JPH04230603A - Attachment inhibitor for marine attaching organism and method for preventing attaching - Google Patents

Abstract

PURPOSE:To obtain an attachment inhibitor, containing a quanternary ammonium compound and a higher aliphatic amine compound and effective in preventing materials from fouling with marine attaching organisms, especially Hydroides elegans Haswell. CONSTITUTION:An attachment inhibitor containing (A) a compound, e.g. cetyltrimethylammonium bromide expressed by formula I (R is 12-18C aliphatic hydrocarbon group; R<1> is methyl or 12-18C aliphatic hydrocarbon group; R<2> is methyl or benzyl; R<3> is methyl; all R<1> to R<3> may be pyridine or picolyl through N, except that both R<1> and R<2> are simultaneously aliphatic hydrocarbon group and benzyl; X is acid residue) and (B) a compound expressed by formula II [R<4> is 12-18C aliphatic hydrocarbon group; R<5> is H or methyl; R<6> is H, methyl, -(CH2)2-NH2 or -(CH2)3-NH2 (provided that R<6> is methyl when R<5> is methyl)] or its acid addition salt, e.g. tetradecylamine hydrochloride in an amount of 0.1-8 pts.wt., preferably 0.2-5 pts.wt. based on 1 pt.wt. ingredient (A).

Description

[Detailed description of the invention]

0001

[Industrial Application Field] The present invention relates to an agent and method for preventing the adhesion of marine sessile organisms, in particular to seaweed, and in particular to coating it on underwater structures such as seawater intake channels, fishing nets, and ship bottoms, or adding it to seawater systems. Accordingly, the present invention relates to an anti-adhesion agent and a method for preventing the adhesion of marine adhesion organisms, which are effective in preventing stains caused by marine adhesion organisms, particularly the Japanese snail.

0002

[Prior art] In recent years, in closed bays and fish farms,
There has been an increase in the number of snails, which is a type of marine sessile organism, attached to the sea. In factories that use seawater as cooling water, it adheres to the cooling tubes of heat exchangers and causes pitting corrosion.

On the other hand, in aquaculture farms, it causes great damage to oyster cultivation, and a large amount of it adheres to the ike net for fish cultivation, obstructing the flow of seawater, causing a lack of oxygen in the ike, and causing the fish to be raised. It is causing death. Also,
Furthermore, if it adheres to the bottom of the ship, it will reduce the sailing speed of the ship.
There are obstacles such as having to go to a dock for this removal.

[0004] As antifouling agents for sea waterways, ship bottom paints, and fishing nets, injection of chlorine agents, organic tin compounds,
Antifouling agents containing cuprous oxide were widely used. These compounds are highly toxic to a variety of marine organisms, and they were able to control both barnacles and mussels, as well as Kanzane spp.

[0005] However, these antifouling agents have poor degradability in nature and are bioconcentrated, so their use has been regulated to prevent environmental pollution. Along with that,
As the development of highly safe alternative antifouling agents has become urgent and the safety of compounds has been pursued, the selectivity of medicinal efficacy against individual marine sessile organisms has become apparent.

[0006] From this point of view, many highly safe marine fouling organisms adhesion prevention agents have been proposed, and quaternary ammonium compounds and higher aliphatic amine compounds have also been proposed and are known.

That is, quaternary ammonium compounds are described in Japanese Patent Publication No. 52-39895 as a control agent for mussels, and the efficacy of higher aliphatic amine compounds against marine sessile organisms is reported in Japanese Patent Publication No. 56-3862, Japanese Patent Publication No. 59
-20641, Special Publication No. 60-23641, Special Publication No. 60
No. 0-52725, Japanese Patent Application Publication No. 5-55101, Japanese Patent Application Publication No. 1999
It is publicly known from the publication No.-197407.

