JPS5833272B2 - Antifouling paint for underwater pests - Google Patents

Description

Detailed Description of the Invention The present invention is based on the general formula (wherein, X represents NO2 or halogen, and m is 0-2
An integer of 1.2, n indicates an integer of 0.1.

) The present invention relates to a paint for preventing fouling of underwater harmful organisms, which is characterized by containing a furan compound represented by the above general formula. The present invention provides a method for preventing underwater harmful organisms from adhering to structures, equipment, fishing nets, etc. by injecting or applying the compound to structures, equipment, fishing nets, etc.

Currently, ships, underwater structures, equipment, machinery, etc. are contaminated with shellfish and seaweed such as mussels, Fujibo, oysters, hydrozoa, or bacteria and molds, such as bryozoans, bryozoans, Ulva, Aonori, Shiomidro, and Itahoya. The particles have adhered to the vessel and are causing trouble to ship operations or inconvenience in handling.

Conventionally, paints containing metal compounds such as tin, mercury, copper, and arsenic have been used as antifouling paints for ships and underwater structures, but these paints corrode ship hull materials and cause stains in harbor water. It was not desirable because it reacted with hydrogen sulfide.

However, the present inventors have discovered that the furan-based compound represented by the above general formula not only has low toxicity to humans and animals, but also has extremely low toxicity to fish and edible shellfish, is extremely easy to handle, and is soluble in water. The amount is extremely small;
It was discovered that the paint exhibits stable effects over a long period of time, and the antifouling paint for aquatic pests of the present invention has been completed.

When the underwater antifouling paint of the present invention is used for fishing net antifouling,
It is extremely effective because its antifouling effect lasts for a long time and the amount leached into seawater is extremely small.

In order to use the furan-based compound of the present invention as an antifouling paint by mixing it with a paint,
Add 60%, preferably 10-50%.

A commonly used paint film type bottom material is used.

That is, oil varnish, plastic, synthetic resin, artificial rubber, or a product prepared by crushing and blending pigments and extender pigments therein and mixing and stirring the mixture is used.

The addition method can be carried out in accordance with the conventional manufacturing method of antifouling paints, and the furan compound and other components may be mixed or pulverized and added, or they may be added after being dissolved in a solvent.

It is also used for antifouling fishing nets (in this case, a fixing agent mainly composed of an appropriate synthetic resin is used to adhere and retain the compound of the present invention on fishing nets made of polyethylene, polyvinylidene chloride, nylon, polyester, etc.). Formulated.

These fixing agents are commonly used ones such as acrylic ester resins and acrylic ester-vinyl acetate copolymer resins, and are not particularly limited.

If these fixing agents are solvent-type, they can be formulated by dissolving the compound of the present invention and using an organic solvent that is compatible with the fixing agent.

If it is an emulsion type, it may be appropriately mixed with an emulsion of the compound of the present invention, or the compound of the present invention may be finely ground and suspended in an emulsion to form a formulation.

Moreover, a plasticizer and other auxiliary agents can be used together if necessary.

That is, in the case of a solvent-type fixing agent, the antifouling agent of the present invention contains 10 to 30 parts by weight of the compound of the present invention, 10 to 30 parts by weight of the fixing agent, 20 to 40 parts by weight of an organic solvent for dissolving these, and 1 part by weight of other adjuvants. It can be produced by mixing in a proportion of ~5 parts by weight, but preferably 15 to 25 parts by weight and 15 to 25 parts by weight, respectively.
Parts by weight, 20 to 30 parts by weight, and 2 to 3 parts by weight.

In the case of an emulsion-type fixing agent, water can be used instead of an organic solvent, and if a thickener is used among other auxiliary agents, it can be produced at the same proportions as above.

Next, a formulation example will be shown.

Note that % is a weight percentage. Formulation Example 1゜A paint is prepared by kneading each component in a mixing ratio of 15% of paint compound (3), 65% of vinyl resin varnish, 10% of aluminum powder, and 10% of red yellow lead using a kneading machine.

Formulation example 2゜Paint compound 4) 15%, red iron oxide 15%, talc 10%, aluminum stearate 0.5%, graphite 0.5
%, rosin 29%, boiled oil 12%, and solvent naphtha 18% by kneading each component in a kneading machine to form a paint.

Formulation Example 3゜The ingredients are kneaded in a kneading machine at a mixing ratio of 15% paint compound (6), 59% phenol resin varnish, 13% aluminum powder, and 13% yellow lead to form a paint.

Formulation Example 4゜A paint is prepared by kneading each component in a mixing ratio of 10% of paint compound (8), 65% of vinyl chloride resin, 12% of aluminum powder, and 13% of Bengara using a kneading machine.

