JPS5933561B2 - Underwater antifouling agent - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a compound of the general formula □CONH□CONI (I) (wherein R1 represents hydrogen, halogen, methyl, trifluoromethyl, methoxy, and R2 represents -, rogen, nitro, or methylthio).

However, when R2 is halogen, R1 is halogen, R
When 2 is methylthio, R1 represents hydrogen. The present invention relates to an underwater antifouling agent characterized by containing as an active ingredient one or more of the hydroxyraftoeic acid anilide compounds represented by the following formulas.

The present invention relates to a low-fish toxicity, long-lasting underwater antifouling paint and fishing net antifouling paint intended to prevent aquatic organisms such as seaweed, molluscs, and shellfish from adhering to ship bottoms, fishing nets, and other underwater structures. The aim is to provide agents for

Communication cables on the bottoms of ships and bridges, transportation pipes, oil fences, or industrial water intake pipes that use seawater as cooling water, heat exchangers, drainage pipes, waterways, etc. are susceptible to various major obstacles such as marine life and algae. In order to achieve this, a huge amount of effort, money, and time are being spent on removal, repair, and repainting.

For example, on ships, the buildup of locks and barnacles slows down the ship and increases fuel consumption. It obstructs the introduction of seawater in cooling water intake pipes, and impedes heat transfer in heat exchange pipes, reducing efficiency. In addition, nets and ropes for aquaculture fisheries such as sea bream and yellowtail, which have recently become popular, and fixed nets for set-net fisheries are kept underwater for long periods of time, so many bryozoans, sea lettuce, Fujitbo, ascidians, diatoms, etc. adhere to them. It obstructs the flow of seawater, causing a lack of oxygen for farmed fish, facilitating the growth of parasites, and causing problems in the durability of the nets.

Screen changes are performed to prevent these problems, but
Taking into account various factors such as labor, time, cost of replacing nets, and even the halt in the growth of farmed fish caused by changing nets, there will be a huge loss. Preventing the adhesion of marine organisms is a serious problem for the aquaculture industry as well, and it is hoped that the effect will last for a long time. Fixed nets are also a problem as the adhesion of aquatic organisms has a significant impact on fishing catches.

As described above, adhesion of marine organisms has become a major problem in various fields of ocean development, and the completion of an excellent underwater antifouling agent for preventing this pollution will bring immeasurable benefits.
There are many requirements for underwater antifouling agents used for such purposes.

For example, the active ingredients have low toxicity to the human body, low toxicity to fish and do not contaminate seawater, and are eluted from the surface in a limited amount and have a long-lasting antifouling effect.
It is stable, has good miscibility with the paint base, does not adversely affect the strength or color tone of the paint film, and is easy and inexpensive to manufacture. Although various such studies have been carried out in the past, none of them can be said to be sufficient. As a result of extensive research into underwater antifouling agents that meet these requirements, the present inventors have found that an underwater antifouling agent containing one or more compounds represented by the general formula (1) as an active ingredient has been developed. The inventors have found that the object can be achieved and have completed the present invention.

Some compounds (1) are industrially manufactured and sold as a coupling agent for azoic dyes, have low toxicity to humans and fish, and have higher aromaticity than salicylanilide compounds. This brings about various benefits.

For example, in terms of potency, it works at lower concentrations and is more persistent due to slower dissolution into water. It also has improved miscibility with the paint base, forming a water-resistant paint film that is resistant to physical effects such as impact. In terms of production, it has the advantage that it can be produced in a high yield in a short process using starting materials that are produced in large quantities and are easily available, and in some cases, products that are commercially available as basting agents can be used as they are.
The compound of general formula (1) is a compound represented by the general formula (wherein X represents a hydroxyl group, phenoxy, or halogen) and a compound represented by the general formula (wherein R1 and R2 have the same meanings as above).

) is produced by reacting with the compound represented by A detailed explanation will be given below using manufacturing examples.

Production Example 1 3.7y of 2-hydroxy-3-naphthoic acid and 3.1y of 2-methyl-5-nitroaniline were added to 75ml of toluene.
Reflux with water.

A solution of 1.27 ml of phosphorus trichloride dissolved in 25 ml of toluene was added dropwise to this over 30 minutes. After dropping, add 4 ml under reflux.
Allow time to react. After cooling, recrystallization is performed from methanol to obtain 2-hydroxy-2'-methyl-5'-nitro-3-naphthoic acid anilide 5.8V as pale yellow crystals with a melting point of 231-233°C. . Manufacturing example 2
2-Hydroxy-3-naphthoic acid 3.77, 2 chlor-
3.57 ml of 4-nitroaniline are refluxed with 75 ml of toluene.

A solution of 1.27 phosphorus trichloride dissolved in 25 ml of toluene is added dropwise over 10 minutes. After reacting for an additional 3 hours, the mixture was cooled and collected. Recrystallization from methanol-tetrahydrofuran gives 2-hydroxy-2/chloro-4'-nitro-3-naphthoic acid anilide 47 as pale yellow crystals with a melting point of 284-285°C. Production Example 3 1-Hydroxy-2-naphthoic acid 3.77, 3.5-dichloroaniline 3.27 was reacted in the same manner as in Example 1 to produce 3',5'dichloro-1- with a melting point of 186-188°C.
Hydroxy-2-naphthoic acid anilide 5y is obtained as white crystals.

Similarly, compounds that can be used in the present invention include, but are not limited to, the following.

