JPH0142243B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to an underwater antifouling agent containing a novel triorganotin-containing copolymer as an antifouling component. Seaweed such as green algae, brown algae, and diatoms, as well as polluting organisms such as sea squirts, barnacles, serpula, oysters, and bryozoans,
It adheres to the bottom of ships, fishing nets, and the surface of underwater structures, causing various types of damage. For example, they suffer from damage such as a decrease in ship speed due to increased frictional resistance, poor growth of farmed fish due to obstruction of seawater flow due to blocked fishing nets, and corrosion of underwater structures. Various antifouling paints are used to prevent the attachment of contaminant organisms, and many of them contain tri-organotin compounds as the antifouling component. However, antifouling paints containing tributyltin compounds or triphenyltin compounds as antifouling components, for example, are highly toxic to the human body during operation and do not have long-term antifouling performance. Therefore, triorganotin-containing polymer-type antifouling agents having -COOSnR ₃ (R is an alkyl or phenyl group) in the molecule are currently used, but copper compounds are added to these polymers for the purpose of long-term antifouling. However, the paint had the disadvantage of thickening and gelling during storage. As a result of conducting research from a new perspective, the present inventors found that if a completely new triorganotin-containing copolymer containing triorganotin sulfonate in the molecule is used as an antifouling component, it will not have the above disadvantages and will last for a long time. It was discovered that the antifouling effect can be exhibited over a long period of time, and the present invention was developed based on this discovery. That is, the present invention provides that the copolymer (a) has the general formula

[Formula] or/and

[Formula] (wherein R is the same or different lower alkyl group, cycloalkyl group or phenyl group, X is a hydrogen atom or lower alkyl group, A is a methylene group, phenylene group or group

A structural unit containing a tri-organotin sulfonate represented by [formula] and (b) a tri-organic compound containing an acrylic compound, a vinyl compound having a functional group, a vinyl hydrocarbon, and a polymerizable unsaturated carboxylic acid. This is an underwater antifouling agent characterized in that the antifouling component is a triorganotin-containing copolymer comprising at least one structural unit selected from the group consisting of organic tin salts. Further, the present invention is an underwater antifouling agent characterized in that the triorganotin-containing copolymer and a copper compound are used as antifouling components. The triorganotin-containing copolymer of the present invention has the general formula [] or []

【formula】

One or two unsaturated triorganotin sulfonate monomers and other polymeric unsaturated compound monomers represented by the formula: By copolymerizing two or more species, or the general formula [] is []

