JPS5918363B2 - aquatic creature repellent - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention is applicable to underwater structures such as the bottom of ships, fishing nets, buoys and other underwater structures, dam auxiliary equipment, cooling water intake channels for thermal power plants, cooling water for chemical industries, etc. This invention relates to a new aquatic organism repellent that prevents harmful aquatic organisms from adhering to and multiplying.

Parts that are in constant contact with water, such as the lower parts of ships, equipment placed in the sea, underwater structures, and cooling water intake channels, are exposed to fujibo, oysters, mussels, hydrobugs, serpura, bryozoans, sea squirts, bulrushes, sea lettuce, Shellfish and algae, such as blue laver and seaweed, propagate, and these attached organisms increase fluid resistance, reduce thermal conductivity, and cause unfavorable conditions such as deterioration of equipment functionality.

Conventionally, in order to prevent problems caused by attached growth of seawater and freshwater harmful organisms, heavy metal compounds such as copper oxide and mercury oxide, organotin compounds such as tributyltin oxide, organochlorine or organosulfur compounds, and Resistant paints containing arsenic compounds such as narsazine chloride are used.

Furthermore, in intake channels for cooling water, etc., chlorine, formalin, etc. have been added directly to the channels to prevent the attachment and propagation of aquatic organisms.

However, antifouling paints containing heavy metal compounds such as copper oxides and mercury oxides have the disadvantage of poor storage stability because the metal oxides contained tend to react with the surface components in the paint.

In addition, in contaminated sea areas such as ports where industrial sewage flows, hydrogen sulfide generated by the action of microorganisms in the contaminated water causes discoloration and deterioration, resulting in inconveniences such as loss of efficacy.

In addition, copper and mercury-based inorganic compounds are effective against seawater organisms such as barnacles, sea squirts, coelomates, and bryozoans, but
It has little effect on algae.

Furthermore, when applied to a light metal material mainly composed of aluminum, magnesium, etc., metals such as copper and mercury in the paint may precipitate on the material and accelerate electrochemical corrosion of the material.

Next, antifouling paints containing organotin compounds such as tributyltin oxide are less effective and more expensive than antifouling paints containing oxides of copper and mercury.

In addition, if used in large quantities, the performance of the coating film will deteriorate, and a bad odor will be produced during handling.

In addition, conventional antifouling paints containing organic chlorine or organic sulfur compounds are less effective; for example, they may be effective against bryozoans but not against barnacles, so they may not be effective against pests. It was so vague that it could hardly be put to practical use.

Furthermore, antifouling paints containing phenarsazine chloride (Adamsite) have been used, but phenarsazine chloride is extremely irritating to human mucous membranes, making it difficult to manufacture and paint the paint.

Furthermore, if chlorine or formalin is added to the cooling water intake channel, the cooling device will be corroded, and the effect of preventing the attachment of organisms in the water will not be excellent.

What is more important is that the active ingredients in the above antifouling paints include organic chlorine compounds and heavy metal compounds, and these compounds are highly toxic to humans and fish, and there are significant restrictions on their use. Met.

The present inventors have also proposed an aquatic organism repellent containing a succinimide compound as an active ingredient (Japanese Patent Application Laid-open No. 50-67329, 51-17917).

However, in this case as well, the succinimide compound as an active ingredient was required to be a halogen-containing compound.

The present inventors have conducted various studies to solve the drawbacks of conventional antifouling paints and chemicals as described above, and have found that N-(
Substituted phenyl)maleimides have extremely low toxicity;
Among them, products containing N-(substituted phenyl)maleimide, which has a phenyl group introduced with a group such as an alkyl group or an alkoxy group, surprisingly have an excellent repellent effect on aquatic organisms even though they do not contain halogen atoms. We have discovered that it is possible to prepare an antifouling paint that is safe for humans and has extremely low toxicity to fish.

The present invention has been made based on this knowledge.

That is, the present invention relates to the general formula (wherein Y1 and Y2 represent a hydrogen atom, an alkyl group, a lower alkokene group, a nitro group, a hydroxyl group, a carboxyl group, a phenyl group, a phenylamino group, an alkenyl group, or a thiocyano group, and both of them are It cannot be a hydrogen atom at the same time,
When one is a hydroxyl group or a carboxy group, the other is a carboxyl group or a hydroxyl group, respectively.

The present invention provides an aquatic organism repellent characterized by containing an N-arylmaleimide compound represented by the following as an active ingredient.

The above general formula C which is an active ingredient of the aquatic organism repellent of the present invention
The N-arylmaleimide compounds represented by I) are shown in the table below as compound numbers 1 to 20.

Note that compound numbers 21 to 23 are control compounds.

These compound numbers are referred to in the Examples below.

