JPH02103271A - Underwater antifouling agent composition - Google Patents

Abstract

PURPOSE:To obtain the subject composition, containing a specific compound and dithiocarbamate-based compound as antifouling active components, having effects equal to or better than those of an organotin-based antifouling agent and safe for humans, cattle, etc., without causing environmental pollution. CONSTITUTION:The objective composition simultaneously containing (A) one or more compounds expressed by the formula (R is 1-4C alkyl, cyclohexyl, trichloromethyl, ethoxycarbonyl or isopropoxycarbonyl) and (B) a dithiocarbamate-based compound (e.g., tetramethylthiurammonodisulfide) as antifouling active components.

Description

[Detailed Description of the Invention] [Field of Industrial Application] The present invention prevents fouling and damage caused by marine organisms that grow attached to the bottom of ships, fishing nets such as aquaculture nets and fixed nets, and other marine structures. The present invention relates to underwater antifouling compositions.

[Conventional technology]

The bottom and waterline of ships, fishing nets such as aquaculture nets and fixed nets,
Other marine structures are infested with aquatic organisms, such as animals such as fujibo, kanzane, sea squirts, mussels, and oysters, algae such as sea lettuce, blue seaweed, and seaweed, various bacteria called slime, mold, and diatoms. received,
This caused a great deal of damage, and the removal, repair, and
It is causing a lot of damage to the repaint.

For example, in ships, the increase in resistance of the ship's hull by several percent due to the adhesion of aquatic organisms causes a reduction in speed and fuel efficiency, resulting in extremely large losses.

In addition, in recent years, with the progress of marine development in coastal waters,
BACKGROUND OF THE INVENTION The construction and installation of large offshore structures, their auxiliary structures, and other similar structures for various purposes is increasing.

For example, navigation buoys, light buoys, mooring buoys, floating jetties, floating breakwaters, floating docks, and other port facility structures, vibrating lines, bridges, tanks, power plant conduit pipes, coastal industrial plants, mooring vessels, Structures that come into contact with seawater, such as restaurants, hotels, moored floating fishing structures, cage structures for fish farming, fixed fishing nets, and similar aquaculture facility structures, are exposed to sessile marine organisms that cause contamination. By growing attached to the structure, it causes damage such as accelerated corrosion of the base material of the structure, subsidence due to weight increase, and unstable balance.

In addition, when seawater is used for cooling and other purposes in various facilities, factories, power plants, etc. on the coast, it has a tendency to adhere to water that causes contamination on coastal structures such as seawater collection pipes, discharge pipes, waterways, and ditches. Marine organisms grow attached, and in severe cases several 10%
Adhesive growth occurs on orders of magnitude, reducing the effective area of the waterway, increasing flow resistance, and clogging the screen for removing suspended solids.
suffer other damage.

Furthermore, aquatic organisms such as aquaculture nets, fixed nets, fishing nets, ropes, etc., such as Fujitbo, Kasane Kantashi, sea squirt, green algae, and brown algae, adhere to them, hindering the economical operation of fishing nets, and requiring a great deal of labor and expense to maintain them. It takes.

Conventionally, in order to prevent these problems, poorly soluble inorganic copper compounds, organic tin compounds, organic tin polymers, organic nitrogen sulfur compounds, etc. have been used.

However, some of these have drawbacks such as being highly toxic to humans and animals, causing environmental pollution, and not being sufficiently effective over a long period of time when used as an underwater antifouling agent. For example, organotin compounds have extremely high antifouling effects on marine organisms and are considered effective antifouling ingredients.
Although it has been widely used, in recent years its persistent nature, accumulation in living organisms, safety for humans and animals, and environmental pollution have become problems.

In addition, dithiocarbamates, which are organic sulfur compounds,
Like tin compounds, it is widely used as an antifouling agent component. For example, in JP-A-51-49227, ethylene bisdithiocarbamate manganese salt is used as an antifouling agent component, and this is mixed with a vehicle component to form a coating film on fishing nets to prevent attachment of organisms. . Similarly, in JP-A-51-51517, a heavy metal salt of ethylene bisdithiocarbamate and a cellulose resin are blended with a vehicle component to form an antifouling coating film to prevent attachment of living things.

(Problems to be Solved by the Invention) As antifouling components for marine organisms, organotin compounds such as tributyltin hydroxide and triphenyltin hydroxide are considered to be the most desirable in terms of their long-lasting effect and stability of efficacy. However, there are various concerns regarding safety to humans and livestock, environmental pollution, etc.

