JPH02155961A - Underwater antifouling agent - Google Patents

Abstract

PURPOSE:To obtain an underwater antifouling agent which is lowly toxic and nonresidual, does not pollute the ocean and marine life and can prevent aquatic life from depositing on an underwater structure or a fishing net by using a product of reaction of a polyaminomonocarboxylic acid with a organohalosilane as an effective component. CONSTITUTION:A product of reaction of a polyaminomonocarboxylic acid, desirably a compound of formula I [wherein R<1-2> are each H, a (substituted) (unsaturated) 1-20 C alkyl, a (substituted) phenyl or a (substituted) heterocyclic group; m is 1-2; and n is 0-2] [e.g. a compound of formula II (wherein R<4> is a 6-18 C alkyl)] or a compound of formula III (wherein R<3> is R<4>) with an organohalosilane of desirably formula IV (wherein R<6> is H, a 1-6 C hydrocarbon group, a haloalkyl or a substituted phenyl; X is a halogen atom and p is 1-3), e.g. dimethyldichlorosilane, is used as an effective component.

Description

[Detailed Description of the Invention] [Industrial Application Field] The present invention relates to an underwater antifouling agent, and is particularly applicable to various structures installed underwater, fishing nets, buoys, ropes, underwater parts of ships, and even cooling water. The present invention relates to a low toxicity, non-residual, and safe anti-fouling agent for preventing contamination due to adhesion of aquatic organisms to the inner surfaces of pipes, dam gates, etc.

[Conventional technology] Submerged materials such as fishing nets, buoys, lobes, rafts, buoys, and ship bottom parts have been contaminated with fouling organisms such as algae, barnacles, oysters, sea squirts, sea anemones, and lichens. As a result, they have suffered serious damage. In order to avoid such damage, organotin compounds, cuprous oxide, organocopper compounds, and other organic underwater antifouling agents have been used so far. However, because organic compounds have a narrow spectrum of action, they cannot prevent contamination by a wide range of fouling organisms and have weak sustainability.Copperous oxide and organic copper compounds have strong toxicity. In addition, it has the disadvantage that it reacts with sulfide ions present in water and changes into the corresponding sulfide, resulting in a reduction in the intended antifouling effect. Organotin compounds are widely used due to their strong effects and long-term sustainability, but they are highly irritating and toxic, which causes problems in handling them in antifouling treatments, and they also elute into water. Contamination of the ocean by this compound, especially the negative effects of accumulation on fish cultured in antifouling treated fishing nets, has become a major problem. In view of this current situation, the development of a safe underwater antifouling agent that is neither toxic nor persistent is awaited. Under these circumstances, the algae and fouling organism inhibitor disclosed in JP-A-61-140501, which contains a polyaminomonocarboxylic acid compound as an active ingredient, is not desirable in terms of action spectrum and safety. Although this is noteworthy, its efficacy and durability were insufficient.

[Problems to be Solved by the Invention] The present invention improves the efficacy and sustainability of the above-mentioned polyaminomonocarboxylic acid compounds, and also provides effective speech conductors that maintain the action spectrum, low toxicity, and non-persistence. This was done in order to provide a new underwater antifouling agent as a component.

[Means for Solving the Problems] The present invention relates to a novel underwater antifouling agent that solves the above-mentioned problems.As a result of intensive research, the present inventors have found that polyaminomonocarboxylic acid compounds can be mixed with various organohalogen compounds. It was discovered that the product obtained by reacting with silane is extremely useful as an active ingredient of an underwater antifouling agent, and after further studies, the present invention was completed.

That is, the underwater antifouling agent of the present invention contains as an active ingredient a product obtained by reacting a polyaminomonocarboxylic acid and an organohalosilane.