The N-arylmaleimide represented by the general formula CI) used as the active ingredient of the aquatic organism repellent in the present invention can be prepared by combining maleic anhydride and aromatic amines in a solvent or without using a solvent. The reaction was carried out at a temperature of 100°C for 0.5 to 2 hours, and the resulting reaction solution was reacted at a temperature of 80 to 200°C in the presence of an acid catalyst without isolating the produced N-arylmaleimide acids. It can be produced in high yield by reacting for 1 to 10 hours and dehydrating and ring-closing.

The aquatic organism repellent of the present invention is prepared and used in the form of a paint, solution, emulsion, or the like.

For example, by preparing an antifouling paint by blending one or more of the compounds of the general formula [■] with a film forming agent, and applying this to the bottom of a ship, an underwater structure, or the wall of a cooling water intake passage. Adhesive propagation of aquatic organisms can be prevented.

Examples of the film forming agent used in this case include oil varnish, synthetic resin, and artificial rubber.

Pigments and extender pigments can be added to the antifouling paint as desired.

In this case, the compound of general formula [■] is blended in an amount of 5 to 80%, preferably 10 to 50%, based on the weight of the coating film forming agent.

For the purpose of preventing the growth of aquatic organisms in the cooling water intake channels, the compound of general formula CI) may be added into the intake channels in the form of a solution or emulsion.

However, in order to maintain the antifouling effect for a long time, it is desirable to apply it in the form of a paint.

In addition, when applying the aquatic organism repellent of the present invention to fishing nets, the compound of general formula [■] is dissolved in an organic solvent together with a resin to form a resin solution, and the fishing nets are impregnated with this resin solution and dried.

When preparing this resin solution, the compound of general formula [■] should be contained in an amount of 1 to 10% by weight, preferably 1 to 6% by weight, and the resin should be contained in an amount of 5% by weight.
It is dissolved in an organic solvent at a concentration of ~15% by weight, preferably 7-12% by weight.

Within this range, the effect hardly changes even if the concentration of the compound of general formula CI,l is changed.

Examples of the resin used for preparing the resin solution include vinyl chloride resin, phenol resin, alkyd resin, and chlorinated rubber.

In addition, organic solvents such as Hensen, toluene, xylene, and chloroform are used, but they do not dissolve the resin (
If not, dimethylformamide, dimethylacetamide or dimethylsulfoxide may be mixed in an amount of 5 to 15% by volume.

There are no particular restrictions on the material of fishing nets that can be treated with the aquatic organism repellent of the present invention.

For example, natural fibers such as cotton, linen, silk, wool, polyvinyl chloride, polyvinyl alcohol, polyvinylidene chloride,
It can be applied to fishing nets made of synthetic fibers such as polyfluoroethylene, polyamide, polyethylene, polypropylene, polystyrene, polyacrylonitrile.

The aquatic organism repellent of the present invention contains a heavy metal compound as an active ingredient,
Although it does not contain organic chlorine compounds, it exhibits excellent aquatic organism repellent effects over a long period of time, and is extremely effective in practice as a safe aquatic organism repellent with low toxicity to the human body and fish.

Furthermore, unlike paints containing heavy metal compounds as active ingredients, the antifouling paints containing the N-(substituted phenyl)maleimide compound of the present invention do not deteriorate in quality even in sea areas contaminated with industrial sewage, and are stable at attracting aquatic organisms. Shows preventive effect.

Furthermore, even when applied to light metal materials such as aluminum and magnesium, it does not electrochemically corrode the metal materials at all, and when applied to the walls of intake channels for cooling water, etc., it corrodes cooling equipment. There's no fear.

Next, the aquatic organism repellent of the present invention will be explained in more detail based on Examples.

Synthesis Example: In a 500 rnl fourth flask equipped with a thermometer, a condenser with a water separator, a dropping funnel and a stirrer, 1 xylene was added.
Pour 50ml and add 19.6f of maleic anhydride to this.
(0.2 mol) was added and dissolved.

Then, a solution of p-)luidine 21.4y (o, 2 mol) dissolved in xylene 100IrLl was added dropwise to the mixture under stirring at room temperature.

Although heat was generated at the same time as the dropwise addition, the temperature was maintained at 60 to 68°C after the dropwise addition, and the reaction was allowed to proceed for 2 hours with stirring.

Then, 1.1' (0,0097 mol) of sulfuric acid was added, heated and maintained at 135 to 138°C, and reacted for 4 hours while azeotropically removing water produced by the reaction with stirring.

After the reaction was completed, the xylene was distilled off, and the reaction solution was heated to 500 m
The crystals precipitated by pouring into water of 1 were collected by filtration, recrystallized with ethanol, and N-(p-4lyl)maleimide (compound number (2), m, p, 164-165°C) was obtained at 31.81 ( Yield: 85%).