Due to various issues such as safety to the human body and environmental pollution, dithiocarbamate metal salts are considered the most desirable antifouling agent ingredients, but their durability and stability of efficacy are not fully satisfied. There are many cases where it is not possible. For this purpose, inorganic copper compounds and alkylene bisdithiocarbamic acid heavy metal salts are used as antifouling agent components, or other antifouling agent components, specifically organic tin compounds, are added to these, but still. I can't say it's enough. Therefore, there is a demand for an underwater antifouling agent composition that has a long residual period, has little physicochemical deterioration of the coating film, is highly safe to humans, livestock, etc., and causes less environmental pollution.

(Means for Solving the Problems) As a result of intensive research to solve the above problems, the present inventors have found the following general formula (1) (wherein R is a lower alkyl group having 4 or less carbon atoms, a cyclohexyl group, Trichloromethyl group, ethoxycarbonyl group,
isopropoxycarbonyl group) and one or more dithiocarbamate compounds as active ingredients. It has been found that the antifouling agent exhibits an extremely excellent antifouling effect equivalent to or superior to that of antifouling agent compositions.

As for the compound of general formula (1), it is preferable that R is a compound shown in Table 1. These compounds are known as active ingredients in acaricides for agriculture and horticulture, and are suitable for all chronic toxicity tests. safety has been confirmed.

However, the use of these compounds as antifouling agents for marine organisms was completely unknown.

Further, dithiocarbamate compounds that can be used in the present invention include tetra-lower alkylthiuram sulfide compounds, lower alkylene bisdithiocarbamic acid heavy metal salts, metal composite lower alkylene bisdithiocarbamic acid heavy metal salts, monofunctional lower alkyl dithiocarbamic acid heavy metal salts, lower Examples include heavy metal salts in which alkylenebisdithiocarbamic acid and monofunctional lower alkyldithiocarbamic acid are bonded via a heavy metal, or mixed metal salts thereof. More specifically, as the tetra-lower alkylthiuram sulfide compound, mono- or disulfide of tetramethyl, tetraethyl, tetrapropyl, tetraisopropyl, and tetrabutylthiuram can be used.As the lower alkylene bisdithiocarbamate heavy metal salt, ethylene can be used. Bisdithiocarbamic acid, linear or branched propylene bisdithiocarbamic acid, linear or branched butylene bisdithiocarbamic acid, N-substituted ethylene bisdithiocarbamic acid, N,N'-substituted ethylene bisdithiocarbamic acid, N-substituted propylene bisdithiocarbamic acid acid, N, N'-substituted propylene bisdithiocarbamic acid, N-substituted butylene bisdithiocarbamic acid, N,
Zinc, such as N'-substituted butylene bisdithiocarbamic acid,
Examples include salts of divalent or higher valent metals such as manganese, copper, iron, and nickel.

Further, the metal composite lower alkylene bisdithiocarbamic acid heavy metal salt is one in which another metal is coordinated to the above-mentioned lower alkylene bisdithiocarbamic acid heavy metal salt.

Typical examples thereof include zinc composite manganese ethylene bisdithiocarbamate, copper composite manganese ethylene bis dithiocarbamate, and the like.

Examples of monofunctional lower alkyl dithiocarbamic acid heavy metal salts include zinc manganese, copper, etc., such as methyldithiocarbamic acid, dimethyldithiocarbamic acid, ethyldithiocarbamic acid, diethyldithiocarbamic acid, propyldithiocarbamic acid, dipropyldithiocarbamic acid, butyldithiocarbamic acid, dibutyldithiocarbamic acid, etc. Examples include salts of divalent or higher-valent heavy metals such as iron and nickel.

Furthermore, examples of the dithiocarbamate compounds of the present invention include metal salts in which a lower alkylene bisdithiocarbamic acid and a monofunctional lower alkyldithiocarbamic acid are bonded via a heavy metal. This is produced by metathesis of a mixed aqueous solution consisting of a water-soluble salt of a lower alkylene bisdithiocarbamic acid and a water-soluble salt of a monofunctional lower alkyldithiocarbamic acid with a water-soluble heavy metal salt. Examples of the lower alkylenebisdithiocarbamic acid moiety and the monofunctional lower alkyldithiocarbamic acid moiety include those mentioned above. The most typical one is a mixed salt (bisdimethyldithiocarbamoylzinc ethylenebisdithiocarbamate) in which ethylenebisdithiocarbamic acid and dimethyldithiocarbamic acid are bonded via zinc. At this time, in addition to this, dimethyldithiocarbamic acid zinc salt, which is a heavy metal salt of monofunctional lower alkyldithiocarbamic acid, and ethylenebisdithiocarbamic acid zinc salt, which is a lower alkylene bisdithiocarbamic acid heavy metal salt, are usually mixed. This is commonly referred to as a polycarbamate agent.

