KR830000966B1 - Aquatic repellent - Google Patents

Abstract

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Description

Aquatic repellent

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

Always under water, such as underwater structures such as ship bottoms, fishing nets, mooring buoys, submerged structures such as soldering equipment, condenser cooling water for thermal power plants, and water intakes for heat exchanger cooling water for various industries, etc. In contact with the "busa lake", oyster shells, violet clams, hydropexes, "Selpra", moss bugs, sea squirts, clusters, moss bugs, "Aosa", greens, and "Sionodoro" Since shellfish and algae, etc. grow and adhere to each other, for example, in ships, it not only causes a decrease in the navigation speed and an increase in waste of fuel consumption, but also a cleaning cost or a cleaning period for cleaning the ship bottom. It causes economic loss due to the suspension of ship operation of the ship, and inconvenient handling operation in the underwater construction, and intake paths such as condenser, heat exchanger, etc. As a result, large-scale losses such as deterioration of the equipment caused by the lumps of living organisms dropped out from the wall of the channel can be caused.

Therefore, conventionally, in order to prevent the interference caused by the attachment of such seawater and freshwater harmful organisms, heavy metal compounds such as copper oxide, mercury oxide, organic tin compounds such as tributyl tin oxide, organic chlorine or organic sulfur compounds , Antifouling paints containing arsenic compounds such as phenar chloride, etc. are 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 the metal oxides easily react with varnish components in the paints, and pollution areas such as ports into which industrial sewage flows. In Esau, there is a defect in discoloration and deterioration due to 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 "Adverb", sea urchin, tonic, moss, etc., but have little effect on algae. In addition, when applied to a light metal material based on aluminum, magnesium, or the like, metals such as copper and mercury in the paint are deposited on the material, and even have a disadvantage of promoting chemical erosion of the material.

Compared with the antifouling paint containing organic tin-based compounds such as tributyl tin oxide, the effect is insufficient and expensive. In addition, when used in a large amount, there is a drawback that deterioration of coating performance and generation of odor in handling.

Antifouling paints containing organic chlorine or organosulfur compounds are inferior in effect to any of the antifouling paints described above. Then it is almost impossible to use.

Moreover, the antifouling paints containing phenar chloride (Adamsite) have a severe mucous membrane irritation to the human body, which makes it difficult to manufacture and paint.

In addition, in the method of adding chlorine or formalin or the like to the intake passage of the cooling water, the cooling device is corroded, and the effect of preventing adhesion of aquatic organisms is also inferior.

The present inventors have conducted various studies to obtain anti-fouling paints without various defects inherent to the anti-fouling paints conventionally used, and found that N-allyl maleimide has an effective aquatic repelling effect as an anti-fouling paint. It was introduced in Japanese Patent Application No. 51-81476. However, this N-allyl maleimide is slightly inferior to the shellfish compared to the anti-adhesion effect on algae, and thus, more intensive studies have been made to obtain aquatic repellents having excellent anti-adhesion effect on both shellfish and algae. As a result, in addition to bis (tri-n-butyltin) mesodibromosuccinate, triphenyl tin monochloroacetate, triphenyl tin hydroxide and bis (tri-n-butyltin) in N-allyl maleimide ) And a small amount of at least one compound selected from the group of the organotin compounds which are used as oxides are mixed and added again, and 4-anilino-monochloroacetylanilide, 2,4-dinitrophenylthiocyanate, and 4,6-dinitro-0 -By adding a small amount of at least one compound selected from the group consisting of cresol and zinc oxide, it exhibits excellent anti-adhesion effect on both shellfish and algae. Taking out the naendaneun fact reached as the completion of 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, and n represents 0 or an integer of 1 to 3) At least one compound of N-allyl maleimide and bis (tri-n-butyltin (mezodibromo succinate, triphenylsuccinochloroacetate, triphenyl tin hydroxide and bis (tri-n-butyltin) ) At least one compound selected from the group of the organic tin compounds consisting of oxides and 4-anilino-monochloroacetyl anilide, 2,4-dinitrophenylocyanate, 4,6-dinitro-O-cresol and zinc oxide An aquatic repellent agent comprising at least one compound selected from the group consisting of (hereinafter referred to as the compound of the first group) 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, for example is mentioned. 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-propoxyphenyl maleimide Mead, N-2,3- (or 2,5-, 3,4- or 3,5-) xylylmaleimide, N-2,5-dimethoxyphenylmaleimide, N-phenyl-2-bromo Maleimide, N-3-chlorophenyl-2-bromomaleimide, N-3-bromophenyl-2-bromo maleimide, N-3,5-dichlorophenyl-2-bromomaleimide, N- Phenyl-2,3-dichloromaleimide, N-phenyl-2,3-dibromomaleimide, N-phenyl-2,3-difluoromaleimide De, N-2- (or 3-, or 4-) chlorophenyl-2,3-dichloromaleimide, N-4- iodinephenyl-2,3-cycloromaleimide, N-4-chlorophenyl-2 , 3-difluoromaleimide, N-4-tolyl-2,3-dibromomaleimide, N-4-methoxyphenyl-2,3-dichloromaleimide, N-3,4-dichlorophenyl- 2,3-dichloromaleimide, N-2,5-xylyl-2,3-dichloromaleimide, N-2,4,6-trichlorophenylmaleimide, and the like, among which N-3-chloro Phenylmaleimide, N-4-tolylmaleimide, Ni-propoxyphenylmaleimide, N-2,4-xylylmaleimide, N-2,4,6-trichlorophenylmaleimide are the aquatic organisms of the present invention. It is suitable as a mixed agent of repellent.

The aquatic repellent agent of the present invention is 61-83% of at least one compound of N-allyl maleimide, 7-9% of at least one compound of organotin compound, 32- of at least one compound of group 1 compound The mixture is used in an amount of 8%, and used as a paint, solution, emulsion or the like so as to be 60% or less, preferably 10 to 40% as an active ingredient.

That is, it is possible to prevent adhesion propagation of aquatic organisms by blending the aquatic repellent agent of the present invention with a film-forming agent to prepare an antifouling paint and applying it to a hull bottom, an underwater structure, or a cooling water intake path wall. At this time, for example, an oily varnish, synthetic resin, artificial rubber, or the like is used as the film forming agent. Pigment or extender pigment can be added to the antifouling paint as desired. In this case, the aquatic repellent agent of this invention is mix | blended in the ratio of 60% or less, Preferably it is 10 to 40% based on the weight of a coating film forming agent.

In order to prevent adhesion propagation of aquatic organisms in the intake tank of cooling water, you may add the aquatic repellent agent of this invention to a blowing furnace in the form of a solution or an emulsion. However, in order to maintain the long-term pollution prevention effect, it is preferable to apply in the form of paint. 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

14.4 parts of N-4-tolylmaleimide, 1.6 parts of bis (tri-n-butyltin) mesodibromosuccinate, 40 parts of 4-anilino-monochloroacetylanilide, 10.0 parts of red shell, 15.0 parts of talc, and barium sulfate 20.0 parts, 11.0 parts of methyl isobutyl ketone, and 11.0 parts of xylene are blended, and it fully grinds, mixes, softens using a pocket mill, and prepares an antifouling paint.

Using the anti-fouling paint prepared in this way, brush is applied twice to the steel plate (300 × 100 × 1mm) treated with Wisi primer and twice with the bottom paint, and then immersed in a wooden frame. Suspended in the sea at and kept 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. After immersion, the results in 12 months are shown in the first table.

[Examples 2 to 17]

Table 1 shows the results of the immersion test in the same manner as in Example 1 except that N- allyl maleimide was used in place of the N-4-tolyl maleimide of Example 1, to prepare an antifouling paint. do.

