JPH06128508A - Coating material for preventing adhesion of marine organism - Google Patents

Abstract

PURPOSE:To provide a coating material for effectively protecting marine structures, such as a ship and a fishing net, from fouling organisms. CONSTITUTION:The coating material contains a triarylbismuth compound of the formula as the antifouling component. In the formula, X is 1-6C alkyl, alkoxy, vinyl, phenyl, nitro, N,N-dimethylamino or H; and Y is 1-6C alkyl, alkoxy or H.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a triary for protecting marine structures such as ships and fishing nets from fouling organisms.
Provided is a marine organism adhesion preventing paint containing a rubismuth compound as an antifouling component.

[0002]

2. Description of the Related Art Ship bottoms, fishing nets such as aquaculture nets and set nets, or seaweeds such as sea lettuce, blue seaweed, brown algae, barnacles, serpla, hydra, warecara, leaf worm, blue mussel, squirt, oyster, etc. Marine animals attach to them and cause various harmful effects. For example, with respect to ships, the adhesion of marine organisms increases the frictional resistance of the ship, which reduces the navigation speed and increases the fuel consumption. As for fishing nets such as aquaculture nets and set nets, the nets are clogged and the distribution of seawater is hindered, resulting in poor growth of fish and shellfish and choking death due to lack of oxygen.

In order to prevent such adverse effects, resin compositions such as organotin polymers, organotin compounds such as bis (tributyltin) oxide and triphenyltin hydroxide, cuprous oxide and thiocyanic acid have hitherto been used. Copper compounds such as cuprous and thiocarbamate compounds such as zinc salts and manganese salts of ethylenebisdithiocarbamic acid have been used as antifouling components. Furthermore, in recent years, marine organism adhesion preventing paints containing organic nitrogen-sulfur compounds such as tetrachloroisophthalonitrile and diuron as antifouling components have also begun to be used.

[0004]

However, the above-mentioned tin compounds are designated as specific or designated chemical substances,
Its use is limited, while copper compounds, thiocarb
The use of bamate compounds is also being limited, and the antifouling effect is still insufficient for organic nitrogen-sulfur compounds. Under such circumstances, the fishing net / shipping industry is required to develop a safe marine organism adhesion-preventing paint having excellent antifouling effect.

On the other hand, due to the regulation of the use of organic tin-based anti-adhesive organism coatings for fishing nets, Benedenia seriola was found on the surface of cultured fish such as yellowtail and yellowtail.
A new problem has occurred that e) is parasitic. When the beetle parasitizes, cultured fish such as yellowtail and yellowtail rub the fish body against the aquaculture net, damaging the surface of the fish body, resulting in a significant decrease in commercial value, and on the other hand, susceptibility to infection by pathogenic bacteria, which in turn leads to disease death of the cultured fish. May be invited.

[0006]

[Means for Solving the Problems] Therefore, as a result of diligent studies, the present inventors have found that a marine organism adhesion-preventing coating material containing a triarylbismuth compound as an antifouling component exerts an excellent antifouling effect, and a fishing net. If used for, the beetle (Benedenia seriola) on the surface of cultured fish
The inventors have found that the parasitic of e) can be effectively prevented and have reached the present invention.

That is, the present invention has the general formula [1]

[Chemical 3] (In the formula, X is an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, a vinyl group, a phenyl group, a nitro group, an N, N-dimethylamino group or a hydrogen atom, and Y is
A marine organism attachment-preventing coating material containing a triarylbismuth compound represented by an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms or a hydrogen atom) as an antifouling component. Is.

The triarylbismuth compound (general formula [1]) according to the present invention is prepared by preparing a Grignard reagent from an aromatic halide as shown in the following chemical reaction formula, and then preparing a trihalogenated bismuth halide. Can be easily synthesized by carrying out a redistribution reaction with

[Chemical 4] (In the formula, Z represents a chlorine atom or a bromine atom, and X and Y have the same meaning as described above.)