In the dithiocarbamate compound of the present invention, in addition to the above-mentioned chemically mixed metal salts, these physical mixed metal salts can also be used. When using these compounds, it is possible to prepare them arbitrarily depending on the place and time of use.

The antifouling agent composition of the present invention has the general formula (
It is prepared by mixing one or more compounds represented by I) and one or more dithiocarbamate compounds with a vehicle, an organic solvent, and various additives.

In the present invention, the antifouling active ingredient can be optionally blended into the antifouling agent composition, but the compound represented by general formula (I) is contained in an amount of 0.5 to 50% by weight, preferably 0.5 to 20% by weight. %, and dithiocarbamate compounds can be blended within the range of 0.
．． It can be blended in an amount of 5 to 30% by weight, preferably 0.5 to 20% by weight.

The vehicle and paint components used in the present invention are not particularly limited, but are preferably animal oils, vegetable oils, natural oils and fats, acrylic resins, vinyl resins, epoxy resins, alkyd resins, petroleum resins, and chlorinated resins. Vinyl or ethylene-vinyl acetate copolymer, rosin, etc. are used.

Further, as the solvent, xylene, solvent naphtha, methyl isobutyl ketone, methyl ethyl ketone, cellosolve, etc. may be used alone or in combination of two or more.

Various additives include pigments such as red iron oxide and barium sulfate,
Of course, auxiliary components such as brighteners such as talc and plasticizers such as tricresyl phosphate can be appropriately blended.

Furthermore, known antifouling agent components such as cuprous oxide, copper rhodan, and metallic copper may be mixed and used in the antifouling composition of the present invention.
It goes without saying that the antifouling effect can be expected to increase by mixing these.

The antifouling composition of the present invention can be applied to the bottom of a ship, which is the outer panel of a ship;
Aquaculture nets, fixed [δ nets, fishing nets such as lobes, port facility structures,
By applying it to marine structures such as vibrine and bridges, it can be applied to animals such as Fujibbo, Kasane Kanzaki, sea squirts, mussels, and mussels, algae such as Azasu, Aonori, Shiomidoro, Hihimidoro, etc., and various species called slime. It is highly effective in preventing the adhesion of a wide range of organisms such as bacteria, mold, and seaweed such as diatoms, and is persistent over a long period of time.

Dithiocarbamate compounds have traditionally shown high antifouling effects against bacteria and algae, but
Although the antifouling composition of the present invention has not been able to exhibit sufficient antifouling effects against animals such as snails, mussels, and mussels, the antifouling composition of the present invention is effective against a wide range of animals, bacteria, and algae. Demonstrates antifouling effect.

The antifouling composition of the present invention can be used in the same manner as for conventional antifouling compositions. For example, in the case of ship bottoms and offshore structures, it is mixed with a known paint, applied by a conventional coating method, and used after drying. Regarding robes, fishing nets, etc., the fishing nets are dipped in a mixture containing the antifouling composition of the present invention, pulled up, and then dried before use.

The antifouling agent composition of the present invention has an effect equal to or greater than that of conventional organotin-based antifouling agent compositions, is safe for humans and livestock, and is an antifouling agent that does not cause environmental pollution. It is a drug composition.

〔Example〕

Examples and comparative examples were conducted using the test methods shown below.

The present invention is not limited to these specific examples.

m (Ship antifouling agent composition test) After applying commercially available vinyl tar-based ship bottom No. 1 paint three times to a 300 x 100 x 1.6 mm sandblasted steel plate, Examples 1 to 1 shown in Table 2 were applied. 11. Comparative example 1
After applying the antifouling composition paint formed in 3 to 3 twice and drying it indoors for 4 days, 1
．． It was suspended and immersed at a depth of 5 m, and the state of marine organisms attached to it was observed for 30 months.

The evaluation was performed by setting the following evaluation criteria based on the adhesion surface M (%). The results are shown in Table 3.

Evaluation 1L [semi- 0: 1: Gai and Shigeru JI are also one blood path. No adhesion 5% or less 10% or less 25% or less 50% or less 50% or more No. table The effect of

滄鼠ゆ（Test of antifouling agent composition for marine structures) 300x t
A sandblasted steel plate of oo x 2n+m was coated with zinc epoxy shop brimer (dry film thickness 15 μm) and epoxy antifouling paint (dry film thickness 200 μm) beforehand. Examples 12 to 22 and Comparative Examples 4 to 7 shown in Table 4 were coated and used as test plates. After drying this test plate at room temperature for 7 days, it was suspended and immersed in a raft at Katsuura Port, Wakayama Prefecture, to a depth of 1.5+n.
The state of biofouling was observed for 6 months. The evaluation was the same as Test 1.