Although this product is new as an active ingredient for underwater antifouling agents, it consists of a very complex mixture of compounds, and it is difficult to define its components and composition. However, products such as silylation reaction products that involve intramolecular and intermolecular dehydrohalogenation, bioacids that have caused intramolecular and intermolecular dehydration reactions, and intramolecular and intermolecular dehydration condensation products, etc. is considered to be included. In any case, the product obtained by reacting the polyaminomonocarboxylic acid and organohalosilane can be an active ingredient of the antifouling agent of the present invention.

One of the raw materials for synthesizing the active ingredient of the underwater antifouling agent of the present invention is polyaminomonocarboxylic acid, which has a total of two or more amino groups and/or a group in which the hydrogen of an amino group is substituted and one There is no particular restriction as long as it is a compound having a carboxyl group, and known compounds can be used, but
Preferably, it is represented by the formula A. In the above formula, ttl, R2 is a hydrogen atom, unsubstituted or has a substituent, and has 1 to 20 carbon atoms.
The same or different atoms or groups selected from an alkyl group which may have an unsaturated bond, an unsubstituted or substituted phenyl group, or an unsubstituted or substituted monovalent heterocyclic group, m is 1 or 2, n is 0.1 or 2
However, examples of the alkyl group that may have an unsaturated bond include methyl group, ethyl group, vinyl group, decyl group, octadecyl group, etc., and monovalent heterocyclic groups include , pyridyl group, pyranyl group, thienyl group, etc. When the above alkyl group, phenyl group or monovalent heterocyclic group has a substituent, effective substituents include halogen, nitro group, alkyl group, alkoxy group, phenyl group, phenyloxy group, acyl group,
Examples include an acyloxy group, a cyano group, and a monovalent heterocyclic group.

Other preferred polyaminomonocarboxylic acids are general 2B R3N)IC11zCHzC82NH(:HC82CO
It is represented by 2HH3, in which R3 is a group selected from alkyl groups having 6 to 18 carbon atoms. As this R3,
Examples include hexyl group, decyl group, dodecyl group, and octadecyl group.

Furthermore, a more preferred polyaminomonocarboxylic acid has the formula C R'NHCH2CH2NHCH2CH2NHCH2C0
2H, in which R4 is a group selected from alkyl groups having 6 to 18 carbon atoms, and - formula D (RNI
([:82CH2)2N(:H2C02H.

RNHCH2CHzCH2NHCHCHzCO2H.

II3, in which US is a group selected from alkyl groups having 6 to 18 carbon atoms. Examples of R4 and R5 include the same groups as R3 above.

Examples of such polyamino monocarboxylic acids include derivatives of ethylenediamine monocarboxylic acid, derivatives of diethylenetriamine monocarboxylic acid, derivatives of triethylenetetramine monocarboxylic acid, and derivatives of 1,3-diaminopropane monocarboxylic acid. For example, RNH(:H2C02H(:HzCH2NIC1hC
O2H1n-C,,H,,-NHCH,CH2NHCH
2C02H (in the above formula, R means a mixture of aliphatic hydrocarbon groups having 6 to 18 carbon atoms), and the like. However, all of the above are representative examples, and the invention is not limited to these. Note that two or more types of polyaminomonocarboxylic acids can be used in combination as raw materials.

The other raw material for synthesizing the active ingredient is organohalosilane, with the formula E R6,SiX,-.

In the formula, R6 is an atom or group selected from a hydrogen atom, a monovalent hydrocarbon group having 1 to 6 carbon atoms, a halogenated alkyl group, or a phenyl group having a substituent, X is a halogen atom, and p is It is considered to be an integer from 1 to 3,
Known materials can be used for this, and specifically, for example, trimethylchlorosilane, dimethyldichlorosilane, methyldichlorosilane, methyltrichlorosilane,
Methylvinyldichlorosilane, vinyldichlorosilane,
Examples include diethyldichlorosilane, ethyldichlorosilane, ethyltrichlorosilane, bromomethylmethyldichlorosilane, etc., and silanes in which the chlorine atom of these chlorosilanes is replaced with other halogen atoms such as fluorine, bromine, and iodine. Mixtures of two or more of these can also be mentioned.

