JPS6058885B2 - aquatic creature repellent - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a novel aquatic organism repellent containing N-substituted phenylproviolamide as an active ingredient.

Currently, vessels, equipment, and structures that are immersed in water for long periods of time, such as the bottom of ships, fishing nets, wave power generation systems, industrial cooling water intakes and passageways, and underwater structures, are
Barnacle, key, mussel, hydromushi, cellupa, bryozoan, sea squirt, bryozoan, sea lettuce, green laver,
Aquatic organisms such as shellfish and algae grow attached to the water, causing a lot of damage and loss. For example, in ships, this not only causes a decrease in sailing speed and waste of fuel, but also causes economic losses such as losses due to suspension of operations for cleaning the bottom of the ship and cleaning costs.

In addition, the durability of underwater structures such as dam auxiliary equipment and bridge piers may be impaired, and the amount of water intake may be reduced in cooling water intake channels such as condensers of thermal power plants and heat exchangers of various industries. This leads to various damage losses, such as a decrease in cooling efficiency due to water condensation, and a decrease in the performance of condensers and heat exchangers due to biomass falling from the waterway walls. Furthermore, in fixed fishing nets used for cultivating fish and shellfish for the purpose of artificially securing marine resources, the durability of the nets themselves may be impaired, or the meshes may become clogged, resulting in insufficient movement of seawater within the nets. This causes various damages and losses, such as the death of fish and shellfish due to lack of oxygen, and the propagation of bacteria, which causes damage to fish due to Nocardia disease, Benedeniasis, etc. Conventionally, in order to prevent damage and loss due to attached breeding of such aquatic pests,
Antifouling paints containing cuprous oxide, bis(tri-n-butyltin) oxide, organic chlorine or organic sulfur compounds, phenarsazine chloride J, etc. are used, and chlorine, formalin, etc. are used in the cooling water intake channels. was used directly.

However, antifouling paints containing cuprous oxide have poor storage stability because the cuprous oxide contained tends to react with varnish components in the paint, and they also have poor storage stability in polluted areas such as ports where industrial sewage flows. However, there are drawbacks such as discoloration and deterioration due to hydrogen sulfide generated by the action of microorganisms in contaminated water, and loss of efficacy.

In addition, it is effective against marine organisms such as barnacles, sea squirts, coelenterates, and bryozoans, but it has little effect on algae, and it is applied to light metal materials mainly made of aluminum, magnesium, etc. In this case, there are disadvantages such as metals in the paint depositing on the material and electrochemically accelerating erosion of the material. Antifouling paints containing bis(tri-n-butyltin) oxide are expensive, have the disadvantage of deteriorating the performance of the paint film when used in large quantities, and have an extremely strong odor, which is not desirable in terms of occupational hygiene. It has the following drawback.

Antifouling paints containing organochlorine or organic sulfur compounds are far less effective than any of the above-mentioned antifouling paints; for example, they are effective against bryozoans but not against barnacles. As such, its efficacy against aquatic pests is selective, and it is almost impossible to put it to practical use.

Furthermore, antifouling paints containing phenalsazine chloride (Adamsite) have been found to be extremely irritating to human mucous membranes.
It has the disadvantage that painting work is not easy.

In addition, chlorine, formalin, etc. corrode cooling devices and are also less effective in preventing the attachment of organisms in water.

The present inventors have solved the various drawbacks of conventional aquatic organism repellents such as antifouling paints and antifouling compositions, and are nontoxic to fish and shellfish and humans and livestock, and are also effective against shellfish and algae. In order to provide a new aquatic organism repellent that has an excellent adhesion prevention effect against all kinds of aquatic harmful organisms, we synthesized various compounds and conducted intensive research to investigate their aquatic organism repellent effects. As a result, N-monosubstituted phenylpropioloylamide is excellent in water! They discovered that it has a biorepellent effect and completed the present invention. That is, the present invention relates to the general formula (where x represents a lower alkyl group, a lower alkoxy group, or a trifluoromethyl group, and Y represents a hydrogen atom or a lower alkyl group).

) is an underwater biological repellent characterized by containing N-monosubstituted phenylpropioloylamide as an active ingredient.

Examples of the N-monosubstituted phenylpropioloylamide represented by the general formula [1] used as the active ingredient of the aquatic organism repellent of the present invention include the following.

