JPH04149106A - Aquatic biofouling prevention agent - Google Patents

Abstract

PURPOSE:To obtain a safe attaching-proof agent of an aquatic organism having an excellent dirt-proof effect on pollutive organisms with high persistency of the effect and with only a slight toxicity with no remaining property nor induc ing any environmental pollution. CONSTITUTION:A compound expressed by the formula [R<1> and R<2> are methyl, ethyl, vinyl, CH2Cl or CH2F; R<3> and R<4> are halogen or 1-4C alkyl; (n) is integer of 1-10; A is CH2, CH2CH2, CH(CH3), O, NH or N(CH3)], preferably at least a compound selected from 5-pyperidinopentyl-4-chlorophenyl dimethylsilane, 6-morpholonohexyl-4-chlorophenyl dimethylsilane, 7-morpholinoheptyl-4- chlorophenyl dimethylsilane and 7-morpholinoheptyl-4-chlorophenyl chloromethylsilane is contained as an active ingredient having the above- mentioned effect in the objective attaching-proof agent of aquatic organisms.

Description

[Detailed Description of the Invention] [Industrial Application Field] The present invention relates to an aquatic biofouling prevention agent, and is particularly applicable to various underwater structures, fishing nets, robes, buoys, underwater parts of ships, and even cooling. To prevent contamination due to adhesion of aquatic organisms to the inner surface of water pipes, dam gates, etc., it is a safe, low-toxicity, non-persistent, and non-contaminating product that does not cause environmental pollution.
This invention relates to an anti-fouling agent for biological warts in contaminated water.

[Prior art] Submerged materials such as fishing nets, buoys, lobes, rafts, buoys, and bottom parts of ships have been contaminated with fouling organisms such as barnacles, oysters, sea squirts, sea anemones, bryozoans, and seaweed. , which has caused serious damage. In order to avoid such damage, organic tin compounds, cuprous oxide, cuprous compounds, and other organic aquatic biofouling inhibitors have been used so far. However, these conventionally used compounds have serious drawbacks.

In other words, there are 11! Copper-based compounds and cuprous oxide have strong toxicity, and since they are heavy metal compounds, they remain in the environment and cause pollution, and copper compounds are also found in seawater2.
A phenomenon has been observed in which the desired effect is drastically reduced because it reacts with sulfide ions and turns into the corresponding sulfide.

In addition, organotin compounds are widely used aquatic biofouling inhibitors due to their strong effects and long-term sustainability.
Because they are highly irritating and toxic, they not only pose health management problems for workers during antifouling treatment, but also cause marine pollution due to these compounds eluted into seawater, especially for aquaculture fish when used in aquaculture fishing nets. The negative effects on the human body due to the accumulation of carbon dioxide have become a serious problem in recent years.

Under these circumstances, there is an increasing demand for a safe, organic, aquatic wart prevention agent that has no residual or toxic properties, and development is currently being actively progressed. However, these conventional organic antifouling agents have a narrow spectrum of action on -H, so they are unable to prevent the adhesion and contamination of aquatic fouling organisms made up of a wide range of species, and furthermore, they are not sustainable. Currently, a drug with strong effects that can replace organic tin compounds, which are generally weak, has not yet been developed.

[Problems to be Solved by the Invention] The purpose of the present invention is to develop an anti-fouling agent for aquatic organisms that is non-toxic, non-residual, safe, and highly effective over a long period of time.

[Means for Solving the Problems] The present inventors have focused on organosilicon compounds and have conducted intensive research on their application as aquatic biofouling inhibitors. As a result, it has been found that an organosilicon compound having a cyclic amine structure as represented by the following general formula 1 exhibits a strong aquatic biofouling prevention activity that has not been seen in conventional compounds.