Examples of the triarylbismuth represented by the general formula [1] include tri (2,4-dimethylphenyl) bismuth, tri (2,5-dimethylphenyl) bismuth and tri (2-methyl-4-). Isopropylphenyl)
Bismuth, tri (2-methyl-5-isopropylphenyl) bismuth, tri (2-methyl-4-isoamylphenyl) bismuth, tri (2-ethyl-5-butoxyphenyl) bismuth, tri (2,4-dimethoxyphenyl)
Bismuth, tri (2,5-diethoxyphenyl) bismuth, tri (3,5-dinitrophenyl) bismuth, tri (2-ethoxy-4-hexylphenyl) bismuth, tri (2-methylphenyl) bismuth, tri (3 -Methylphenyl) bismuth, tri (4-methylphenyl) bismuth, tri (2-ethylphenyl) bismuth, tri (4
-Ethylphenyl) bismuth, tri (4-isopropylphenyl) bismuth, tri (4-tert-butylphenyl) bismuth, tri (4-hexylphenyl) bismuth, tri (4-isoamylphenyl) bismuth, tri (2-methoxyphenyl) ) Bismuth, tri (4-methoxyphenyl) bismuth, tri (4-ethoxyphenyl)
Bismuth, tri (4-vinylphenyl) bismuth, tri (3-nitrophenyl) bismuth, tri (4-dimethylaminophenyl) bismuth, tribiphenylbismuth,
Examples thereof include triphenylbismuth, and these triarylbismuths can be used alone or in combination to form an antifouling component. The triarylbismuth compound according to the present invention is preferably added in an amount of 0.1 to 30% by weight with respect to the resin composition used in the marine organism adhesion preventing paint.

Next, the marine organism adhesion preventing paint of the present invention comprises a triarylbismuth compound represented by the general formula [1] as a main antifouling component, but has a killing or repelling action on marine fouling organisms. An existing antifouling agent having a can be used in combination as a secondary antifouling component. Examples of existing antifouling agents include copper compounds such as cuprous oxide, copper rhodanide, copper powder, cuprous naphthenate and cuprous thiocyanate, zinc dithiocarbamate, zinc compounds such as zinc pyrithione, N
Maleimide compounds such as-(2,6-diethylphenyl) -2,3-dichloromaleimide, urea compounds such as 3,4-dichlorophenyl-1,1-dimethylurea,
Examples thereof include organic nitrogen-sulfur compounds such as 3,4-dichlorophenylisothiocyanate and 2-thiocyanomethylthiobenzothiazole, thiuram compounds, phthalimide compounds and tetrachloroisophthalonitrile.

The resin composition used in the marine organism adhesion preventing paint of the present invention is sufficient if it can be easily mixed with the triarylbismuth compound of the present invention to form a coating film. Known resin compositions include, for example, pine resin drying oil, so-called oily vehicles such as terpenes, alkyd resins, chlorinated rubber resins, vinyl chloride-vinyl acetate copolymer resins, rubber elastic resins such as styrene-butadiene, polybutene, Olefin-based resins such as polyisobutylene, phenol-based resins, vinyl alkyl ether-based resins, methacrylic resins, acrylic resins, silicone resins and the like, and as a resin for the marine organism adhesion prevention coating of the present invention. They can be used alone or in combination of two or more.

Further, in order to modify the physical properties of the surface coating film of the biofouling-preventing paint, or to maintain the antifouling performance for a long period of time, the marine biofouling-preventing paint of the present invention is optionally added. , Dimethyl silicone oil, methylphenyl silicone oil, polyether modified silicone oil, alkyl modified silicone oil and other silicone oils, beeswax, paraffin wax, microcrystalline wax and other solid paraffins, white petrolatum and the like. Water-repellent agent, titanium oxide, zinc white, red iron oxide, carbon black, pigments such as phthalocyanine blue, oil blue,
Dyes such as oil red, fillers such as bentonite and talc, desiccants such as manganese naphthenate and cobalt naphthenate, plasticizers such as liquid paraffin, chlorinated paraffin and tricresyl phosphate, thickeners such as hydrogenated castor oil Etc. can be added and used.