The active ingredient of the underwater antifouling agent of the present invention can be synthesized as follows using the above-mentioned raw materials.

Using a reactor that can remove volatile compounds generated during the reaction from the system, charge the reactor with hebolyaminomonocarboxylic acid and an organic solvent, and gradually add the hydrogen halide scavenger and organohalosilane. and react. The reaction temperature is room temperature to 200°C, preferably 70 to 120°C,
The reaction time ranges from 1 to 48 hours, preferably from 2 to 8 hours. After the reaction is completed, the mixture is cooled to room temperature or below room temperature if necessary, and the precipitated hydrogen halide salt is filtered. The active ingredient is obtained as a solution dissolved in the filtrate.

Therefore, an antifouling agent may be produced using this as it is, or the residue obtained by stripping the solvent under reduced pressure may be used as an active ingredient.

Organic solvents used in the above synthesis reaction include aliphatic hydrocarbons such as pentane, hexane, heptane, octane, and isooctane, aromatic hydrocarbons such as benzene, toluene, and xylene, ethyl ether, diisopropyl ether, butyl ether, and tetrahydrofuran. , dioxane and other noether compounds, methylene chloride, chloroform, carbon tetrachloride, chlorobenzene and other halogenated hydrocarbons, and N,N-dimethylformamide, N,N-dimethylacetamide, dimethylsulfoxide and other aprotic polar solvents. Examples of hydrogen halide scavengers include tertiary amines such as triethylamine, diethylaniline, and pyridine.

The underwater antifouling agent of the present invention can be obtained by preparing the above-mentioned active ingredients into a composition such as a paint, a solution, or an emulsion, but the form of the antifouling agent is not particularly limited.

For example, underwater antifouling paints contain one or more of the above active ingredients.
It can be obtained by blending f1 or more with a known coating film forming agent and forming a paint by a known method. As the coating film forming agent, for example, oil varnish, synthetic resin, artificial rubber, etc. can be used.

If necessary, pigments and extender pigments can be added to the antifouling paint, and in this case, the amount of the active ingredient is 5 to 80% by weight, preferably 10 to 50% by weight, based on the weight of the film forming agent. It is blended with. By applying this underwater antifouling paint to the bottom of a ship, an underwater structure, or the wall of a cooling water intake channel according to a known method, it is possible to prevent the adhesion and propagation of aquatic organisms.

For the purpose of preventing the adhesion and propagation of aquatic organisms in the cooling water intake channel, the above-mentioned active ingredient may be added into the intake channel in the form of a solution or emulsion. This emulsion can be produced using a known emulsifier. However, in order to maintain the antifouling effect over a long period of time, it is desirable to apply it in the form of a paint.

Furthermore, when applying the underwater antifouling agent of the present invention to fishing nets,
The active ingredient may be dissolved in an organic solvent together with a resin in the form of a solution, and fishing nets can be impregnated with this solution and dried to provide antifouling treatment. In preparing this solution, the active ingredient is dissolved in an organic solvent at a concentration of 1 to 50% by weight and the resin is dissolved in a concentration of 1 to 50% by weight. Examples of the resins used include vinyl chloride resins, acrylic resins, acrylic rubbers, vinyl chloride-vinyl acetate copolymer resins and saponified products thereof, phenol resins, alkyd resins, chlorinated rubbers, and rosins.

Further, as the organic solvent, benzene, toluene, xylene, chloroform, etc. are used, but when the resin is difficult to dissolve, dimethylformamide, dimethylacetamide, dimethylsulfoxide, etc. can be used.

There are no particular limitations on the material of the fishing net treated with the underwater antifouling agent of the present invention. Natural fibers such as cotton, linen, silk, and wool,
Alternatively, it can be applied to fishing nets made of synthetic fibers from polymers such as polyvinyl chloride, polyvinyl alcohol, polyvinylidene chloride, polyfluoroethylene, polyamide, polyethylene, polypropylene, polystyrene, polyacrylonitrile.