【formula】

[Formula] An unsaturated sulfonic acid monomer represented by the formula (wherein X and A have the same meanings as above) and one or more other polymeric unsaturated compound monomers are polymerized. It can be obtained by reacting the obtained copolymer with bis(triorganotin) oxide or triorganotin hydroxide in a substantially stoichiometric amount. Examples of the unsaturated triorganotin sulfonate monomer represented by the above general formula [] or [] include triethyltin (2-acrylamido-2-methylpropane) sulfonate, tripropyltin (2
-acrylamide-2-methylpropane) sulfonate, tributyltin (2-acrylamide-2
-methylpropane) sulfonate, triamyltin (2-acrylamido-2-methylpropane) sulfonate, tricyclohexyltin (2-acrylamido-2-methylpropane) sulfonate,
Triphenyltin (2-acrylamido-2-methylpropyl) sulfonate, tripropyltin vinylsulfonate, tributyltin vinylsulfonate, tricyclohexyltin vinylsulfonate,
Triphenyltin vinylsulfonate, tripropyltin allylsulfonate, tributyltin allylsulfonate, tricyclohexyltin allylsulfonate, triphenyltin allylsulfonate, tripropyltin metallylsulfonate, tributyltin metallylsulfonate, tricyclohexyltin metallylsulfonate, triphenyltin metall sulfonate Lylsulfonate, tripropyltin (p-styrene)
Examples include sulfonate, tricyclohexyltin (p-styrene) sulfonate, triphenyltin (p-styrene) sulfonate, and these compounds can be used alone or in combination of two or more. Examples of the unsaturated sulfonic acid represented by the above general formula [] or [] include 2-acrylamido-2-methylpropanesulfonic acid, vinylsulfonic acid, allylsulfonic acid, methallylsulfonic acid, p-styrenesulfonic acid, etc. are mentioned,
These compounds can be used alone or in combination of two or more. In addition, other polymerizable unsaturated compound monomers that can be copolymerized with the monomers represented by the general formula [], [), [] or [] include acrylic compounds, vinyl compounds having functional groups, etc. compounds, vinyl hydrocarbons, triorganotin salts of polymerizable unsaturated carboxylic acids, and the like. Examples of acrylic compounds include acrylic acid, methacrylic acid, α-ethyl acrylic acid, α-
Acrylic acid or methacrylic acids such as chloroacrylic acid; methyl, ethyl, propyl, butyl, amyl, hexyl, octyl, acrylic acid;
Acrylic acid esters such as dodecyl, octadecyl, cyclopentyl, cyclohexyl, phenyl, benzyl, tetrahydrofurfuryl ester; methyl, ethyl, butyl methacrylate,
Examples include methacrylic acid esters such as hexyl, octyl, and lauryl esters. Examples of the vinyl compound having a functional group include vinyl chloride, vinylidene chloride, acrylonitrile, vinyl acetate, butyl vinyl ether, and lauryl vinyl ether.
Examples of vinyl hydrocarbons include propylene,
Examples include styrene, α-styrene, and 1,3-butadiene. Examples of triorganotin salts of polymerizable unsaturated carboxylic acids include tripropyltin methacrylate, tributyltin methacrylate, triamyltin methacrylate, triphenyltin methacrylate, tripropyltin acrylate, tributyltin acrylate, triamyltin acrylate, triphenyltin acrylate, bis (Tripropyltin) itaconate, bis(tributyltin) itaconate, bis(tricyclohexyltin) itaconate, bis(triphenyltin) itaconate, bis(tributyltin) malate, bis(triphenyltin) malate, and the like. These compounds may be used alone or in combination of two or more. Copolymerization of the compound monomer represented by the above general formula [] or [] with other polymerizable unsaturated compound monomers, or copolymerization of the compound monomer represented by the general formula [] or [] with other polymers. Copolymerization with a sexually unsaturated compound monomer can be carried out by bulk polymerization, solution polymerization, emulsion polymerization, or suspension polymerization in the presence of a suitable polymerization catalyst, preferably a radical catalyst. Most preferred is solution polymerization in a solvent. Examples of organic solvents used in solution polymerization include alcohols such as methanol, isopropanol, isobutanol, and ethyl cellosolve; hydrocarbons such as toluene and xylene; ketones such as methyl ethyl ketone and methyl isobutyl ketone; tetrahydrofuran, dibutyl ether, etc. ethers; esters such as ethyl acetate and butyl acetate, and these organic solvents may be used alone or in combination. Furthermore, when a substantially stoichiometric amount of bis(triorganotin) oxide or triorganotin hydroxide is allowed to act on the copolymer, it can usually be carried out in the above-mentioned organic solvent. The proportion of triorganotin sulfonate-containing repeating units represented by the general formula [] or [] in the triorganotin sulfonate-containing copolymer of the present invention is not particularly limited, and has antifouling coating film forming ability and antifouling performance. For example, if the tin content in the copolymer is 2 to
Adjusted to 25% by weight. Further, the type and proportion of other polymerizable unsaturated monomers to be copolymerized are arbitrarily selected depending on the required physical properties of the coating film and the intended use. Another copper compound used in the present invention includes, for example, cuprous oxide, copper rhodan, copper phosphide, copper rosinate, copper naphthenate, copper hydroxide, etc., with cuprous oxide and copper rhodan being particularly preferred. . The underwater antifouling agent of the present invention uses the triorganotin-containing copolymer of the present invention, or the copolymer and a copper compound as an antifouling component, and is produced in various forms depending on the antifouling purpose. That is, the triorganotin-containing copolymer of the present invention is dissolved in the solvent used in the solution polymerization described above, such as an organic solvent such as hydrocarbons, ketones, esters, alcohols, and ethers, or The triorganotin-containing copolymer solution obtained by each production method can be used as an antifouling agent as it is or after being diluted. In addition, copper compounds such as cuprous oxide and copper rhodan may be mixed with dyes, pigments, carriers, organic tin compounds such as tributyltin fluoride and triphenyltin fluoride, paint conditioners, poison elution control agents, and diluents if necessary to prevent fishing nets. Used as a fouling agent and antifouling paint for ship bottoms. The underwater antifouling agent of the present invention has the following features. That is, firstly, since the triorganotin sulfonic acid-containing copolymer according to the present invention is a polymer type antifouling agent, its physiological effect on the human body is extremely reduced, and there is no fear that it will harm workers. Second, when the antifouling agent of the present invention is applied to a substrate such as a metal plate, a wooden board, or a synthetic fiber net, a protective coating film with excellent adhesiveness, flexibility, and coating strength can be obtained. Thirdly, since the antifouling agent of the present invention is a polymer with hydrophilic sulfonic acid residues, it has the performance as a soluble matrix, and when immersed in seawater, the coating surface remains constant. It is renewed and can maintain long-term stain resistance. Fourthly, even when a copolymer and a copper compound are used in combination in the present invention, changes over time such as thickening and gelation do not substantially occur during storage. 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 ships made of reinforced plastics, fishing nets, underwater structures, and seawater introduction pipes. It also applies to the protection of objects susceptible to damage from contaminant organisms due to the long-term use of water. 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
- In a three-necked flask, 20.9 parts of 2-acrylamido-2-methylpropanesulfonic acid, 30 parts of bis(tributyltin) oxide, 50 parts of 2-ethylhexyl acrylate, 50 parts of isobutanol, and xylene.
50 parts were added and heated to 70°C while stirring to form a homogeneous solution. Next, 1 part of 2,2'-azobisisobutyronitrile was added as a polymerization catalyst, and after purging the inside of the container with nitrogen gas, it was heated with stirring to a temperature of 80±2
The polymerization reaction was carried out at 105°C for 6 hours and then at 105±2°C for 1 hour to obtain a colorless and transparent tributyltin sulfonate-containing copolymer solution (copolymer solution A) having a viscosity (25°C) of 1024 cps. This copolymer solution was directly used as an antifouling agent. Examples 2 to 5 Each part of the polymerization components, solvent, and polymerization catalyst shown in Table 1 below was charged into a reaction vessel, and a polymerization reaction was carried out in the same manner as in Example 1 to obtain a triorganotin sulfonate-containing copolymer. Coalescence solutions (copolymer solutions BE) were obtained. These copolymer solutions B to E were directly used as antifouling agents. The above is shown in Table 1.

