinylpyrrolidine, 3-vinylpyrrole, 2-vinylquinoline and the like. Other polymerizable unsaturated compounds (comonomers) that can be copolymerized with the nitrogen-containing unsaturated compound represented by formula [a], [b] or [c] include acrylic compounds, vinyl compounds having functional groups, compounds, vinyl hydrocarbon compounds, triorganotin salts of polymerizable unsaturated carboxylic acids, polymerizable unsaturated dicarboxylic acids or their anhydrides, and the like. As an acrylic compound, the following formula (In the formula, R ⁴ is a hydrogen atom, a substituted or unsubstituted hydrocarbon group having 1 to 20 carbon atoms, or an aryl group, R ⁵
is a hydrogen atom, a halogen atom, or an alkyl group having 1 to 6 carbon atoms).
These compounds include, for example, acrylic or methacrylic acids such as acrylic acid, methacrylic acid, α-ethyl acrylic acid, α-chloroacrylic acid, etc.; methyl, ethyl, propyl, butyl, amyl, hexyl, octyl acrylate; , dodecyl, octadecyl, cyclopentyl, cyclohexyl, phenyl, benzyl, acrylic esters such as tetrahydrofurfuryl ester; methacrylic esters such as methyl, ethyl, butyl, hexyl, octyl, dodecyl ester of methacrylate; α- Examples include α-substituted acrylic esters such as ester of chloroacrylic acid and butyl ester of α-ethyl acrylic acid. Preferably used compounds include, for example, methyl acrylate, ethyl acrylate, n-butyl acrylate, 2-ethylhexyl acrylate, n-octyl acrylate, methyl methacrylate, ethyl methacrylate, n-butyl methacrylate, n-octyl methacrylate, n-methacrylate
- Examples include dodecyl. These compounds can be used alone or in combination of two or more. As a vinyl compound having a functional group, the following formula [In the formula, Q is a halogen atom, -CN, -OR*,
-SR*, -COR* or -OCOR* (in the formula, R* represents a substituted or unsubstituted hydrocarbon group having 1 to 20 carbon atoms), and Q' is a hydrogen atom, a halogen atom, or a carbon number 1 to 20 6 alkyl groups]. These compounds include, for example, vinyl halides such as vinyl chloride and vinylidene chloride; acrylonitriles such as acrylonitrile and methacrylonitrile; methyl vinyl ether, ethyl vinyl ether, β-chloroethyl vinyl ether, butyl vinyl ether, and octyl vinyl ether. , decyl vinyl ether, lauryl vinyl ether, phenyl vinyl ether, o-methyl phenyl vinyl ether,
Vinyl ethers such as benzyl vinyl ether, β-naphthyl vinyl ether, etc.; vinyl thioethers such as methyl vinyl sulfide, divinyl sulfide, butyl vinyl sulfide, etc.; vinyl ketones such as methyl vinyl ketone, phenyl vinyl ketone, etc.; Examples include vinyl esters such as vinyl formate, vinyl acetate, vinyl propionate, vinyl butyrate, vinyl laurate, vinyl benzoate, vinyl salicylate, etc., and preferred compounds include:
Examples include vinyl chloride, acrylonitrile, butyl vinyl ether, decyl vinyl ether, lauryl vinyl ether, and vinyl acetate. These compounds may be used alone or in combination of two or more. As a vinyl hydrocarbon compound, the following formula (In the formula, P and P' are a hydrogen atom or a hydrocarbon group having 1 to 18 carbon atoms).
These compounds include, for example, olefins such as ethylene, propylene, 1-butene, cyclohexene, α-pinene, etc.; dienes such as 1,3-butadiene; styrene, α-methylstyrene, o-methylstyrene. , m-methylstyrene, p-methylstyrene, etc., and examples of preferred compounds include styrene. In addition, the triorganotin salt of polymerizable unsaturated carboxylic acid has the following formula: (In the formula, R ⁶ is a hydrogen atom or a group - COOR ⁹ , R ⁷ is a hydrogen atom, a lower alkyl group or a group - CH ₂ COOR ¹⁰
and R ⁸ , R ⁹ , R ¹⁰ are the same or different triorganotin groups). These compounds include, for example, tripropyltin methacrylate, tributyltin methacrylate, triamyltin methacrylate, triphenyltin methacrylate, tripropyltin acrylate, tributyltin acrylate, triamyltin acrylate, triphenyltin acrylate, bis(tripropyltin)itaconate, bis(tripropyltin)itaconate, (tributyltin) itaconate, bis(tricyclohexyltin) itaconate, bis(triphenyltin) itaconate, bis(tributyltin) maleate, bis(triphenyltin) maleate, etc. Preferably used compounds include, for example, tributyltin methacrylate , triphenyltin methacrylate, tributyltin acrylate, triphenyltin acrylate, bis(tributyltin)itaconate, bis(triphenyltin)itaconate, bis(tributyltin)malate, and bis(triphenyltin)malate. These compounds may be used alone or in combination of two or more. Examples of the polymerizable unsaturated dicarboxylic acid or its anhydride include maleic acid, itaconic acid, maleic anhydride, and itaconic anhydride, with itaconic acid and maleic anhydride being preferred. R ₃ SnX to be applied to the copolymer of the illustrated nitrogen-containing unsaturated compound and other polymerizable unsaturated compound