The results are shown in Table 5.

Note) 1) and 2); Animal deposits such as Fujibbo and sea squirts are frequently observed. 3); Vegetable deposits such as slime, green laver, sea lettuce, and citrus species occur.

From the results in Table 3, the antifouling agent composition of the present invention is equivalent to or more than the conventional organic tin-based compounds. occurs frequently. 4) Nislime, Aonori, Ulva,
Plant-based deposits such as citric acid are generated.

From the results shown in Table 5, the antifouling composition of the present invention was found to have an effect equal to or greater than that of conventional organotin compounds.

Test 3 (Fishing net antifouling agent composition test) Polyethylene knotless nets (5 knots 400 denier/70 nets) were added to the solutions of Examples 23 to 35 and Comparative Examples 8 to 10 shown in Table 6, respectively. After being impregnated and dried, it was tested by immersing it in Omura Bay, Nagasaki Prefecture, 1 m below the sea surface. Evaluation was performed based on the following evaluation criteria. The results are shown in Table 7.

Evaluation 11 (Semi-A: No fouling organisms B: There are fouling organisms, but continuous use is possible C: There are many fouling organisms, but it cannot withstand continuous use D = There are many fouling organisms) From the results shown in Table 7, the prevention of the present invention is When the stain composition was used for antifouling fishing nets, it was found to be as effective as or more effective than conventional organotin compounds.

〔Effect of the invention〕

As explained in detail above, by using the antifouling agent composition of the present invention, it has an effect equal to or greater than that of conventional organotin-based antifouling agent compositions, and is also safe for humans and animals. This has significantly reduced concerns about environmental pollution.

Claims (1)

[Claims] 1. General formula (I) ▲ Numerical formulas, chemical formulas, tables, etc. ▼ (I) (In the formula, R is a lower alkyl group having 4 or less carbon atoms, a cyclohexyl group, a trichloromethyl group, an ethoxycarbonyl group ,
one or more compounds represented by (representing isopropoxycarbonyl group) and one dithiocarbamate compound
An underwater antifouling agent composition characterized in that it simultaneously contains one or more species as antifouling active ingredients. 2. General formula (I) ▲Mathematical formulas, chemical formulas, tables, etc.▼(I) (In the formula, R is a lower alkyl group having 4 or less carbon atoms, a cyclohexyl group, a trichloromethyl group, an ethoxycarbonyl group,
one or more compounds represented by (representing isopropoxycarbonyl group) and one dithiocarbamate compound
An antifouling agent composition for fishing nets, characterized in that it simultaneously contains one or more species as antifouling active ingredients. 3. General formula (I) ▲Mathematical formulas, chemical formulas, tables, etc.▼(I) (In the formula, R is a lower alkyl group having 4 or less carbon atoms, a cyclohexyl group, a trichloromethyl group, an ethoxycarbonyl group,
one or more compounds represented by (representing isopropoxycarbonyl group) and one dithiocarbamate compound
An antifouling agent composition for marine structures, characterized in that it simultaneously contains one or more species as antifouling active ingredients. 4. General formula (I) ▲There are mathematical formulas, chemical formulas, tables, etc.▼(I) (In the formula, R is a lower alkyl group having 4 or less carbon atoms, a cyclohexyl group, a trichloromethyl group, an ethoxycarbonyl group,
one or more compounds represented by (representing isopropoxycarbonyl group) and one dithiocarbamate compound
An antifouling composition for ships, characterized in that it simultaneously contains one or more species as antifouling active ingredients. 5. The antifouling composition according to any one of claims 1 to 4, wherein the dithiocarbamate compound is tetra-lower alkylthiuram monosulfide or tetra-lower alkyl disulfide. 6. The dithiocarbamate-based compound is a lower alkylene bisdithiocarbamic acid heavy metal salt, a metal composite lower alkylene bisdithiocarbamic acid heavy metal salt, a monofunctional lower alkyldithiocarbamic acid heavy metal salt, a lower alkylene bisdithiocarbamic acid and a monofunctional lower alkyldithiocarbamic acid are combined via a heavy metal. The antifouling agent composition according to any one of claims 1 to 4, which is a heavy metal salt or a mixed metal salt thereof.