KR860000028B1 - A preventing agent from organisms in water - Google Patents

Abstract

A compn. contg. one or more N-arylmaleimides (I)[X1 and X2 = H or halo; Y = halo, alkyl or alkoxy; n= 0-3! and one or more of organotin compd., such as triphenyltin chloroacetate or triphenyltin hydroxide is an antifouling agent. A steel plate (300x100x1mm) was painted with a compn. contg. N-4-toylmaleimide 18, bis(tri-n-butyl Mn) mesodibromosuccinate 2, red oxide 10, talc 15, BaSO4 20, vinyl resin 5.5, rosin 5.5, tricresylphosphate 2, Me iso-Bu ketone 11, and xylene 11 parts and submerged in seawater for 12mo. The percentage of the steel surface infested with mollusks and algae was between 30 and 10%, whereas corresponding values for an untreated control plate were nearly 100% infestation.

Description

Aquatic repellent

The present invention relates to a mixed aquatic repellent agent based on N-allylmaleimide.

Always under water such as underwater structures such as ship bottoms, fishing nets, mooring buoys, submerged structures such as soldering equipment, water condenser cooling water for thermal power plants, and water intake furnaces for heat exchanger cooling water for various industries. The parts that come in contact with them are: "Fusa Lake", oyster shells, purple clams, hydro-worms, "Selpra", moss insects, sea squirts, cluster moss insects, "Aosa", greens, and "Sionodo-ro". Since shellfish and algae grow and adhere, for example, in ships, not only does the speed of navigation slow down and fuel consumption increases, but also the cleaning cost for cleaning the ship bottom or the ship between these vacuum cleaners. It causes economic loss due to the suspension of operation, and inconvenient handling operation in underwater deliveries. In addition, intake passages such as condensers and heat exchangers reduce water intake and decrease cooling efficiency, By lumps are eliminated from the organism is spilled in the cause of large losses such as to cause degradation of the equipments.

Therefore, conventionally, in order to prevent the interference caused by the adhesion breeding of such seawater and freshwater harmful organisms, heavy metal compounds such as copper oxide, mercury oxide, organotin compounds such as tributyltin oxide, organochlorine or free sulfur compounds, An antifouling paint containing an arsenic compound such as phenarazine chloride or the like is used, and in a water intake of cooling water, a method of adding chlorine or formalin or the like directly to a water channel has been performed.

However, antifouling paints containing heavy metal compounds such as copper oxides and mercury oxides do not have good storage stability because metal oxides easily react with varnish components in the paints, and contaminated areas such as harbors where industrial sewage flows. In Esau, there is a defect in discoloration and deterioration caused by hydrogen sulfide generated by the action of microorganisms in contaminated water. In addition, copper and mercury-based organic compounds have an effect on marine organisms such as "parsaco", sea squirts, tonics, moss bugs, etc., but have little effect on algae. In addition, when applied to a light metal material mainly composed of aluminum, magnesium, and the like, metals such as copper and mercury in the paint are deposited on the material, and there are even defects such as promoting chemical erosion of the material.

Compared with an antifouling paint containing an organic tin compound such as tributyltin oxide, the effect is insufficient and expensive. In addition, when used in a large amount, there is a drawback that deterioration of the coating performance and generation of odor in the collection. Antifouling paints containing organochlorine or organosulfur compounds are inferior to any of the antifouling paints described above, and have no effect on harmful organisms, for example, even though they are effective against mossy insects. It's optional and it's hardly practical.

In addition, the antifouling paints containing phenarazine chloride (Adamsite) are not easy to manufacture and paint because phenarazine chloride itself has severe mucosal stimulation to the human body. In addition, the method of adding chlorine or formalin or the like to the intake path of the cooling water corrodes the cooling device and is inferior in preventing the adhesion of aquatic organisms.

The present inventors have conducted various studies to obtain anti-fouling paints without various defects unique to the anti-fouling paints conventionally used, and found that N-allyl maleimide has an effective aquatic repelling effect as an antifouling paint. It was introduced in Japanese Patent Application No. 51-81476. However, the N-allyl maleades are slightly inferior to shellfish compared to algae, and thus, further studies have been conducted to obtain aquatic repellents having excellent antifouling effect on both shellfish and algae. As a result, bis (tri-n-butyltin) mesodibromosuccinate, trimethyltin monochloroacetate, triphenyltin hydroxide and bis (tri-n-butyltin) oxide were added to N-allyl maleides. By adding a small amount of at least one compound selected from the group of organotin compounds to be found, it was found that the shellfish and algae exhibited excellent anti-adhesion effect to the present invention.