The triorganotin compound represented by (R and Thiocyanate, tripropyltin isocyanate, tributyltin isothiocyanate, tributyltin isocyanate, tributyltin azide, tributyltin cyanide, triamyltin isothiocyanate, triamyltin isocyanate, triphenyltin isothiocyanate, triphenyltin isocyanate, triphenyltin azide, triphenyltin cyanide, Examples include tricyclohexyltin isothiocyanate, tricyclohexyltin cyanide, dibutylphenyltin isothiocyanate, diphenylethyltin isocyanate, tributyltin isothiocyanate, tributyltin isocyanate, tributyltin azide, tributyltin cyanide, triphenyltin isothiocyanate, triphenyl tin isocyanate, Triphenyltin azide and triphenyltin cyanide are preferred. The copolymerization of the nitrogen-containing unsaturated compound represented by the above formula [a], [b] or [c] with another polymerizable unsaturated compound (comonomer) is carried out in the presence of a suitable polymerization catalyst, preferably a radical catalyst. Although the polymerization can be carried out by bulk polymerization, solution polymerization, emulsion polymerization, or suspension polymerization, solution polymerization is preferable in view of carrying out the subsequent reaction of introducing the triorganotin pseudohalide. Since the copolymer thus obtained contains a nitrogen atom in its side chain, this nitrogen atom is reacted with triorganotin pseudohalide. In this reaction, a nitrogen atom in the nitrogen-containing copolymer and a tin atom in the triorganotin pseudohalide form a ligand bond using the nitrogen atom as a ligand.
The compounds thus produced are generally referred to as adduct compounds, double or complex compounds, or broadly coordination compounds. The solution polymerization and triorganotin pseudohalide introduction reaction described above are usually carried out using organic solvents such as benzene,
Aromatic hydrocarbons such as toluene and xylene, ketones such as methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone, tetrahydrofuran,
Ethers such as dibutyl ether and diglyme,
This can be carried out in the presence of a solvent or mixed solvent such as alcohol such as isopropanol, butanol, and ethyl cellosolve. The quantitative proportion of the triorganotin pseudohalide reacted with the nitrogen-containing copolymer is equivalent to or less than the amount of nitrogen atoms contained in the copolymer, and depends on its type or antifouling purpose. arbitrarily selected. The formation of the coordination compound by the reaction between the nitrogen atoms in the nitrogen-containing copolymer and the triorganotin pseudohalide has been confirmed by various instrumental analyses, such as infrared absorption spectra of Sn-C and Sn-Cl. Coordination bonds can be confirmed by shifts in absorption bands and by analytical techniques such as Sn ¹¹⁹ nuclear magnetic resonance spectroscopy and X-ray diffraction. The thus obtained solution of the triorganotin-containing copolymer of the present invention in an organic solvent is a colorless, pale yellow or yellowish brown viscous liquid. Further, the triorganotin-containing copolymer of the present invention has a molecular weight of 5,000 to 500,000. These copolymer solutions can be obtained as organic solvent solutions containing usually 10 to 80% by weight, preferably 40 to 60% by weight, of the triorganotin-containing copolymer. The copolymer solution was applied to wooden boards, metal plates, synthetic fiber ropes, nets, etc., and when dried, a triorganotin-containing copolymer coating with good elasticity and adhesion was formed. The triorganotin-containing copolymer of the present invention can also be produced by the following method. That is, formulas [a], [b] or [c]