[0013]

EXAMPLES Next, the present invention will be described with reference to examples, and% and parts in each example represent% by weight and parts by weight, respectively. The melting point was measured using a melting point measuring device manufactured by Metra Co., and the bismuth content was measured by a dry ashing method (gravimetric method).

1. Production of Triaryl Bismuth Production Example 1 1l equipped with a thermometer, reflux condenser, dropping funnel and stirrer
13.3 g of Mg was placed in the three-necked flask of No. 3 and o-chlorotoluene 6 dissolved in 150 ml of THF (tetrahydrofuran) was added from a dropping funnel while performing nitrogen substitution and stirring.
9.9 g was added dropwise under gentle reflux over 1 hour.
After the dropping was completed, the reaction was further continued under reflux for 3 hours. Then bismuth trichloride 49.
6 g was added dropwise while maintaining the internal temperature at 30 ° C., and after completion of the addition, reaction was carried out under reflux for 3 hours. After the reaction was completed, 200 ml of a saturated aqueous solution of ammonium chloride was added, the organic layer was collected by separating and filtering, and THF was distilled off to obtain a crude product. Recrystallization was performed using a mixed solvent of chloroform / methanol, and tri (2-methylphenyl) bismuth (Compound A) 59.
2 g was obtained (yield 78%, melting point 132 ° C., Bi content 4
3.7%).

Production Example 2 In the same manner as in Production Example 1, o-chlorotoluene 69.9 was used.
Instead of 8 g, 86.5 g of o-chlorophenetol was used for the reaction. Then, after reacting with bismuth trichloride for 3 hours in the same manner as in Production Example 1, the crude product was recrystallized with a mixed solvent of chloroform / methanol to give tri (2-
57.6 g of ethoxyphenyl) bismuth (compound B) was obtained (yield 64%, melting point 123 ° C., Bi content 36.4).
%).

Production Example 3 In the same manner as in Production Example 1, o-chlorotoluene 69.9 was used.
2,5-dimethyl-chlorobenzene 77 instead of g.
The reaction was carried out using 6 g. Then, after reacting with bismuth trichloride for 3 hours in the same manner as in Production Example 1, the crude product was recrystallized with a mixed solvent of chloroform / hexane to give tri (2,5-dimethylphenyl) bismuth (compound C )
44.2 g was obtained (yield 54%, melting point 194.5 ° C., B
i content 39.6%).

Production Example 4 In the same manner as in Production Example 1, o-chlorotoluene 69.9 was used.
p-bromo-N, N-dimethylaniline 1 instead of g
The reaction was carried out using 10.5 g. Then, after reacting with bismuth trichloride for 8 hours in the same manner as in Production Example 1, the crude product was recrystallized with a mixed solvent of chloroform / methanol to give tri (4-dimethylaminophenyl) bismuth (compound D) 56.1 g was obtained (yield 63%, melting point 21).
6 ° C., Bi content 36.5%).

Production Example 5 In the same manner as in Production Example 1, o-chlorotoluene 69.9 was used.
The reaction was carried out using 62.0 g of chlorobenzene instead of g. Then, after reacting with bismuth trichloride for 3 hours in the same manner as in Production Example 1, the crude product was recrystallized with a mixed solvent of chloroform / methanol to give 51.0 g of triphenylbismuth (Compound E). Obtained (yield 74%, melting point 7
8 ° C., Bi content 47.1%).

2. Preparation of Ship Bottom Paint Example 1-10 and Comparative Example 1-2 Triarylbismuth (Compound A-) obtained in Production Example 1-5
E) was used to prepare a bottom coating according to the formulation in Table 1.

[Table 1] * 1 Nitto Kasei Co., Ltd .: trade name NT-100 * 2 BASF Co., Ltd .: trade name Laroflex MP-4
5 * 3 Union Carbide Co., Ltd .: trade name VYHH * 4 Kusumoto Kasei Co., Ltd .: trade name DISPARON # 4300

3. Preparation of paint for fishing nets Triaryl bismuth obtained in Production Example 1-5 (Compound A-
Using E), a coating material for fishing nets was prepared according to the formulation shown in Table 2.