The active ingredient according to the present invention can be used in combination with other agents conventionally known to have an underwater antifouling effect. In this case, since the former is constantly and slowly eluted into water and exhibits its effect, the other drugs can exhibit strong effects even if the amounts are significantly reduced.

[Effect of the invention] The active ingredient according to the present invention is a. Low toxicity.

b. It is non-persistent as it is easily decomposed in the environment and does not contaminate the ocean or the organisms that live there.

C1 Prevent a wide range of aquatic organisms from attaching to underwater structures and fishing nets.

d. When a paint is made from an active ingredient and a film-forming agent, the active ingredient is constantly and slowly eluted from the paint film, so the strong effect lasts for a long time.

e. When the active ingredient is dissolved into a solution with a resin, for example, when treated on a fishing net, the same strong effect as above will continue for a long period of time due to constant dissolution from the surface.

f. When other compounds having aquatic biofouling prevention activity are used together with the active ingredient according to the present invention, fouling can be prevented with a much smaller amount than when they are not used together.

Because of this excellent effect, the underwater antifouling agent of the present invention using this active ingredient is extremely useful for safely preventing contamination of underwater materials due to attachment of underwater organisms.

[Example] Next, the present invention will be explained by examples.

Reference example 1 The active ingredient was synthesized as shown in the example below.

Dissolve 50 g of 7-alkyldiethylenetriamine-1-acetic acid (alkyl indicates a mixture of aliphatic hydrocarbon groups having 6 to 18 carbon atoms) in 50 mL of toluene,
15.7 g of triethylamine and 10 g of dimethyldichlorosilane were added, and the mixture was heated and refluxed. After reacting for 4 hours under the same conditions and allowing it to cool, the reaction solution was filtered, and the filtered residue was added to an additional 50 ml! Washed with toluene. Stripping of the solvent under reduced pressure gave a reddish-brown pasty product.

This is designated as product 1. The results of elemental analysis of this product 1 are: C: 43.137%, H: 10.811%,
N: 9.225%. Moreover, the IR spectrum of this product was as shown in FIG.

Reference Examples 2 to 19 Active ingredients were synthesized in exactly the same manner as in Reference Example 1 using the raw materials shown in Tables 1 and 2, respectively, to produce products 2 to 19.
I got it. The results of elemental analysis of these products are shown in Tables 1 and 2. In addition, in the chemical formula in the table, R means a mixture of aliphatic hydrocarbon groups having 6 to 18 carbon atoms, Me means a methyl group, Et means an ethyl group, and Vi means a vinyl group. In addition, in the chemical formula in the table, methylene group (-C1b-) is represented by △,
Ethylene group (-CH2CH2-) is abbreviated as ~ or ψ, trimethylene group (CH2CH2GHz-) as ya, and propylene group (-j:H2-) as heart.

Example 1 Using products 1 to 19 obtained in Reference Examples 1 to 19, antifouling paints were prepared for each product with the following formulation, and antifouling paints 1 to 19 corresponding to each product were prepared. Obtained.

(% is weight percentage) Product 20% Bengara 10% Talc 15% Barium sulfate 20% Vinyl resin 5% Rosin 5% Methyl isobutyl ketone 12% Xylene 13% (total 100%) A pocket mill is used to prepare the antifouling paint. Thorough pulverization and mixing were carried out using a .

Example 2, Comparative Example 1 The antifouling paint obtained in Example 1 was subjected to an immersion test in seawater using a test plate. The test plate is 300 xlO
Each of the antifouling paints obtained in Example 1 was applied with a brush twice to a 5 mm Ox steel plate that had been undercoated once with a wash primer and twice with a ship's bottom paint.

This test plate was attached to a steel frame and suspended in the sea.1.
The water depth was maintained at 5 m, and the water was pulled out at regular intervals to observe the attachment of organisms. The results are shown in Table 3. The results are shown below.