【formula】 【formula】

[Formula] [In the formula, R, R ¹ , R ² , p, Y, A, B, X and the group

The triorganotin-containing copolymer of the present invention can be obtained by copolymerizing the unsaturated compound represented by [Formula] with the same meaning as above and another polymerizable unsaturated compound (comonomer). The starting material for producing the unsaturated compound represented by formula [a], [b] or [c] is the formula [a], [b] or [c].
The nitrogen-containing unsaturated compounds represented by a], [b] or [c] and the above-mentioned tri-organotin pisodohalides, as well as other polymerizable unsaturated compounds (comonomers) exemplified in the above-mentioned production method, can be used. used for each. The polymerization method is carried out in a similar manner. The triorganotin-containing copolymer of the present invention obtained by this method has the above formula [a], [b] or [
It is difficult to incorporate a high degree of N-coordinated triorganotin-containing structural units represented by Preferably, it is obtained by a method involving the action of tin pseudohalide. The formula in the triorganotin-containing copolymer of the present invention [
N coordination represented by a], [b] or [c] -
The proportion of the triorganotin-containing structural unit is not particularly limited and is determined by the antifouling coating film forming ability and the antifouling performance. 10 to 80% by weight and repeating units of comonomers of other polymerizable unsaturated compounds can be contained in proportions of 90 to 20% by weight. The antifouling agent of the present invention is produced using the triorganotin-containing copolymer of the present invention in various forms depending on the purpose of antifouling. That is, the triorganotin-containing copolymer of the present invention is dissolved in the solvent used in the solution polymerization described above, for example, an organic solvent or mixed solvent such as hydrocarbons, ketones, esters, alcohols, ethers, etc.
Alternatively, the triorganotin-containing copolymer solution obtained by each of the above-mentioned production methods can be used as it is or after being diluted as an antifouling agent. It is also used in fishing net antifouling agents and boat bottom antifouling paints by mixing dyes, pigments, carriers, and if necessary, copper compounds such as cuprous oxide and copper rhodan, organic tin compounds, paint conditioners, toxic elution control agents, and diluents. be done. The proportion of the triorganotin-containing copolymer of the present invention in the thus obtained antifouling agent is not limited, but may be 5 to 70% by weight based on the total solid content. In the present invention, since the tri-organotin-containing copolymer itself has both an antifouling component and a film forming agent (varnish), other color vehicles such as oil-based varnish, vinyl resin varnish, acrylic resin varnish, etc. Although not necessary, these may be used depending on the antifouling purpose. As described above, the antifouling agent of the present invention can be embodied in various forms, but it is preferable that the solid content of the antifouling agent contains 0.5% by weight or more of triorganotin compound (R ₃ SnX) units. The antifouling agent of the present invention has the following features. That is, firstly, the antifouling agent of the present invention has long-term storage stability, and changes over time such as thickening and gelation do not substantially occur. In this case, the presence of a copper compound (for example, cuprous oxide) in the antifouling agent does not make any difference. Such an effect is not observed in conventional triorganotin-containing polymer type antifouling agents having -COOSnR ₃ in the molecule.
Second, in the present invention, the tri-organotin compound is introduced into the polymer through coordination bonds, so compared to the conventional tri-organotin compound monomer type antifouling agent, the physiological effect on the human body is extremely high. There is no need to worry about harm to workers. Thirdly, when the antifouling agent of the present invention is applied to a substrate to be antifouled, it has strong adhesive properties and forms a tough coating film, and has excellent antifouling performance and physical and chemical resistance. A protective coating film having the following properties is obtained. Fourthly, since the antifouling agent of the present invention is a copolymer containing hydrophilic nitrogen-containing compound residues, it has the performance as a soluble matrix, and when immersed in seawater, the coating surface becomes It is constantly updated and can maintain long-term stain resistance. Therefore, depending on the antifouling purpose, by varying the ratio of the N-coordinated triorganotin-containing structural unit and the comonomer unit in the polymer of the present invention, it is possible to change the structure from an insoluble matrix type to a soluble matrix type. A wide range of mold antifouling adjustments are possible. Furthermore, the present invention has the great advantage of being able to produce an antifouling agent containing a triphenyltin-containing copolymer that is effective against algae. The antifouling agent of the present invention is particularly advantageously used to protect objects that come into contact with seawater, such as the bottoms of steel ships, wooden ships, and reinforced plastic ships, fishing nets, underwater structures, and seawater introduction pipes. It also applies to the protection of objects that are susceptible to damage from contaminant organisms due to their long-term use. Next, the present invention will be explained with reference to Examples and Test Examples. % and parts in Examples and Test Examples indicate weight % and parts by weight, respectively. Example 1 500ml equipped with thermometer, reflux condenser and stirrer
-Pour 32 g of N-vinyl N-methylacetamide, 55 g of methyl methacrylate, 10 g of octyl acrylate, and 200 g of xylene into a three-necked flask.
After adding 0.5g of azobisisobutyronitrile and purging the inside of the container with nitrogen gas, lower the internal temperature to 80℃ while stirring.
Raised to ℃. Next, while stirring at the same temperature, 0.2 g of azobisisobutyronitrile was added three times every 3 hours to conduct a polymerization reaction for a total of 12 hours to obtain a nitrogen-containing copolymer solution. 103 g of triphenyltin isothiocyanate was added to this solution, and an addition reaction was carried out with stirring at 50°C for 2 hours to obtain an N-coordination-triphenyltin-containing copolymer solution (copolymer solution [A-1]) with a molecular weight of 96,000. Ta. This copolymer solution was directly used as an antifouling agent. Examples 2 to 20 According to the same polymerization reaction and addition reaction conditions as in Example 1, the polymerization components shown in Table 1 below were placed in a reaction vessel.
A solvent and a catalyst are charged, a polymerization reaction is carried out to produce a nitrogen-containing copolymer solution, and then tri-organotin pseudohalide is added to carry out an addition reaction to form an N-coordination-triorganotin-containing copolymer solution (copolymer Combined solutions [A-2] to [A-20]) were obtained. These copolymer solutions [A-2] to [A-20] were directly used as antifouling agents. The above is shown in Table 1.