(In the formula, R' and R'' are respectively a methyl group, an ethyl group,
represents a vinyl group, a chloromethyl group, or a fluoromethyl group, R3 and R' each represent a halogen group or an alkyl group having 1 to 4 carbon atoms, n represents an integer from 1 to 10, A represents a -CH2~ group, -CLC) I2- group, -CHf
CH,)- group, -0- group, 7NH- group or NC)]
, - represents a group. ) Specific examples of the silane compound represented by the -M formula 1 include those shown below. However, it is not limited to these.

1.5-piperidinopentyl-4-methylphenyldimethylsilane 2.5-piperidinopentyl-3-chlorophenyldimethylsilane 3.5-piperidinopentyl-4-chlorophenyldimethylsilane 4.6-morpholino Hexyl-4-chlorophenyldimethylsilane 5.7-morpholinohexyl-3,5 -Dichlorophenyldimethylsilane 8.5-Piperidinopentyl-4-butylphenyldimethylsilane A long chain having a substituted silicon group and a cyclic amino group as substituents at both ends represented by the above general formula 1. Conventionally, no suitable synthesis method was known for alkyl compounds. However, the present inventors introduced a chloromethylsilane compound into a corresponding organometallic compound such as an organolithium reagent or a Grignard reagent, and performed a coupling reaction with a dihaloalkane.
A method of further reacting the obtained product with a cyclic amine (
(see Japanese Patent Application Nos. 1-92163 and 1-92165), or by reacting a halosilane with a Grignard reagent derived from a linear hydrocarbon compound having a halogen group and a protected hydroxyl group at both ends. It was discovered that the resulting hydroxyalkylsilane can be synthesized by introducing a compound having an easily leaving group, such as a sulfonic acid derivative, and reacting this with a cyclic amine (see Japanese Patent Application No. 1999-92165). By these methods, it is possible to produce the compound that is the active ingredient in the present invention.

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

For example, an underwater antifouling paint can be obtained by blending one or more of the above-mentioned active ingredients with a known 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. Pigments and extender pigments can be further added to the antifouling paint as necessary. In these cases, the active ingredient is present in an amount of 5 to 80% by weight, preferably 1% by weight, based on the weight of the film-forming agent.
It is blended at a ratio of 0 to 50%. By applying the underwater antifouling paint thus produced to the bottom of a ship, an underwater structure, a wall of a cooling water intake channel, etc. 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 preferable to apply it in the form of a paint.

In addition, when the aquatic biofouling prevention agent of the present invention is applied to fishing nets, the active ingredient may be dissolved in an organic solvent together with a resin, and the fishing net is impregnated with this solution and dried. Can be treated with antifouling. 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 resins that can be used include vinyl chloride resin, acrylic resin, copolymer of acrylic acid and acrylic ester, acrylic rubber, vinyl chloride-vinyl acetate copolymer resin and saponified products thereof, silicone resin, phenol resin, and alkyd resin. , chlorinated rubber, rosin, etc.

In addition, organic solvents include benzene, toluene, xylene,
Ethyl acetate, butyl acetate, methyl ethyl ketone, chloroform, etc. are used, but if the resin is difficult to dissolve, a polar solvent such as N,N-dimethylformamide, dimethylacetamide, dimethyl sulfoxide, etc. can be added.

There are no particular limitations on the material of the fishing net treated with the aquatic biofouling inhibitor of the present invention. made of natural fibers such as cotton, linen, silk, wool, or of polymers such as polyvinyl chloride, vinylon, polyvinylidene chloride, polyfluoroethylene, polyamide, polyethylene, polypropylene, polystyrene, polyacrylonitrile Can be applied to fishing nets.

Furthermore, the active ingredient according to the present invention can also be used in combination with other agents conventionally known to have an underwater antifouling effect.

[Effects of the Invention] The aquatic organism adhesion prevention agent of the present invention exhibits an excellent antifouling effect against fouling organisms and has a high sustainability of the effect. In addition, this aquatic biofouling prevention agent is highly safe for fish and shellfish, and the eluted active ingredients are easily decomposed in the environment.
It does not pollute the environment like heavy metal-based drugs. Therefore, by using the aquatic organisms adhesion prevention agent of the present invention, various underwater structures, fishing nets, lobes, buoys, underwater parts of ships, as well as inner surfaces of cooling water pipes, dam gates, etc., can be contaminated by adhesion of aquatic organisms. can now be safely prevented.