[0008]

[Problems to be Solved by the Invention] However, conventionally proposed antifouling agents such as quaternary ammonium compounds and higher fatty acid amine compounds have a strong antifouling effect on mussels and barnacles. However, in order to prevent the adhesion of Kasane Kanzaki, it is necessary to inject a high concentration in seawater systems, and for antifouling agents, a high concentration of elution from the antifouling coating is required. is required. On the contrary, this causes environmental pollution, and the processing costs are also enormous.

[0009] Kasane Kanzaki is a marine sessile organism that belongs to the classification Annelida, Polychaete, and Spermidae.The larva swims in the sea, attaches to the adhesion substrate, and secretes a calcareous living tube. It is not uncommon for the attached layer to reach a thickness of 10 cm or more in about two months.

[0010] In view of the current situation and recognition, the present invention provides effective use of Kasane Kanzaki that is less toxic to humans, animals, fish and shellfish, and causes less environmental pollution, especially for fishing nets, facilities, and waterways in sea areas where Kasane Kanzaki preferentially attaches. It is an object of the present invention to provide an anti-adhesive agent and a method thereof.

[0011]

[Means for Solving the Problems] According to the present invention, the general formula (I) [Formula 1] [wherein R is a saturated or unsaturated linear aliphatic hydrocarbon having 12 to 18 carbon atoms] group, R1 is a methyl group or a saturated or unsaturated linear aliphatic hydrocarbon group having 12 to 18 carbon atoms, R2 is a methyl group or a benzyl group, R
3 may represent a methyl group, or all of R1, R2 and R3 may be a pyridine group or a picolyl group via a nitrogen atom. However, the case where R1 and R2 are simultaneously a saturated or unsaturated linear aliphatic hydrocarbon group having 12 to 18 carbon atoms and a benzyl group is excluded. X represents an acid residue. ] and one or more quaternary ammonium compounds represented by the general formula (II) [Formula 2] [wherein R4 is a saturated or unsaturated linear aliphatic hydrocarbon group having 12 to 18 carbon atoms, R5 is a hydrogen atom or a methyl group, R6 is a hydrogen atom, a methyl group, -(CH2)
It is a group represented by 2-NH2 or -(CH2)3-NH2 (provided that when R5 is a methyl group, R3 means a methyl group). There is provided an anti-adhesion agent for marine sessile organisms, which contains as an active ingredient one or more of the higher aliphatic amine compounds represented by the following formulas or their acid addition salts. Furthermore, according to the present invention, there is provided a method for preventing the adhesion of marine fouling organisms, which comprises using a quaternary ammonium compound of the above formula (I) in combination with a tertiary amine compound of formula (II).

[0012] As a result of extensive research into effective antifouling agents for Kasane Kanzaki using compounds that have little impact on the environment, the present invention was developed using a quaternary ammonium compound represented by the general formula (I) and a quaternary ammonium compound represented by the general formula (II). This was made based on the discovery that by using higher aliphatic amine compounds in combination, the objective can be achieved with significantly smaller amounts than when each is used alone.

In the present invention, specific examples of the quaternary ammonium compound represented by the general formula (I) include laurylbenzyldimethylammonium chloride, lauryltrimethylammonium chloride, cetylbenzylmethylammonium chloride, cetyltrimethylammonium chloride, stearyl Benzyldimethylammonium chloride, stearyltrimethylammonium chloride, laurylpyridinium chloride, laurylpicolium chloride, cetyltrimethylammonium saccharide, cetyltrimethylammonium bromide, tallow alkyltrimethylammonium bromide, dilauryldimethylammonium chloride, dicetyldimethylammonium chloride, distearyldimethyl Examples include ammonium chloride.

Specific examples of acid residues include anions of acids such as hydrochloric acid, hydrobromic acid, nitric acid, sulfuric acid, phosphoric acid, formic acid, acetic acid, oleic acid, naphthenic acid, adipic acid, lactic acid, citric acid, or saccharin. Examples include residues.