【table】

【table】

[Table] Example 21 40 g of N-vinylphenylethylamine, 95 g of tributyltin isothiocyanate, and 200 g of xylene were placed in the same reaction vessel as in Example 1, and stirred at 50°C for 2 hours to prepare N-vinylphenylethylamine. A tributyltin isothiocyanate adduct was formed. Next, 50g of methyl methacrylate,
15 g of octyl acrylate and 0.5 g of benzoyl peroxide were added, and the temperature was raised to 95° C. with stirring. At the same temperature, 0.2 g of benzoyl peroxide was added three times every 3 hours to carry out a polymerization reaction for a total of 12 hours, and a solution of an N-coordination-tributyltin-containing copolymer with a molecular weight of 75,000 (copolymer solution [A-21]) I got it.
This copolymer solution was directly used as an antifouling agent. Examples 22 to 25 According to the same addition reaction conditions and polymerization conditions as in Example 21, the nitrogen-containing unsaturated compound, triorganotin compound, and solvent shown in Table 2 were charged, the addition reaction was carried out, and then the comonomer component A polymerization reaction is carried out by adding a polymerization initiator and an N-coordination-triorganotin-containing copolymer solution (copolymer solution [A-22] to [A-25])
I got it. These copolymer solutions [A-22] to [A
-25] was used as an antifouling agent. The above is shown in Table 2.