Formulation Example 5゜A paint is prepared by kneading each component in a mixing ratio of 10% of paint compound (2), 65% of vinyl chloride resin, 12% of aluminum powder, and 13% of Bengara using a kneading machine.

Formulation example 6゜Paint compound (10) 13%, Yellow yellow lead 13%, Shining green 2%, Prussian blue 0.5%, Talc 7%, Aluminum stearate 1%, Rosin 29%, Boil oil 13%, Solvent naphtha Each component was kneaded using a kneader at a blending ratio of 21.5% to form a paint.

Formulation example 7゜Paint compound (7) 15%, titanium white 18%, yellow lead 7%, shanine green 3%, vinyl resin 14.5%, rosin 1
0%, Methyl Isobutyl Ketone 15%, Quijirole 17
．． 2% of tricresyl phosphate and 0.3% of tricresyl phosphate are kneaded using a kneading machine to form a paint.

Formulation Example 8゜15% of paint compound (1), 15% of acrylic acid ester resin and 30% of thinner were uniformly dissolved to prepare a paint.

Formulation Example 9 15% of paint compound (2), 15% of ethylene-vinyl acetate copolymer resin, and 30% of thinner were uniformly dissolved to prepare a paint.

Formulation Example A paint was prepared by uniformly dissolving 15% of a 10° paint compound (1 m3), 15% of an acrylic acid ester-vinyl acetate copolymer resin emulsion, and 30% of a thinner.

These formulation examples specifically describe a method particularly effective for the purpose of the present invention, and are not limited to these, and various formulation examples are possible.

Examples of furan compounds that can be used in the paint of the present invention include the following.

These compounds are obtained by a combination of nitration or decarboxylation of substituted or unsubstituted furancarboxylic acids.

For example, nitration of furan-2-carboxylic acid with sulfuric acid and nitric acid yields 2-nitrofuran and 2,5-dinitrofuran, and nitration of 2-methylfuran with acetic anhydride and nitric acid yields 2-methyl-5-dinitrofuran. Trofuran can be manufactured.

This will be explained using the following test example.

Test example 1゜The paint of formulation example 8 was applied to polyethylene fishing nets (50 pieces, 8 sections)
After air-drying, the coating was hung 0.5 to 2.0 m below the sea surface for 3 months to observe the state of adhesion over time.

Tests were conducted periodically.

Efficacy was determined in stages according to the status of attachment of attached organisms as follows.

The test results are shown in Table 1.

: Almost no sessile organisms are observed±: Slightly sessile organisms are observed+: A small amount of sessile organisms are observed 1+-1-1++-: A large amount of sessile organisms are observed Untreated area In the case where cuprous oxide and copper naphthenate were used as a control, there was a lot of attachment of barnacles and green algae, whereas in the case of the compound of the present invention and TBTO, there were only a few of these attached organisms, and slime was the main attachment. It was a kimono.

Test Example 2 The paints of Formulation Examples 9 and 10 were applied to polyethylene fishing nets (
After air-drying, the mixture was hung 0.5 to 2 m below the sea surface for 3 months to observe the state of adhesion over time.

The tests were conducted from summer to autumn, and control plots were set up for each period.

TBTO in the control group was mixed with an emulsion using an emulsion.

Efficacy was determined in the same manner as in Test Example 1, depending on the attachment status of attached organisms.

The test results are shown in Tables 2 and 3.

In the non-treated area and in the control area using cuprous oxide and copper naphthenate, there were a lot of attaching organisms such as barnacles, staghorn beetles, cypress beetles, and hydra, whereas in the inventive compound and TBTO areas, there were only a few of these attached organisms. There, slime was the main sessile organism.

It can be seen from the above examples that the compounds of the present invention have excellent antifouling properties.

Test Example 3゜The ingredients blended according to Formulation Example 7 are kneaded using a kneading machine to form a product.

After applying the antifouling paint containing the furan-based compound of the present invention or the antifouling paint containing cuprous oxide of the present invention twice on polished steel of 300 x 100 x 1 (mm) once with wash primer and twice with ship bottom paint No. 1 (commercial product), 1.5 from the immersion raft fitted into a wooden frame
Immerse yourself in the sea at a depth of m.

Next, this test coated board was immersed in seawater and pulled up at regular intervals, and the area of living organisms adhering to the board was measured.

The results are shown in Table 4. Display is in percentage. The untreated area is the area where wash primer and boat bottom paint No. 1 were applied.

In the area where the paint of the present invention was used, adhesion of algae and shellfish could be sufficiently prevented, and the painted surface was also in good condition.

Claims (1)

[Claims] 1 General formula (where X represents NO2 or halogen, m is 0.1
, 2, and n is an integer of 0.1. ) An antifouling paint for aquatic pests, characterized by containing a furan-based compound shown in (a).