[Table] Example 6 Charge 7.5 parts of 2-acrylamido-2-methylpropanesulfonic acid, 40 parts of 2-ethylhexyl acrylate, 40 parts of methyl methacrylate, 150 parts of methanol, and 50 parts of xylene into a reaction container, and stir well to form a homogeneous solution. And so. Next, 1.2 parts of 2,2'-azobis(2,4-dimethylvaleronitrile) was added, and the inside of the container was replaced with nitrogen gas and heated to 65±2℃.
A polymerization reaction was carried out for 6 hours to obtain a sulfonic acid-containing copolymer solution. Add 12.9 parts of bis(triphenyltin) oxide to this solution, heat to 70°C, react while distilling off 100 parts of the solvent, and reduce the viscosity (25°C).
A colorless and transparent copolymer solution containing triphenyltin sulfonate (copolymer solution F) of 688 cps was obtained. This copolymer solution was directly used as an antifouling agent. Example 7 In a reaction vessel, 15.8 parts of 2-acrylamido-2-methylpropanesulfonic acid and 40 parts of acrylonitrile were added.
parts, 20 parts of styrene, 50 parts of methanol and xylene
100 parts were added and stirred well to make a homogeneous solution.
Next, 1.5 parts of 2,2'-azobis(2,4-dimethylvaleronitrile) was added, the inside of the container was replaced with nitrogen gas, heated, and the polymerization reaction was carried out at 65±2°C for 6 hours to form a sulfonic acid-containing copolymer solution. I got it. Add 12 parts of bis(tributyltin) oxide and 13.2 parts of triphenyltin hydroxide to this solution,
The mixture was heated to .degree. C. and reacted while distilling off 50 parts of the solvent to obtain a triorganotin sulfonate-containing copolymer solution (copolymer solution G) having a viscosity (25.degree. C.) of 424 cps.
This copolymer solution was directly used as an antifouling agent. Example 8 In a reaction vessel, 20.9 parts of 2-acrylamido-2-methylpropanesulfonic acid, 3.4 parts of methacrylic acid,
35 parts of 2-ethylhexyl acrylate, 150 parts of methanol, and 50 parts of xylene were charged and thoroughly stirred to form a homogeneous solution. Then, 1.5 parts of 2,2'-azobisisobutyronitrile was added, and the inside of the container was purged with nitrogen gas, heated, and a polymerization reaction was carried out at 65±2° C. for 8 hours to obtain a sulfonic acid-containing copolymer solution. 41.9 parts of bis(tributyltin) oxide was added to this solution, heated to 70°C, and reacted while distilling off 100 parts of the solvent. A polymer solution H) was obtained. This copolymer solution was directly used as an antifouling agent. Examples 9 to 16 Using each of the tri-organotin-containing copolymer solutions obtained in Examples 1 to 8, the ingredients listed in Table 2 below were added to form antifouling paints for ship bottoms of the present invention. Obtained. The above is summarized in Table 2. Note that the numbers in the table indicate parts by weight.