[Table] Reference example: Triphenyltin methacrylate 120 in the reaction vessel
After preparing 64 g of octyl acrylate, 16 g of methyl methacrylate and 200 g of xylene and dissolving them well, add 0.8 g of azobisisobutyronitrile.
was added, and polymerization was carried out at 75° C. for 3 hours with stirring to obtain a triphenyltin-containing copolymer solution (copolymer solution [Reference Example]) having a molecular weight of 77,000. Examples 26 to 50 Using each of the N-coordination-triorganotin-containing copolymer solutions obtained in Examples 1 to 25, the ingredients listed in Table 3 below were added to the solutions for the ship bottom of the present invention. Obtained antifouling paint. The above is summarized in Table 3.

【table】

[Table] Antifouling test (clear coating) The antifouling agents of the present invention (copolymer solutions [A-1] to [A-25]) obtained in Examples 1 to 25 were tested in 17×9×0.3
Dry film thickness on both sides of hard vinyl chloride resin board of cm
It was applied to a thickness of 150μ. Each coated plate was immersed in an underwater raft for 6 months in Owase Bay, Mie Prefecture.
The state of contamination was observed. The results are shown in Table 4. The symbols in the table indicate the following (the same applies to subsequent tables). 〇 Mark: No adhesion of marine animals and plants △ Mark: 〃 Less than 5% adhesion × Mark: 〃 5 to 20% adhesion × × Mark: 〃 20 to 50% adhesion × × × Mark: 〃 50% There is more adhesion than

【table】

[Table] Antifouling test (ship bottom paint) The antifouling paint for ship bottoms of the present invention obtained in Examples 26 to 50 was coated on both sides of a 17 x 9 x 0.3 cm hard vinyl chloride resin plate to a dry film thickness of approximately 200μ. I applied it to make it look like this.
Each coated plate was immersed in an underwater raft for 12 months in Owase Bay, Mie Prefecture, and its contamination status was periodically observed. The results are shown in Table 5.

[Table] Antifouling test (fishing net) 200 parts of xylene was added to 100 parts of the antifouling agent of the present invention (copolymer solution [A-1] to [A-25]) obtained in Examples 1 to 25. and diluted. 30 x 40 for each diluted solution
cm polyethylene fishing nets (24 pieces, 8 sections) were soaked, taken out after a few minutes, air-dried, and mounted on a steel frame. The amount of coating after air drying was approximately 6% based on the weight of the fishing net. These were immersed in an underwater raft for three months in Owase Bay, Mie Prefecture, and their contamination status was observed every month. The results are shown in Table 6.

[Table] Storage stability test (antifouling agent) The antifouling agents obtained in Examples 1 to 25 (copolymer solutions [A-1] to [A-25]) were placed in 100 ml glass bottles, and 50 ml of The sample was stored in an oven at ℃ for 3 months, taken out after a certain period of time, and observed for changes over time.
The same procedure was also carried out for the copolymer solution [Reference Example]. The results are shown in Table 7. The symbols in the table indicate the following (the same applies to subsequent tables). A: No change compared to the viscosity of the antifouling agent or antifouling paint immediately after manufacture B: Slightly increased viscosity than the viscosity of the antifouling agent or antifouling paint immediately after manufacture C: The viscosity of the antifouling agent or antifouling paint immediately after manufacture Viscosity significantly increased D: Antifouling agent or antifouling paint gels.

[Table] Storage stability test (antifouling paint) The antifouling paints obtained in Examples 26 to 50 were placed in 100 ml glass bottles, stored in an oven at 50°C for 3 weeks, taken out after a certain period of time, and aged. Observed changes. The results are shown in Table 8.