In this invention, specific examples of higher aliphatic amine compounds represented by general formula (II) include dodecylamine, tetradecylamine, hexadecylamine,
Primary amines such as octadecylamine, oleylamine, cow finger alkylamine and coconut alkylamine; Secondary amines; Tertiary amines such as dodecylmethylamine, hexadecyldimethylamine, octadecyldimethylamine, coconut alkyldimethylamine, cow finger amine dimethylamine, hardened tallow alkyldimethylamine; dodecylethylenediamine, hexadecylethylenediamine, octadecyl N-monosubstituted ethylenediamine such as ethylenediamine, oleylethylenediamine, tallow alkylethylenediamine; dodecyltrimethylenediamine,
Examples include N-monosubstituted trimethylene diamines such as hexadecyl trimethylene diamine, octadecyl trimethylene diamine, oleyl trimethylene diamine, coconut alkyl trimethylene diamine, tallow alkyl trimethylene diamine, hardened tallow alkyl trimethylene diamine, and the like.

Among these amines, "coconut alkyl...amine,""tallowalkyl...amine," and "hardened beef tallow alkyl...amine" mean that the amine can be extracted from coconut oil, coconut fat, beef tallow, etc. by known means. This means that it is an amine mixture (mixed alkyl amine) whose main component is a saturated or unsaturated linear aliphatic hydrocarbon group having 12 to 18 carbon atoms.

[0017] These acids may be used in the form of acid addition salts, and examples of this acid include the above-mentioned inorganic acids and organic acids.

Next, in order to exhibit a sufficient synergistic effect, the mixing ratio of the quaternary ammonium compound represented by the general formula (I) and the higher aliphatic amine compound represented by the general formula (II) is determined. The higher aliphatic amine compound should be used in combination in a weight ratio of 0.1 to 8, preferably 0.2 to 5, to 1 of the quaternary ammonium compound.

[0019] When adding these compounds to the marine cooling system, it is possible to add a predetermined amount of each compound individually, but it is preferable to mix them to form a one-component preparation. That is, when the quaternary ammonium compound represented by the general formula (I) and the higher aliphatic amine compound represented by the general formula (II) are added as a single solution, they are dissolved in water in the form of a salt. or use a suitable solvent (
It is preferable to dissolve or emulsify and suspend the composition in water or an organic solvent such as ethyl alcohol, butyl diglycol, ethylene glycol, propylene glycol monomethyl ether, etc., and add a surfactant if necessary to prepare a preparation at an appropriate concentration. Examples of surfactants in this case include polyoxyethylene alkyl ethers, polyoxyethylene alkyl esters, sorbitan alkyl esters, polyoxyethylene sorbitan alkyl esters, polyoxyethylene polyoxypropylene copolymers, alkyl betaines, etc. can be mentioned.

[0020] The amount of the anti-adhesion agent of the present invention added to the seawater cooling system is generally 0.0% as the amount of active ingredient relative to the seawater flow rate.
0.005 ppm to 0.2 ppm, preferably 0.01 to 0.005 ppm to 0.2 ppm, preferably 0.01 to 0.
1 ppm may be injected for 12 to 24 hours per day. The amount added may vary slightly depending on the conditions of the sea area, but it is desirable to increase it when the amount of Kasane Kanzaki is particularly large. However, in any situation, an addition amount of up to 0.5 ppm is sufficient, and anything more than this is unfavorable from the standpoint of environmental pollution and economics.

Next, when used as a coating agent for fishing nets, paints, etc., it is usually used in liquid form. The compound of the present invention is blended with natural resins, synthetic resins, plasticizers, solvents, color pigments, etc. by appropriately selecting them, and is formulated into a formulation by operations such as dissolving, dispersing, and kneading.

Natural resins and synthetic resins used as coating film forming agents include rosin, boiled oil, chlorinated rubber, polybutene, vinyl chloride resin, acrylic resin and the like. Examples of the plasticizer include dioctyl phthalate, diadipate phthalate, tricresyl phosphate, trioctyl phosphate, and the like.