[Table] Antifouling test (clear coating) The antifouling agents of the present invention (copolymer solutions A to H) obtained in Examples 1 to 8 were applied to both sides of a hard vinyl chloride resin solution measuring 17 x 9 x 0.3 cm. It was applied to a dry film thickness of approximately 120μ. Each coating solution was immersed in an underwater raft for 9 months in Owase Bay, Mie Prefecture, and the contamination state was periodically observed. The results are shown in Table 3. The symbols in the table indicate the following (the same applies to subsequent tables). 〇 Mark: No marine animals and plants attached △ Mark: Less than 5% of marine animals and plants attached × Mark: 5-20% of marine animals and plants attached ×× Mark: 20-50% of marine animals and plants attached ××× Mark: More than 50% of marine animals and plants are attached.

[Table] Antifouling test (ship bottom paint) The antifouling paint for ship bottoms of the present invention obtained in Examples 9 to 16 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 150μ. 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 4.

[Table] Antifouling test (fishing net) 100 parts of the antifouling agent (copolymer solution) of the present invention obtained in Examples 1 to 8 was diluted by adding 200 parts of xylene. A 30 x 40 cm polyethylene fishing net (24 pieces, 8 sections) was immersed in each diluted solution, taken out after a few minutes, air-dried, and attached to an iron frame. The amount of coating was approximately 20% of the weight of the fishing net. These were immersed in an underwater raft for four months in Owase Bay, Mie Prefecture, and their contamination status was observed. The results are shown in Table 5.

[Table] Storage stability test (antifouling agent) The antifouling agents (copolymer solutions) obtained in Examples 1 to 8 were placed in 100 ml glass bottles and stored in an oven at 50°C for 3 weeks. After a certain period of time, it was taken out and changes over time were observed. The results are shown in Table 6. The symbols in the table indicate the following. A: No change compared to the viscosity of the antifouling agent immediately after manufacture B: Slightly thicker than the viscosity of the antifouling agent immediately after manufacture C: Significantly thicker than the viscosity of the antifouling agent immediately after manufacture D: The antifouling agent is a gel transformation

【table】

【table】

Claims (1)

[Scope of Claims] 1 The copolymer has the general formula [formula] or/and [formula] (wherein R is the same or different lower alkyl group, cycloalkyl group or phenyl group, and X is a hydrogen atom or a lower alkyl group, A represents a methylene group, a phenylene group, or a group [formula] respectively), and (b) an acrylic compound, a vinyl compound having a functional group. An underwater antifouling agent characterized in that the antifouling component is a tri-organotin-containing copolymer comprising at least one constituent unit selected from the group consisting of and vinyl hydrocarbons. 2. The copolymer has (a) the general formula [formula] or/and [formula] (wherein R is the same or different lower alkyl group, cycloalkyl group, or phenyl group, A is a methylene group, a phenylene group, or a triorganotin sulfonate represented by the following formula (respectively); and (b) an acrylic compound, a vinyl compound having a functional group, and a vinyl hydrocarbon. An underwater antifouling agent characterized in that the antifouling component is a triorganotin-containing copolymer comprising at least one structural unit selected from the group consisting of a copper compound and a triorganotin-containing copolymer.