[Table] Example 51 In a reaction vessel similar to Example 1, 40.0 g of N,N-dimethylaminoethyl methacrylate, 47.2 g of methyl methacrylate, and 10.0 g of octyl acrylate were added.
After adding 0.5 g of azobisisobutyronitrile and purging the inside of the container with nitrogen gas, the internal temperature was raised to 80° C. while stirring. Next, while stirring at the same temperature, 0.2 g of azobisisobutyronitrile was added three times every 3 hours to conduct a polymerization reaction for a total of 12 hours to obtain a nitrogen-containing copolymer solution.
Add triphenyltin isothiocyanate to this solution.
Add 102.8g and conduct an addition reaction while stirring at 50℃ for 2 hours to obtain a molecular weight of 78000 and a tin content in the solid content.
A 15.0% N-coordination-triphenyltin-containing copolymer solution (copolymer solution [A-26]) was obtained. This copolymer solution was directly used as an antifouling agent. Example 52 According to the same polymerization reaction and addition reaction conditions as in Example 51, the polymerization components shown in Table 9 below and 200 g of xylene were charged into a reaction vessel, the same amount of azobisisobutyronitrile was added, and the polymerization reaction was started. Then, 87.8 g of tributyltin isothiocyanate was added to perform an addition reaction to obtain a N-coordination-tributyltin-containing copolymer solution (copolymer solution [A-27]). Obtained. This copolymer solution was directly used as an antifouling agent. Comparative Example 1 40.0 g of N,N-dimethylaminoethyl methacrylate, 50.0 g of methyl methacrylate, and 12.8 g of octyl acrylate were placed in the same reaction vessel as in Example 1.
After adding 0.5 g of azobisisobutylronitrile and purging the inside of the container with nitrogen gas, the internal temperature was raised to 80° C. while stirring. Then add azobisisobutyronitrile while stirring.
0.2 g was added every 3 hours to carry out the polymerization reaction for a total of 12 hours to obtain a nitrogen-containing copolymer solution. Add 97.2 g of triphenyltin chloride to this solution and heat at 50°C.
The addition reaction was carried out with stirring for 2 hours at
75000, an N-coordination-triphenyltin-containing copolymer solution (copolymer solution [B-1]) having a tin content of 15.0% in solid content was obtained. This copolymer solution was directly used as an antifouling agent. Comparative Example 2 According to the same polymerization reaction and addition reaction conditions as in Comparative Example 1, the polymerization components shown in Table 9 below and 200 g of xylene were charged into a reaction vessel, the same amount of azobisisobutyronitrile was added, and the polymerization reaction was started. to produce a nitrogen-containing copolymer and tributyltin chloride
82.0g was added to carry out an addition reaction, and an N-coordination-tributyltin-containing copolymer solution (copolymer solution [B-
2]) was obtained. This copolymer solution was directly used as an antifouling agent. The above is summarized in Table 9.

[Table] Test for measuring the amount of leached tin (leaching rate) Antifouling agents obtained in Examples 51 to 52 and Comparative Examples 1 to 2 (copolymer solutions [A-26] to [A-27] and [B- 1) to [B-2]) were applied to one side of a 15 x 7 x 0.2 cm hard vinyl chloride resin board to a thickness of approximately 60 μm, air-dried for 1 day, and then dried at 50°C for 1 day. It was dried in the sun and used as a test plate. Each test plate was attached to an iron frame and immersed 1 m below the sea surface in Owase Bay, Mie Prefecture, and removed from time to time for 2 months. Each test plate was placed in a glass container and placed in natural seawater 1 whose liquid temperature was adjusted to 20°C. After aeration for 4 hours at 500 ml/min, tin eluted into the seawater was quantified by flameless atomic absorption spectrometry (AA-670G, manufactured by Shimadzu Corporation). The results are shown in Table 10.

【table】

[Table] Antifouling test (clear coating) Antifouling agents obtained in Examples 51 to 52 and Comparative Examples 1 to 2 (copolymer solutions [A-26] to [A-27] and [B-1]) - [B-2]) was applied to both sides of a hard vinyl chloride resin plate measuring 17 x 9 x 0.3 cm to a dry film thickness of about 150 μm. Each coated plate was immersed in an underwater raft for 12 months in Owase Bay, Mie Prefecture, and its contamination status was observed. The results are shown in Table 11.