That is, the present invention is a general formula

(Wherein x ₁ and x ₂ are the same or different and each represents a hydrogen atom, a halogen atom, Y represents a halogen atom, an alkyl group or a lower alkoxy group, n represents an integer of 0 or 1 to 3) At least one compound of N-allyl maleimide and bis (tri-n-butyltin) mesodibromosuccinate, triphenyls monochloroacetate, triphenyltin hydroxide and bis (tri-n-butyltin It is an aquatic repellent, characterized in that it contains at least one compound selected from the group of the organotin compound which becomes an oxide as an active ingredient.

As N-allyl maleimide represented by the said general formula (I) used as an active ingredient of the aquatic repellent agent of this invention, N-phenyl maleimide, N-2- (or 3- or 4-) chloro is mentioned, for example. Phenylmaleimide, N-3-bromophenylmaleimide, N-4-iodinephenylmaleimide, N-4-fluorophenylmaleimide, N-2- (or 3- or 4-) tolylmaleimide, N -4-n-butylphenylmaleimide, N-4-dodecylphenylmaleimide, N-3-methoxyphenylmaleimide, N-4-ethoxyphenylmaleimide, N-3-i-propoxyphenylmaleimide Mead, N-2,3- (or 2,5-3,4- or 3,5-) dichlorophenylmaleimide, N-2,3- (or 2,4-, 2,5- or 3,5 Xylylmaleimide, N-2,5-dimethoxyphenylmaleimide, N-phenyl-2-bromomaleimide, N-3-chlorophenyl-2-bromomaleimide, N-3-bromophenyl 2-bromomaleimide, N-3,5-dichlorophenyl-2-bromomaleimide, N-phenyl-2,3-dichloromaleimide, N-phenyl-2,3-dib Lomomaleimide, N-phenyl-2,3-difluoromaleimide, N-2- (or 3- or 4-) chlorophenyl-2,3-dichloromaleimide, N-4-iodinephenyl-2, 3-cyclomaleimide, N-4-chlorophenyl-2,3-difluoromaleimide, N-4-tolyl-2,3-dibromomaleimide, N-4-methoxyphenyl-2, 3-dichloro maleimide, N-2,4,6-trichlorophenyl maleimide, etc. are mentioned, Especially, N-3- chlorophenyl maleimide, N-4-tolyl maleimide, Ni-propoxyphenyl maleimide Mead, N-2,4-xylylmaleimide, N-2,4,6-trichlorophenylmaleimide are suitable as a mixed agent of the aquatic repellent agent of the present invention.

The aquatic repellent agent of the present invention is mixed at a ratio of 80 to 95% of at least one compound of N-allyl maleade and 20 to 5% of at least one compound of an organotin compound, and preferably 60% or less as an active ingredient. It is prepared by using paint, solution, emulsion, etc. so that it may be 10 to 40%.

That is, the aquatic repellent agent of the present invention can be blended with a film forming agent to prepare an antifouling paint, which can be prevented from adhering to aquatic organisms by plotting it on the hull bottom, the underwater structure, or the cooling water intake path wall. At this time, an oily varnish, synthetic resin, artificial rubber, etc. are used as a coating film forming agent. Pigment or extender pigment can be added to the antifouling paint as desired. In this case, the aquatic repellent agent of the present invention is blended at a ratio of 60% or less, preferably 10 to 40%, based on the weight of the film-forming agent.

In the water intake tank for cooling water, the aquatic repellent agent of the present invention may be added to the blowing furnace in the form of a solution or an emulsion for the purpose of preventing the propagation of aquatic organisms. However, it is preferable to apply in the form of paint in order to maintain the long-term pollution prevention effect. The aquatic repellent of the present invention can be applied to fishing nets regardless of the material.

Next, the present invention will be described in detail by way of examples and comparative examples.

Example 1

18.0 parts of N-4-tolyl maleimide (parts represent parts by weight; the same applies hereinafter), 2.0 parts of bis (tri-n-butyltin) mesodibromosuccinate, 10.0 parts of red shells, 15.0 parts of talc, 20.0 parts of barium sulfate, 5.5 parts of vinyl resin, 5.5 parts of rosin, 2.0 parts of tricresyl phosphate, 11.0 parts of methyl isobutyl ketone, and 11.0 parts of xylene were blended, and thoroughly milled and mixed using a pocket mill to prepare an antifouling paint.

Using the anti-fouling paint prepared in this way, brush applied anti-fouling paint twice to steel plate (300 × 100 × 1mm) which was treated with top sea primer twice and bottom with double bottom paint and then immersed in a wooden frame. Suspended from the sea, and immersed in seawater to a depth of 1.5m. Subsequently, the degree of adhesion of the living organisms pulled up and attached every predetermined period is expressed as a percentage of the total area of the attachment area. The result in 12 months after immersion is shown in a 1st table | surface.