[Example] Next, examples of the present invention will be given.

Examples 1 to 8 Cyclic aminoalkylsilanes [1 to [
Underwater antifouling paints (1) to (8) corresponding to each silane in Table 2 were prepared using 8 bottles. The compounding ratios in Table 2 are common to all underwater antifouling paints (1) to (8).

In addition, a pocket mill was used to prepare the paint, and sufficient pulverization and mixing were performed.

Table 1 Table 2 Each of the underwater antifouling paints (1) to (8) obtained above was washed once with wash primer and twice with antirust paint (no silane compound used in the present invention). A test plate was prepared by brushing twice on a treated steel plate (300 x 100 x 1 mm). This test plate was attached to a steel frame, suspended in the sea, and maintained at a water depth of 1.5 m.

The test plates immersed in seawater were pulled up at regular intervals to observe the state of attachment of organisms. The results are shown in Table 3.

For comparison, a test panel without antifouling treatment was also tested at the same time (Comparative Example 1).
It was as listed in the table.

However, the adhesion status of organisms in Table 3 is expressed as follows. The same applies to Table 5 below.

10: ++ +÷+: 10++÷: Total (Not attached, with a small amount of deposits on some parts, with a small amount of deposits on the whole, with deposits on the whole, with a large amount of deposits on the whole) Table 3 Examples 9 to 16 Using the cyclic aminoalkylsilanes [1] to [8] in Table 1 used in Examples 1 to 8, solutions (9) having the compositions in Table 4 corresponding to these silane compounds were prepared. - (16) were prepared.Fishing nets were immersed in each of these solutions, left to stand for 2 hours, removed, and air-dried for 18 hours for antifouling treatment.

Table 4 Next, the 400 x 200 mm fishing net subjected to the antifouling treatment above was attached to a stainless steel frame, suspended in the sea, and maintained at a water depth of 1.5 m.

Fishing nets immersed in seawater were pulled up at regular intervals to observe the amount of organisms attached to them. The results are shown in Table 5.

For comparison, a test was also conducted on a fishing net that had not been antifouled (Comparative Example 2), but the results were as follows.
It was as listed in the table.

Table 5 Patent applicant: Shin-Etsu Chemical Co., Ltd. Agent/Patent Attorney Ryo Yamamoto -

Claims (1)

[Scope of Claims] 1. An aquatic biofouling inhibitor characterized by containing one or more organic silicon compounds represented by the general formula 1 as an active ingredient. ▲There are mathematical formulas, chemical formulas, tables, etc.▼... General formula 1 (In the formula, R^1 and R^2 each represent a methyl group, ethyl group, vinyl group, chloromethyl group, or fluoromethyl group, and R^ 3, R^4 each represents a halogen group or an alkyl group having 1 to 4 carbon atoms, n represents an integer from 1 to 10, and A is -CH_2- group, -CH_2CH_2- group, -CH(CH_3)- group , -O- group, -NH- group or -NCH_3- group.) 2. The compound represented by the general formula 1 is 5-piperidinopentyl-4-chlorophenyldimethylsilane. The listed aquatic biofouling prevention agent. 3. The underwater biofouling inhibitor according to claim 1, wherein the compound represented by the general formula 1 is 6-morpholinohexyl-4-chlorophenyldimethylsilane. 4. The underwater biofouling inhibitor according to claim 1, wherein the compound represented by the general formula 1 is 7-morpholinoheptyl-4-chlorophenyldimethylsilane. 5. The underwater biofouling inhibitor according to claim 1, wherein the compound represented by the general formula 1 is 7-morpholinoheptyl-4-chlorophenylchloromethylmethylsilane.