[Table 2] * 5 Nitto Kasei Co., Ltd .: trade name Nittoru A * 6 Nitto Kasei Co., Ltd .: trade name Nittoru B * 7 Shell Chemical Co., Ltd .: trade name TR-1107 * 8 Idemitsu Petrochemical Co., Ltd .: Trade name Polybutene 10H * 9 Shin-Etsu Chemical Co., Ltd .: trade name KF-96 * 10 Shin-Etsu Chemical Co., Ltd .: trade name KF-354 * 11 Kusumoto Kasei Co., Ltd .: trade name DISPARON # 420
0-10 * 12 Kusumoto Kasei Co., Ltd .: Trade name Disparon # 690
0-20X

[0021] 4. Antifouling Test of Ship Bottom Paint The ship bottom paints of Examples 1-10 and Comparative Example 1-2 of the present invention were uniformly applied twice with a brush to both sides of a hard vinyl chloride resin plate (20 cm x 10 cm). The test plate was immersed in 1.5 m below the sea level in Owase Bay, Mie Prefecture, and the degree of fouling of the test plate by marine attached organisms was observed for 18 months. Third immersion result
Shown in the table. The numbers in the table indicate the area of attachment of fouling organisms (%).

[Table 3]

5. Antifouling test of paint for fishing nets 5 pieces of polyethylene fishing net pieces (30 cm x 30 cm) were added to the paints for fishing nets of Examples 11-17 and Comparative Example 3-4 of the present invention.
After soaking for 1 minute, it was dried at room temperature for 1 day and used as a test net. . This test net was dipped in 1.5 m below the sea level in Owase Bay, Mie Prefecture, and the degree of fouling of the test net by marine attached organisms was observed for 6 months. Evaluate the immersion result based on the following criteria,
It is shown in Table 4. ⊚: No fouling organisms adhered or only slime adhered. ◯: Fouling organisms adhere slightly, but there is no problem in using it as a farming net. B: Due to the attachment of fouling organisms, it is difficult to withstand use as a culture net. X: A large amount of fouling organisms adhered, and it cannot be used as a farming net.

[Table 4]

6. Antifouling test using aquaculture nets Fishing net paints of Example 11 and Comparative Example 4 of the present invention (60 for each)
Each of 5 m × 5 m × 3 m aquaculture net was dyed with the preparation of kg. Next, we constructed a raft in Owase Bay, Mie Prefecture, attached weights to the four sides of the aquaculture net, and submerged it in the sea to make a cage. Then,
Hamachi, a fish weighing about 1 kg and free from wasps 15
Fifteen hamas, which were already infested with the beetle and the beetle, were placed in their respective cages (30 in total) and cultured for 3 months. After three months, the aquaculture net was pulled up and the growth status of the yellowtail (the degree of parasitism of the beetle, etc.) was observed. Observation result of Example 11 One of 30 fishes had colony-shaped beetle parasitic on the surface of the fish. No parasitism of the beetle was found on the surface of the remaining 29 fish, and the fish weight was 1.6-2.0 kg. ○ Observation result of Comparative Example 4 Colony-like beetle was parasitic on the surface of 25 fish out of 30 fish. No parasitic of the beetle was observed on the surface of the remaining 5 fish bodies. In addition, hade was parasitic 2
The weight of the five fish was 1.1-1.3 kg, which was inferior to the growth of Hamachi, which did not show the parasitic of the beetle.

[0024]

[Effect] The marine organism adhesion preventing paint containing the triarylbismuth compound of the present invention as an antifouling component can be used for a long period of time from the results of the antifouling test of paints for ship bottoms and fishing nets (Tables 3 and 4). It effectively protects marine structures such as ship bottoms from the attachment of fouling organisms, and in the antifouling test of aquaculture nets using cages, it has a remarkable effect on the prevention and control of beetle parasitic on fish.

Claims (1)

[Claims] 1. A general formula [1]: (In the formula, X is an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, a vinyl group, a phenyl group, a nitro group, an N, N-dimethylamino group or a hydrogen atom, and Y is
A marine organism attachment-preventing coating material containing a triarylbismuth compound represented by an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms or a hydrogen atom) as an antifouling component. .