[Examples 2 to 17]

Except for using various N-allyl maleimide instead of the N-4-tolyl maleimide of Example 1, the result of having carried out an immersion test in the same manner as in Example 1 was prepared in Table 1 is shown.

Example 18

Instead of 18.0 parts of N-4-tolylmaleimide of Example 1, 9.0 parts of N-4-tolyl maleimide and 9.0 parts of N-2,4-xylyl maleide were selected from bis (tri-n-butyltin) mesodibromo Except for using 2.0 parts of triphenyltin monochloroacetate instead of 2.0 parts of succinate, the results of the immersion test in the same manner as in Example 1 were prepared.

Instead of 18.0 parts of N-4-tolylmaleimide of Example 1, 9.0 parts of N-4-tolylmaleimide and 9.0 parts of N-2,4-xylylmaleimide were used as bis (tri-n-butyltin) mesodibro An antifouling paint was prepared in the same manner as in Example 1 except that 1.0 part of bis (tri-n-butyltin) mesodibromosuccinate and 1.0 part of triphenyltin monochloroacetate were used in place of 2.0 parts of the mother succinate. The results of the immersion test are shown in Table 1. In addition, except for the active ingredient, in the same manner as in Example 1, the anti-fouling paint was prepared and the results of the immersion test were presented as a control example.

Example 19

Instead of 18.0 parts of N-4-tolylmaleimide of Example 1, 9.0 parts of N-4-tolylmaleimide and 9.0 parts of N-2,4-xylylmaleimide were used as bis (tri-n-butyltin) mesodibro Table 1 shows the results of the immersion test prepared in the same manner as in Example 1 except that 1.0 part of the mucinsinate and 1.0 part of the triphenyltin monochloroacetate were used. In addition, except for the active ingredient, in the same manner as in Example 1, the antifouling paint was prepared and the result of the immersion test was shown as a control.

Comparative Example 1

20.0 parts of N-4-tolyl maleimide, 10.0 parts of red shell, 15.0 parts of talc, 20.0 parts of barium sulfate, 5.5 parts of secret resin, 5.5 parts of rosin, 2.0 parts of tricresylphosphate, 11.0 parts of methyl isobutyl ketone and 11.0 parts of xylene Then, using a milling mill, sufficiently mixed and mixed to prepare an antifouling paint.

Using the anti-fouling paint prepared in this way, brush the anti-fouling paint twice on the steel plate (300 × 100 × 1mm) which was treated with the upper sea primer and the bottom of the bottom paint twice. Suspended from the raft into the sea and immersed to a depth of 1.5m. Subsequently, the degree of adhesion of the living organisms pulled up and attached every predetermined period is expressed as a percentage of the total area of the attachment area. The results in 12 months after immersion are shown in Table 2.

Comparative Examples 2 to 22

Instead of the N-4-tolylmaleimide of Example 1, various N-allyl maleimide I, bis (tri-n-butyltin) mesodibromosuccinate, triphenyltin monochloroacetate, triphenyltin hydroxide Except for using the seed and bis (tri-n- butyltin) oxide in the same manner as in Comparative Example 1, the antifouling paint was prepared and the results of the immersion test are shown in Table 2. In addition, except for the active ingredient in the same manner as in Comparative Example 1, the anti-fouling paint prepared by the immersion test is presented as a control example.

[Table 1]

Note: During the submerged period, algae were more than 80% adhered, but shellfish were attached from around 6 months, and the algae gradually built up from the surface tested by the shellfish, making it impossible to measure.

[Table 2]

Note: During the submerged period, algae were more than 80% adhered, but shellfish were attached from around 6 months, and the algae gradually built up from the surface tested by the shellfish, making it impossible to measure.

[Examples 20 to 23]

Various N-allyl maleimides were used in place of the N-4-tolyl maleimide of Example 1, and various organic tin compounds were used in place of bis (tri-n-butyltin) mesodibromosuccinate. Table 3 shows the results of immersion tests prepared with antifouling paints in the same manner as in Example 1.

[Table 3]

Note: During the submerged period, algae were more than 80% adhered, but shellfish were attached from around 6 months, and the algae gradually built up from the surface tested by the shellfish, making it impossible to measure.

Claims (1)

80 to 95% by weight of at least one compound of N-allyl maleimide represented by the following general formula, bis (tri-n-butyltin) mesodibromosuccinate, triphenyltin monochloroacetate, triphenyltin hydroxide An aquatic repellent, characterized in that it comprises an active ingredient containing 20 to 5% by weight of at least one compound selected from the group of organotin compounds composed of siloxane and bis (tri-n-butyltin) oxide.

Wherein X ₁ and X ₂ are the same or different and each represents a hydrogen atom, a halogen atom, Y represents a halogen atom, an alkyl group or a lower alkoxy group, and n represents an integer of 0 or 1 to 3.