【table】

Claims (1)

[Scope of Claims] 1 In the polymer main chain, (a) the following general formulas [a], [b] and [c] [Formula] [Formula] [Formula] [In the formula, R is the same or different carbon 1 to 8 alkyl groups, cycloalkyl groups, aryl groups, or aralkyl groups, X is a group -NCS, a group-
NCO, the group -N ₃ or the group -CN, R ¹ and R ² are independently selected from hydrogen atoms, methyl groups, ethyl groups and halogen atoms, p is an integer from 1 to 4, Y
is an alkylene group having 1 to 12 carbon atoms, a phenylene group, a group [formula] group [formula] group [formula] group -O-Z- or a group -S-Z- (in the formula, Z is a group having 2 to 12 carbon atoms) alkylene group or group [Formula] (m: an integer of 1 to 8)), A and B may or may not be bonded to each other; (i) When A and B are not bonded to each other; A and B are hydrogen atoms, alkyl groups having 1 to 18 carbon atoms, cycloalkyl groups, aryl groups, aralkyl groups, hydroxyalkyl groups or alkoxyalkyl groups having 2 to 12 carbon atoms, and groups [formula] (in the formula R ³ represents an alkyl group or an aryl group having 1 to 18 carbon atoms; (ii) when A and B are bonded to each other;
and B represent a 5- to 6-membered hetero ring or a condensed ring thereof formed together with the nitrogen atom of formula [a] or [b], and group [formula] represents the corresponding carbon atom to which R ¹ is bonded. At least one N-coordinated tri-organotin-containing repeating unit represented by 5- to 6-membered heterocycle or fused ring thereof bonded by a ring member other than a nitrogen atom; and (b) an acrylic compound; Derived from at least one comonomer selected from the group consisting of a vinyl compound having a functional group, a vinyl hydrocarbon compound, a triorganotin salt of a polymerizable unsaturated carboxylic acid, and a polymerizable unsaturated dicarboxylic acid or anhydride thereof. An antifouling agent characterized by containing a triorganotin-containing copolymer containing a repeating comonomer unit as an antifouling component. 2. The antifouling agent according to claim 1, wherein in formula [a], the group [formula] is a dialkylamino group or an alkylphenylamino group. 3. The antifouling agent according to claim 1, wherein in the formula [a], the group [formula] is the group -N (CH ₃ ) COCH ₃ or the group -N ((C ₆ H ₅ ) COCH ₃ . The antifouling agent according to claim 1, wherein in the formula [a], the group [formula] is the group [formula]. 5. The antifouling agent according to claim 1, wherein in the formula [a], the group [formula] is the group [formula]. 6. The antifouling agent according to claim 1, wherein in the formula [b], the group [formula] is a group [formula] or the group [formula]. 7. The antifouling agent according to claim 1, wherein [formula] is a group [formula]. 8. The antifouling agent according to claim 1, wherein in formula [b], the group [formula] is a group [formula] or a group [formula]. The antifouling agent according to claim 1. 9 The antifouling agent according to claim 1, wherein in the formula [b], the group [formula] is a group [formula]. 10 The antifouling agent according to claim 1, wherein in the formula [b], the group [formula] is a group The antifouling agent according to claim 1, which is [Formula]. 11 In the formula [b], the group [Formula] is a group - O-CH ₂ CH ₂ -N(CH ₃ ) ₂ or a group -O-CH ₂ CH ₂
-N(C ₂ H ₅ ) ₂ The antifouling agent according to claim 1, wherein the antifouling agent is 12. The antifouling agent according to claim 1, wherein in formula [c], the group [formula] is a group [formula] or a group [formula]. 13 In formulas [a], [b] and [c]
The antifouling agent according to claim 1, wherein R ₃ SnX is tributyltin isothiocyanate or triphenyltin isothiocyanate. 14. The triorganotin-containing copolymer according to claim 1, wherein the triorganotin-containing copolymer contains 10 to 80% by weight of N-coordinated triorganotin-containing repeating units and 90 to 20% by weight of comonomer repeating units. Antifouling agent. 15 The triorganotin-containing copolymer has a molecular weight of 5,000 to 500,000
The antifouling agent according to claim 1, which has a molecular weight of .