[0023] When the anti-adhesion agent of the present invention is used as an antifouling agent, a liquid form is usually suitable, and organic solvents used in this case include ethanol, xylene, toluene,
Examples include cyclohexanone, kerosene, methyl isobutyl ketone, butyl acetate, dimethylformamide, naphtha, propylene glycol monoethyl ether, etc. In addition to these, various solvents used in the paint field can be used, and some may contain water. It's okay to stay.

When used as an antifouling agent for fishing nets, the active ingredient is 10 to 30% by weight, and the resin content is 5 to 20% by weight.
% by weight, the plasticizer is in a liquid form by dissolving or dispersing 0 to 10% by weight in an organic solvent, and the total solid concentration is 25 to 6.
It is preferable to set the content to 0% by weight in terms of film-forming properties, film-forming strength, etc.

On the other hand, the antifouling agent of the present invention may be prepared as an antifouling paint in the form of a dispersion by blending other pigments. Examples of the pigment include talc, titanium white, yellow lead, navy blue, red iron, and phthalocyanine blue.

The composition of the antifouling paint is as follows: active ingredients (total amount): 10-30% by weight, resin: 5-20%, plasticizer: 0-10%, pigment: 10-30% by weight. is mixed with an organic solvent to form a formulation.

This antifouling paint is useful for various seawater structures, and is preferably applied by brushing, spraying, or the like. The anti-adhesion agent of the present invention applied to the anti-fouling object in this way forms an anti-fouling film when dried,
Demonstrates long-term antifouling effect.

In addition to the active ingredients of the present invention, copper naphthenate, copper oleate, dimethyldithiocarbamate,
Known antifouling agents such as tetraethylthiuram disulfide, zinc pyrithione, 2,3-dichloro-N-(2',6'-diethylphenyl)maleimide, 4,5-dichloro-2-noctyl-4-isothiazolin-3-one, etc. Agent components can be used in combination as appropriate.

[Examples] The present invention will be explained below with reference to Examples and Comparative Examples, but the present invention is not limited thereby. Example 1 Comparison of effects when used in sea waterway system (Formulation Examples 1 to 5, Comparative Examples 1 to 5)

[0029] A submersible pump pumps up seawater from a seawater conduit in a steelworks, where troubles often occur due to Kanzaki, and a test channel containing a test net is placed in a PVC pipe with an inner diameter of 74 mm and a length of 2 m. For 40 days, seawater was passed in a one-time flow (water flow rate: 3 tons/hour each), and each mixed lumber agent was injected using a chemical pump, and the number of snails and other attached organisms was counted. The results are shown in Tables 1 and 2.

The chemical solutions were prepared in emulsion type and water-soluble type, diluted with water, and injected in a predetermined amount.

For the emulsion type, both compounds were dissolved in isopropyl alcohol and polyoxyethylene sorbitan monooleate (HLB15) was added to form an emulsion. The water-soluble type was made water-soluble by reacting equimolar amounts of both compounds with hydrochloric acid or acetic acid. Consideration of waterway test From the above test results, it can be seen that the combination of a quaternary ammonium compound and a higher aliphatic amine compound has a synergistic effect on preventing the adhesion of Kasane Kanzaki (see Formulation Examples 1 to 5).

In comparison, a single system of quaternary ammonium compounds or higher aliphatic amine compounds had no effect on Kasane Kanzaki (see Comparative Examples 1 to 5). Example 2 Comparison of effects when used for fishing nets (Table 3 shows the blending ratio. Formulation examples: 1 to 6, Comparative examples: 1 to 6)

003
3] As a test net, polyethylene (100 pieces, 4 sections,
The experiment was carried out using an aquaculture net measuring 40 cm x 60 cm. A test net was immersed in each antifouling agent to adhere the antifouling agent to the net, and the net was air-dried for 3 days. Then, for three months from May to July, it was suspended from a raft in Rekiura Bay, Mie Prefecture, at a depth of 1.0 to 1.5 meters below the sea surface, and the antifouling effect against Kasane Kanzaki and other attached organisms was increased.
Observed after a month. The results are shown in Table 4.