■＝Not attached at all! There is a small amount of deposits partially on III: There is a small amount of deposits on the whole lv: There is deposits on the whole V: There is a large amount of deposits on the whole The above display is from Table 4 (results of Example 4) The same applies to Table 5 (results of Example 6).

For comparison, tests were also conducted on the formulation of Example 1 except that the product was removed, and the results are also shown in Table 3.

Table 3 Example 3 Using Products 1 to 19, a solution (antifouling agent) was prepared for each product with the following formulation, and a solution IA-1 corresponding to each product was prepared.
I got 9A. (% is weight percentage) Product 15% Rosin 15% Toluene 70% (Total 100%) Example 4 The solution (antifouling agent) obtained in Example 3 was subjected to a fishing net antifouling test. The antifouling treatment was carried out by immersing the fishing net in the solution obtained in Example 3, allowing it to stand for 2 hours, then taking it out and air drying it for 18 hours.

Next, this antifouling treated fishing net (400 x 200 mm
) was attached to stainless steel and maintained in the sea at a depth of 1.5 m, and was pulled out at regular intervals to observe the state of attached organisms. The results are shown in Table 4. For comparison, the formulation of Example 3 except that the product was removed was also tested in the same manner as above, and the results are also listed in Table 4.

Example 5 Using Products 1 to 19, a solution (antifouling agent) was prepared for each product with the following formulation, and solution IB-1 corresponding to each product was prepared.
I got 9B. (% is weight percentage) Product 1
0% Copolymer of butyl acrylate and acrylic acid (5%)
10% toluene 80% (total 100%) Example 6 Regarding the solution (antifouling agent) obtained in Example 5, Example 4
Antifouling tests on fishing nets were conducted in the same manner as above. The results are shown in Table 5. For comparison, tests were also conducted on the formulation of Example 5 except that the product was removed, and the results are also shown in Table 5.

[Brief explanation of the drawing]

FIG. 1 is a diagram showing the IR spectrum of Product 1 obtained in Reference Example 1.

Claims (1)

[Claims] 1. An underwater antifouling agent whose active ingredient is a product obtained by reacting a polyaminomonocarboxylic acid and an organohalosilane. 2. The above polyaminomonocarboxylic acid has the general formula A ▲ There are mathematical formulas, chemical formulas, tables, etc. Same or different atoms or groups selected from an alkyl group which may have an unsaturated bond, an unsubstituted or substituted phenyl group, or an unsubstituted or substituted monovalent heterocyclic group, m is 1 or 2, n is 0, 1 or 2) The underwater antifouling agent according to claim 1. 3. A claim in which the polyaminomonocarboxylic acid is represented by the general formula B ▲There are mathematical formulas, chemical formulas, tables, etc.▼ (wherein R^3 is a group selected from alkyl groups having 6 to 18 carbon atoms) The underwater antifouling agent described in 1. 4. The polyaminomonocarboxylic acid represented by the general formula A has the general formula C R^4NHCH_2CH_2NHCH_2CH_2NH
The underwater antifouling agent according to claim 2, which is represented by CH_2CO_2H (wherein R^4 is a group selected from alkyl groups having 6 to 18 carbon atoms). 5. The polyaminomonocarboxylic acid represented by the general formula A is represented by the general formula D ▲There are mathematical formulas, chemical formulas, tables, etc.▼ (wherein R^5 is a group selected from alkyl groups having 6 to 18 carbon atoms) The underwater antifouling agent according to claim 2. 6. The organohalosilane has the general formula E R^6_pSiX_4_-_p (wherein R^6 is a hydrogen atom, a monovalent hydrocarbon group having 1 to 6 carbon atoms, a halogenated alkyl group, or a phenyl group having a substituent) 6. The underwater antifouling agent according to claim 1, 2, 3, 4, or 5, wherein X is a halogen atom and p is an integer of 1 to 3.