Note that the compound numbers are referred to in each formulation example and each test example below. Compound (1) N-2-tolylpropioloylamide compound (2) N-4-tolylpropioloylamide compound (3) N-4-n-butylphenylpropioloylamide compound (4) N-2 -Methoxyphenylpropioloylamide compound (5) N-3-isopropoxyphenylpropioloylamide compound (6) N-
3-Trifluoromethylphenylpropioloylamide compound (7) N-2,4-xylycylpropioloylamide compound (8) N-2-methoxy5-methylphenylpropioloylamide These compounds and others The N-monosubstituted phenylpropioloylamide represented by the general formula [1] used as the active ingredient of the aquatic organism repellent of the present invention can be prepared by, for example, the following method using the corresponding raw materials. can be manufactured.

That is, as shown in the following reaction formula (1), propiolic acid and substituted aniline are reacted in the presence of a dehydrating agent such as phosphorus pentoxide, and as shown in the following reaction formula (2), N
●It can be produced by a method in which propiolic acid chloride and substituted aniline are reacted in the presence of a tertiary amine such as N-diethylaniline. Reaction formula (1) (wherein x and Y represent the same meanings as above.

) Reaction formula (2) (wherein, X and Y represent the same meanings as above.

) In either method, an appropriate solvent may be used to ensure smooth operation, and the reaction temperature is preferably room temperature or lower to suppress the formation of reaction by-products. The aquatic organism repellent of the present invention has the general formula [1
] It can be obtained by preparing N-monosubstituted phenylpropioloylamide shown in the following form into a paint, solution, emulsion, or the like.

For example, a paint can be obtained by blending one or two of the N-monosubstituted phenylpropioloylamides represented by the general formula [1] with a coating film forming agent, and this can be applied to the bottom of a ship,
By applying it to the walls of underwater structures and cooling water intake channels, it is possible to prevent the adhesion and propagation of aquatic organisms.

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 paint as desired. In this case, the N-monosubstituted phenylpropioloylamide represented by the general formula [1] is preferably blended into the coating material in an amount of 5 to 8%, preferably 5 to 3%. For the purpose of preventing the adhesion and propagation of aquatic organisms in cooling water intake channels, N-monosubstituted phenylpropioloylamide represented by the general formula [1] is added to the intake channels in the form of a solution or emulsion. You may.

However, in order to maintain the antifouling effect for a long time, it is desirable to apply it in the form of a paint. Alternatively, a resin solution can be obtained by dissolving the N-monosubstituted phenylpropioloylamide represented by the general formula [1] in an organic solvent together with a resin, and by impregnating a fishing net with this resin solution and drying it. This can prevent aquatic organisms from adhering to fishing nets and breeding.

When preparing this resin solution, the N-monosubstituted phenylpropioloylamide represented by the general formula [1] is
Heel weight%, preferably 5 to 1 weight%, resin 3 to 2 weight%
, preferably in a concentration of 5 to 1% by volume in an organic solvent.

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

In addition, as an organic solvent, benzene, toluene, xylene, chloroform, etc. are used, but if the resin is difficult to dissolve, dimethylformamide, dimethylacetamide or dimethyl sulfoxide may be mixed in a range of 2 to 2% by volume. can. In addition, if it is difficult to dissolve, it can be used after being dispersed in a suspended state. 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.
Hereinafter, the present invention will be specifically explained with reference to Examples.

Synthesis Example 1 Synthesis of Compound (1) 50 equipped with a thermometer, cooling tube, stirrer and dropping load
28.4 fI of phosphorus pentoxide (0.2
mol), 250 ml of chloroform and 14.0 f (0.2 mol) of propiolic acid were added thereto, and 23.6 y (0.22 mol) of o-toluidine was added dropwise at room temperature with stirring, followed by reaction under reflux for 4 hours. .

After the reaction was completed, the resulting reaction solution was washed with water, dried, and chloroform was distilled off to obtain a reddish-brown solid, which was recrystallized from carbon tetrachloride to give pale yellow disk-like crystals, melting point 134.5-136.0.
℃ Compound (1) N-2-tolylpropioloylamide 13.5y (yield 42.5% based on propiolic acid) was obtained.

Synthesis Example 2 Synthesis of Compound (2) In the same manner as in Synthesis Example 1 except that p-toluidine was used in place of o-toluidine in Synthesis Example 1, light yellow disk-like crystals,
Compound (2) N-4- with a melting point of 125.0 to 126.5°C
13.9y of tolylpropioloylamide (yield 43.8% based on propiolic acid) was obtained.