That is, Table 4 shows the weight of attached organisms (wet weight) and the composition ratio (%) of attached organisms. Consideration of soaking test From the above test results, the antifouling agent for fishing nets of the present invention obtained by mixing and preparing a quaternary ammonium compound and a higher aliphatic amine compound has antifouling properties against Kasane Kanzaki for a long period of three months or more. It can be seen that it is effective (formulation examples 1-
(see 6).

In comparison, the quaternary ammonium compound or the higher aliphatic amine compound alone had no long-term antifouling effect on Kasane Kanzaki (see Comparative Examples 1 to 6). Example 3 Comparison of effects when used for paints (Tables 5 and 6 show the blending ratios. Formulation examples: 1 to 7, Comparative examples: 1 to 6)

003
6] A hard PVC board measuring 7 cm x 20 cm was used as a test plate. The coating amount of each paint formulation is 1.5~
It was applied twice at a weight of 2.0 kg/m2. Then, it was suspended from a raft at a depth of 1.5 to 2.0 meters below the sea surface in Rekiura Bay, Mie Prefecture, for one year starting in May, and the antifouling effect on Kasane Kanzaki and other attached organisms was confirmed after 6 months and 12 months. Observed. The results are shown in Table 7.

That is, in Table 7, the adhesion area (%) of sessile organisms
and the composition ratio (%) of sessile organisms. Discussion of immersion test From the above test results, the antifouling agent of the present invention obtained by mixing and preparing a quaternary ammonium compound and a higher aliphatic amine compound has an antifouling effect on Kasane Kanzaki for a long period of 9 months or more. (See formulation examples 1 to 7)

In comparison, the quaternary ammonium compound or the higher aliphatic amine compound alone had no long-term antifouling effect on Kasane Kanzaki (see Comparative Examples 1 to 6).

[Effects of the Invention] According to the present invention, damage caused by marine fouling organisms can be extremely efficiently prevented for use in seawater cooling systems, fishing net antifouling agents, and antifouling paints, and in particular, damage caused by Kasane Kanzaki can be efficiently prevented. becomes possible.

[Table 1]

[Table 2]

[Table 3]

[Table 4]

[Table 5]

[Table 6]

[Table 7]

Claims (4)

[Claims] Claim 1: General formula (I) [Formula, R is a saturated or unsaturated linear aliphatic hydrocarbon group having 12 to 18 carbon atoms, and R1 is a methyl group or a carbon atom number] 12 to 18 saturated or unsaturated linear aliphatic hydrocarbon groups, R2 is a methyl group or benzyl group, R3 is a methyl group, or pyridine in which all of R1, R2, and R3 are via a nitrogen atom or picolyl group. However, R1 and R2 each have 12 to 1 carbon atoms at the same time.
This excludes the case where it is a saturated or unsaturated linear aliphatic hydrocarbon group and a benzyl group. X represents an acid residue. ] and one or more quaternary ammonium compounds represented by the general formula (I
I) [Formula R4 is a saturated or unsaturated linear aliphatic hydrocarbon group having 12 to 18 carbon atoms, R5 is a hydrogen atom or a methyl group, R6 is a hydrogen atom, a methyl group, - (CH2)2-NH
2 or -(CH2)3-NH2 (however, R
When 5 is a methyl group, R6 means a methyl group). ] An anti-adhesion agent for marine sessile organisms, which contains as an active ingredient one or more of the higher aliphatic amine compounds represented by the following formulas or acid addition salts thereof. 2. The anti-adhesion agent according to claim 1, wherein the marine adhesion organism is Kasane Kanzaki. [Claim 3] One or more quaternary ammonium compounds of the general formula (I) of claim 1 and one or more higher aliphatic amine compounds of the general formula (II) are combined with marine deposits. A method for preventing the adhesion of marine sessile organisms, which is characterized by adding it to a wet water system. 4. The method for preventing adhesion according to claim 3, wherein the marine adhesion organism is Kasane Kanzaki.