Example 18

Instead of 14.4 parts of N-4-tolylmaleimide of Example 1, 7.2 parts of N-4-tral maleimide and 7.2 parts of N-4-xylylmaleimide, and 4.0 parts of 4-anilino-monochloroacetylanilide Except for using 4.0 parts of 2,4-dinitrophenylthiocyanate, the result of the immersion test prepared in the same manner as in Example 1 is shown in Table 2.

Example 19

Instead of 14.4 parts of N-4-tolylmaleimide of Example 1, 7.2 parts of N-4-trilmaleimide and 7.2 parts of N-2,4-xylylmaleimide were added to bis (tri-n-butyltin) mezodibro. 0.8 parts of bis (tri-n-butyltin) mesobromosuccinate and 0.8 parts of triphenyltin monochloroacetate instead of 1.6 parts of mosuccinate and 2,4 instead of 4.0 parts of 4-anilino-monochloroacetylanilide Except for using 4.0 parts of dinitrophenylthiocyanate, the result of the immersion test prepared in the same manner as in Example 1 was prepared 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 result of the immersion test was presented as a control example.

Comparative Example 1

20.0 parts of N-4-tolylmaleimide, 10.0 parts of red shell, 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 tricylphosphate, 11.0 parts of methyl isobutyl ketone, and 11.0 parts of xylene, Pulverization miscation was sufficiently carried out using a pocket mill to prepare an antifouling paint.

Using the anti-fouling paint prepared in this way, brush is applied twice on the steel plate (300 × 100 × 1mm) treated with Wisi primer and once under the bottom paint twice, and then immersed in the wooden frame and put into the wooden frame. Suspended to sea at and kept submerged to a depth of 1.5m. Subsequently, the degree of adhesion of the organisms that were pulled up and attached every predetermined period of time was 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 Example 2-25]

Instead of the N-4-tolylmaleimide of Comparative Example 1, various N-allylmaleimide I, bis (tri-n-butyltin) mesodibromosuccinate, trifetyltin monochloroacetate, triphenyltin hydroxide Seed, bis (tri-n-butyltin) oxide, 4-anilino-monochloroacetylanilide, 2,4-dinitrophenylthiocyanate, 4,6-dinitro-O-cresol or zinc oxide Except for the same 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 was prepared, and the result of the immersion test is presented as a control example.

[Table 1]

Note: In the mid-immersion period, more than 80% of the algae were attached, but shellfish were attached from around 6 months, and the algae were gradually built up from the surface of the test tube by the shellfish, making it impossible to measure.

[Table 2]

Note: In the mid-immersion period, algae were attached more than 80%, but shellfish were attached from around 6 months, and the algae were gradually built up from the surface of the test tube by the shellfish, making it impossible to measure.

[Examples 20-25]

Instead of the N-4-tolylmaleimide of Example 1, various N-allyl maleimides were used, various organic compounds were substituted for bis (tri-n-butyltin) mesodibromosuccinate, and 4-anilino-mono Chlorine acetylanilide or immersion test was prepared in the same manner as in Example 20 except that 2,4-dinitro thiocyanate, 4,6-dinitro-O-cresol, or zinc oxide was used instead. The results of the implementation are presented in Table 3. In addition, the result of having carried out the immersion test by preparing the antifouling paint in the same manner as in Example 1 except for the exclusion of the active ingredient is shown as a control example.

[Table 3]

^{* In the} middle of immersion, algae were attached more than 80%, but shellfish were attached from around 6 months.

Claims (1)

At least one compound of N-allyl maleimide represented by the following general formula and bis (tri-n-butyltin) mesodibromosuccinate, triphenyltin monochloroacetate, triphenyltin hydroxide and bis ( 4-anilino-monochloroacetylanilide, 2,4-dinitrophenylthiocyanate, 4,6-dinitro and at least one compound selected from the group of organic tin compounds consisting of tri-n-butyltin) oxide An aquatic repellent, characterized in that it contains as an active ingredient at least one compound selected from the group consisting of -O-cresol and zinc 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.