Synthesis Example 3 Synthesis of Compound (5) The same procedure as Synthesis Example 1 was repeated except that 3-isopropoxyaniline 30.2y (0.22 mol) was used in place of o-toluidine in Synthesis Example 1. Yellow disk-like crystals, melting point 87.
Compound (5) N-3-isopropoxyphenylpropioloylamide 15.8y (yield 42.5% based on propiolic acid) was obtained at a temperature of 5 to 90.0°C.

Synthesis Example 4 Synthesis of Compound (6) A yellow Platy crystals, melting point 109
．． Compound (6) N-3-trifluoromethylphenylpropioloylamide 18.2y (yield 42.7% based on propiolic acid) was obtained at a temperature of 0 to 110.5°C.

Synthesis Example 5 Synthesis of Compound (7) 17.7y (0.2 mol) of propiolic acid chloride and 200 mL of chloroform were placed in the same 500 ml reaction flask as in Synthesis Example 1, and while cooling with a dry ice-acetone solution from the outside, 2.・4-xylidine 24.2
y (0.2 mol), N-N-diethylaniline 29.8
y (0.2 mol) and 120 ml of chloroform! After adding the above solution dropwise over 1 hour, the mixture was allowed to react at room temperature for 1 hour with stirring.

After the reaction was completed, the resulting reaction solution was washed with water, dried, and chloroform was distilled off to obtain a yellowish brown solid, which was recrystallized from carbon tetrachloride to give a pale yellowish brown powder crystal, melting point 4146.5-148.
．． Compound (7) N-2.4-xylylpropioloylamide 24.9y (yield 72.0% based on propiolic acid chloride) was obtained at 0°C.

Example 1 Paint formulation example 1 Compound (1) N-2-tolylpropioloylamide was blended in the following proportions, thoroughly ground with a pocket mill, and mixed.
A paint was prepared.

(% indicates weight percentage. The same applies hereinafter) Example 2 Paint formulation example 2 Compound (5) N-3-isopropoxyphenylpropioloylamide was blended in the following proportions, thoroughly pulverized with a pocket mill, and mixed. It was made into a paint.

Example 5 Antifouling Test for Marine Organisms An antifouling test for marine organisms was conducted using paints prepared in the same manner as in Example 1 using various N-substituted phenylpropioloylamides.

(1) Preparation of test plate and test method Once with wash primer, anti-rust paint (no chemical additives)
Brush each paint twice on each steel plate (300 x 100 x 1 ugliness) that has been prime-coated twice with to be maintained.

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

As a control, a paint prepared using bis(tri-n-butyltin) oxide in place of N-substituted phenylpropioloylamide and a paint prepared without N-substituted phenylpropioloylamide were used. List the results.
Example 6 Formulation Example 1 of Resin Solution Compound (2) N-4-tolylpropioloylamide was blended in the following proportions and sufficiently stirred and mixed to prepare a resin solution.

Example 7 Compounding Example 2 of Resin Solution Compound (6) N-3-trifluoromethylphenylpropioloylamide was blended in the following proportions and sufficiently stirred and mixed to prepare a resin solution.

Example 8 Fishing net antifouling test (1) Fishing net antifouling treatment Polyamide fibers (manufactured by Toray Industries, Inc.: An 11-section (3.03 cTn mesh) fishing net made from Amiran (trade name) was dipped in the net, sufficiently impregnated, and then air-dried for an hour to give it an antifouling effect.

(2) Test method A test piece of 50 x 50 cm was cut from each antifouling fishing net, stretched on a 60 x 60 cm iron frame, and suspended in the sea from an immersion raft at a depth of 1.5 m. keep it there.

(3) 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, grass moss, hydro, sea squirt, etc. was observed and measured.

The results obtained are shown in Table-2. Furthermore, these results are
It is indicated by the following evaluation symbol.

1. No adhesion at all ± Scattered adhesion + A small amount of adhesion throughout the net A large amount of adhesion throughout the net Also, as a control, bis(tri-n-butyltin) oxide was used instead of N-substituted phenylpropioloylamide. The results using the prepared resin solution and the resin solution prepared by excluding the N-substituted phenylpropioloylamide are listed below.

Claims (1)

[Claims] 1 General formula ▲ Numerical formula, chemical formula, table, etc. ▼ (In the formula, X represents a lower alkyl group, lower alkoxy group or trifluoromethyl group, and Y represents a hydrogen atom or a lower alkyl group. . ) An aquatic organism repellent comprising an N-substituted phenylpropioloylamide as an active ingredient.