Example 1 [Paint formulation example 1] Compound number (2) CN-(p-4lyl)maleimide]
were blended in the following proportions, thoroughly ground in a pot mill, and mixed to prepare an antifouling paint.

(% indicates weight%.

Same below) Compound number (2) 20.0%
Bengara 10.0% Talc 15.0% Barium sulfate 20.0% Vinyl resin
5.5% rosin
5.5% tricresyl phosphate 2.0% methyl isobutyl ketone 11.0% xylene
11.0% total 1
00.0% [Paint formulation example 2] Compound number (2) (N-(p-4lyl)maleimide)
were blended in the following proportions, thoroughly ground in a bot mill, and mixed to prepare an antifouling paint.

Compound number (2) 15.0% Bengara
18.0% Talc 10.0% Aluminum Stearate 0.5% Graphite 0.5% Rosin
26.0% boil oil
12.0% solvent naphtha 18
．． 0% Total 100.0% [Marine organisms antifouling immersion test [■]] (1) Preparation of test plate and test method Each steel plate (300 x 100 x 1 mm) was primed once with wash primer and twice with anti-rust paint. Each antifouling paint prepared using each compound shown in Table 1 according to Formulation Example 1 (synthesized according to Synthesis Example) was applied twice with a brush, and each test plate was fitted into a wooden frame. Suspended in the sea and maintained 1.5m below sea level.

(2) Test results As described in (1) above, the coated plate immersed in seawater was pulled up at predetermined intervals, and the amount of biological dust adhering to it was expressed as a percentage of the total adhesion area, as shown in Table 2. Indicated.

Note that "no treatment" refers to treatment with only a wash primer and a chemical-free antirust paint.

[Marine Organism Antifouling Immersion Test [■]] Test plates were prepared in the same manner as the Marine Organism Antifouling Immersion Test (IL) using the antifouling paint prepared using each compound in Table 1 according to Formulation Example 2. An underwater immersion test was conducted using the same method.

The results are shown in Table 3 together with the results of comparative examples conducted in the same manner.

This result shows that the aquatic organism repellent of the present invention can maintain its efficacy over a long period of time, compared to the case of the control compound, which rapidly loses its efficacy.

Example 2 Antifouling treatment of fishing nets (1) (1) Preparation of resin solution Compound No. (2) (N-(p-tolyl)maleimide)
was mixed with the following ingredients and thoroughly stirred to prepare a resin solution.

Compound No. (2) 8% Chlorinated rubber 5% Rosin 2% Toluene 85% Total 100% (2) Processing method Polyamide fiber (manufactured by Toshi Co., Ltd.: trade name Amiran) is added to the resin solution prepared in 0) above. ) A fishing net with 11 sections (3.03 cm mesh) was soaked in the net, sufficiently impregnated, and then air-dried for 12 hours for antifouling treatment.

Example 3 Antifouling treatment of fishing nets (2) (1) Preparation of resin solution Compound No. 2) CN-(p-4lyl)maleimide] was blended in the following proportions and sufficiently stirred to prepare a resin solution.

Compound No. (2) 5% Vinyl resin 5% Rosin 5% Xylene 85% Total 100% (2) Processing method Using the resin solution prepared in 1), the method of Example 2 (
Antifouling treatment was applied in the same manner as in 2).

Example 4 Fishing net antifouling test Using the N-arylmaleimide compound synthesized according to the synthesis example described above, a resin solution was prepared in the same manner as in Example 2, and a fishing net was antifouled and subjected to an antifouling test. .

(1) Test method Cut a test piece into a size of 50 x 50 cIrL from each antifouling fishing net, stretch it on a 60 x 60 iron frame, suspend it in the sea from a dipping raft, and maintain it 1.5 m below the sea surface. do.

(2) Test results As described in (1) above, fishing nets immersed in seawater were pulled up at predetermined intervals, and the state of adhesion of seaweed, sea lettuce, fluff, hydro, sea squirt, etc. was observed and measured.

The results are shown in Table 4. The evaluation symbols in this table have the following meanings.

- No adhesion at all ± Scattered attachment ＋ A small amount of adhesion throughout the net Ox A large amount adheres to the entire net.

Claims (1)

[Scope of Claims] 1 General formula (wherein Y1 and Y2 represent a hydrogen atom, an alkyl group, a lower alkoxy group, a nitro group, a hydroxyl group, a carboxyl group, a phenyl group, a phenylamino group, an alkenyl group or a thiocyano group, Both cannot be hydrogen atoms at the same time,
When one is a hydroxyl group or a carboxy group, the other is a carboxyl group or a hydroxyl group, respectively. 1. An aquatic organism repellent comprising an N-arylmanimide compound represented by the following as an active ingredient.