◎1-Hydroxy-25-methyl-4'-nitro-2-naphthoic acid anilide Melting point 226-228℃◎1-Hydroxy-2'-methyl-5'-nitro-2-naphthoic acid anilide Melting point 215-218℃◎2' -Chlor-1-
Hydroxy-4'-nitro-2-naphthoic acid anilide
Melting point 231-232℃◎3'-trifluoromethyl-1
-Hydroxy-4'-nitro-2-naphthoic acid anilide Melting point 206-208℃ ◎1-Hydroxy-4'-nitro-2-naphthoic acid anilide Melting point 235-236℃◎1-Hydroxy-3'
-Methylthio-2-naphthoic acid anilide Melting point 118
~120℃◎1-Hydroxy-2'methoxy-47-
Nitro 2-naphthoic acid anilide Melting point 237-238
゜C ◎1-Hydroxy-Z-methoxy-5'-nitro-2-naphthoic acid anilide Melting point 206-207℃ ◎2-Hydroxy-2'-methyl-4'-nitro-1-naphthoic acid anilide Melting point 235-236℃◎ 2-Hydroxy-2'-methyl-5! -Nitro-1 naphthoic acid anilide Melting point 186-187℃◎2'-Chlor-2-
Hydroxy-4'-nitro-1-naphthoic acid anilide
Melting point 214-216°C◎31-trifluoromethyl-
2-Hydroxy-4'-nitro-1-naphthoic acid anilide Melting point 172-175°C ◎2-Hydroxy-4'-nitro-1-naphthoic acid anilide Melting point 186-188°C ◎3',5'-dichloro-2-hydroxy -1-Naphthoic acid anilide Melting point 2
35-236℃◎2-Hydroxy-2'-methoxy-4
'-Nitro 1-naphthoic acid anilide Melting point 207~2
09℃ ◎2-Hydroxy-2'-methoxy-5'-nitro1-
Naphthoic acid anilide Melting point 240-242℃ ◎2-Hydroxy-2'-methyl-l-nitro-3-naphthoic acid anilide Melting point 264-266℃◎2-Hydroxy-3'-nitro-3-naphthoic acid anilide Melting point 246-247 ℃◎2-Hydroxy-2'-methoxy-
5'-Nitro 3-naphthoic acid anilide Melting point 274~
276℃ ◎2-hydroxy-4'-nitro-3-naphthoic acid anilide Melting point 269-27PC◎3',5'-dichloro-2-hydroxy-3-naphthoic acid anilide Melting point 2
54-256℃◎2-Hydroxy-2'-methoxy-4
'-Nitro-3-naphthoic acid anilide Melting point 285~
286°C ◎2-Hydroxy-3'-methylthio-3-naphthoic acid anilide Melting point 186-188°C When producing an underwater antifouling agent, one or more of the compounds (1) and natural resins, oily,
Synthetic resin and synthetic rubber vehicles, plasticizers,
A solvent is added, or a color pigment is added if desired, and the mixture is sufficiently pulverized and kneaded by dissolving, dispersing, or using a conventional method (such as a ball mill).

Natural resin, oil-based, synthetic resin, and synthetic rubber vehicles include rosin, pole oil, chlorinated rubber, alkyd resin, various modified alkyd resins, vinyl resins such as vinyl chloride and vinyl acetate, acrylic resins, and olefins such as polyptene. Examples include, but are not limited to, resins, polystyrene, various synthetic rubbers, polyurethane, amino resins, epoxy resins, unsaturated polyester resins, asphalt, and coal tar. In addition to the active ingredients of the present invention, trialkyl or triaryltin compounds, organic acid copper, inorganic copper compounds, giabutane, BHC. Organic chlorine compounds such as DDT, triazine compounds, urea compounds, carbamate compounds, salicylanilide compounds, and organic sulfur compounds such as zinc dimethyldithiocarbamate and thiuram compounds may be used in combination.

Next, the effects of the present invention will be explained using examples.

Example [1] Underwater antifouling paint Example 1 2-hydroxy-2'-methyl-5'-nito 20% rho-3-naphthoic acid anilide litalc: Examples 1 to 7 above and Comparative Examples 1 and 2 Each test steel plate was coated with an antifouling paint having the formulation described in 2 twice.

Then, in the 1920s, it was discovered in the sea at a depth of 1.5m in Tsukumi Bay, Oita Prefecture.
Immersed and held for one year from June 1997 to June 19756
After 1 and 12 months, each test plate was examined for adhesion of fouling organisms. The results are shown in Table 1. Numbers in the table indicate percent adhesion area. As is clear from Table 1, compound (1) exhibits an excellent antifouling effect for a long period of time against marine fouling organisms.

Polyethylene 6-section (knotless) aquaculture nets (400 denier, 60 or more) were applied by dipping into the antifouling agents of Examples 1 to 4 above, and then air-dried and placed in the sea at a depth of 1 m in Tsukumi Bay, Oita Prefecture. The samples were kept immersed for 6 months from June 1970 to December 1970, and the adhesion status was investigated every month.

The results are shown in Table 2.廿, +, - in the table indicate the degree of adhesion of fouling organisms.

Ox: There is a significant amount of fouling organisms attached. +: There is no problem in practical use as an aquaculture net even if there is only a slight amount of fouling organisms attached.

: No fouling organisms attached.

Claims (1)

[Claims] 1 General formula ▲ Numerical formula, chemical formula, table, etc. ▼ However, when R^2 is halogen, R^1 is halogen,
When R^2 is methylthio, R^1 represents hydrogen. ) An underwater antifouling agent characterized by containing as an active ingredient one or more of the hydroxynaphthoic acid anilide compounds represented by: