JPH10182323A - Antifouling agent against sea foulings - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain the antifouling agent against sea foulings, comprising a triphenylborane compound and a specific higher aliphatic amine in a specified ratio, exhibiting a synergistic antifouling effect against a wide range of the foulings, and improved in the durability of the effect. SOLUTION: This antifouling agent comprises triphenylborane or its alkali metal hydroxide adduct, and a higher aliphatic secondary or tertiary amine or its salt in a molar ratio of 1:(0.1-10). The antifouling agent can remarkably efficiently prevent troubles caused by the adhesion of the foulings as an antifouling agent for fishing nets and as an antifouling coating. The antifouling agent is effective against Hydroides elegans Haswell, Balanomorpha, Bivalvia, Bryozoa, etc.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an antifouling agent for marine fouling organisms for preventing, for a long time, fouling organisms, in particular, fouling organisms in the sea, from adhering to fishing nets, ship bottoms, seawater intake channels and the like.

[0002]

2. Description of the Related Art In recent years, aquaculture and fishery and the construction of marine facilities have become active, and the habitat of attached organisms has been steadily expanding. The bottom of the ship, underwater structures, aquaculture nets, buoys,
A fixed net or the like is kept in seawater for a long period of time, so that many attached organisms such as barnacles, kansetsu kansetsu, and mussels adhere to them, and these cause various obstacles.

Conventionally, various antifouling agents for preventing the adhesion of these attached organisms have been proposed and put to practical use. Further, it is desired that these antifouling agents have high safety and do not cause water pollution in terms of environmental protection. From such a viewpoint, it is found that a specific higher aliphatic amine having low toxicity and good biodegradability has an excellent antifouling effect, and from the higher aliphatic amine and the specific copolymer, And a long-lasting underwater antifouling composition containing a coating film forming agent (JP-A-1-103672, JP-A-3-2524).
No. 63, JP-A-6-9904 and JP-A-6-904
No. 72807).

On the other hand, a complex compound of triphenylborane and a primary amine, which is one of the active ingredients of the present invention, is known as an antifouling component of an underwater antifouling paint (US Pat. No. 3,2,2).
11,679, JP-A-8-295608 and JP-A-8-295609). However, the use of the above-mentioned triphenylborane or an alkali metal hydroxide adduct thereof as an active ingredient of a marine-fouling organism antifouling agent in combination with a higher aliphatic secondary or tertiary amine or a salt thereof has not been known. .

[0005]

A highly safe antifouling agent such as a higher aliphatic amine exerts a strong antifouling effect on mussels and barnacles, while it has a strong antifouling effect on kanashi kanashi. Has a disadvantage that it requires contact at a higher concentration than the above-mentioned group of organisms. Here, the kansane kansin is a marine periphyton belonging to the phylum Annelida, polychaete, scrophulariaceae, and the larva swims in the sea and attaches when it comes into contact with the adherent base, secretes calcareous vasculature. It grew and the thickness of the adhesion layer reached 10 cm or more in about two months. The object of the present invention is high safety,
An object of the present invention is to provide an antifouling agent which exerts an antifouling effect uniformly on various kinds of attached organisms and maintains the antifouling effect for a certain period.

[0006]

Means for Solving the Problems The inventors of the present invention provide:
Among the higher aliphatic amines, by using a secondary or tertiary amine or a salt thereof and triphenylborane or an alkali metal hydroxide adduct thereof in a specific ratio,
Compared to a single-component antifouling agent, the present inventors have found the surprising fact that a so-called synergistic antifouling effect is exerted on a wide range of attached organisms, and that the effect lasts longer. It was completed.

Thus, according to the present invention, triphenylborane or an alkali metal hydroxide adduct thereof and a higher aliphatic secondary or tertiary amine or a salt thereof are contained as antifouling active ingredients. A marine fouling biofouling agent is provided.

[0008]

BEST MODE FOR CARRYING OUT THE INVENTION As the alkali metal of triphenylborane or an alkali metal hydroxide adduct thereof as an active ingredient of the present invention, lithium, sodium, potassium,
Rubidium, cesium and francium are mentioned, and sodium and potassium are preferred. While triphenylborane is unstable in the air, the alkali metal hydroxide adduct of triphenylborane is stable, and the adduct is preferable in view of workability. Specifically, the adduct includes sodium hydroxide adduct of triphenylborane and potassium hydroxide adduct of triphenylborane.

The secondary or tertiary amine which is the active ingredient of the present invention is, for example, a compound represented by the following general formula (I):

[0010]

Embedded image

(Wherein R ¹ , R ² and R ³ are the same or different and each is a saturated or unsaturated aliphatic hydrocarbon having 1 to 28 carbon atoms which may be substituted by one hydroxyl group or alkoxy group) Group, provided that any one of R ¹ , R ² and R ³ may be a hydrogen atom). Here, the “higher” of the higher aliphatic group refers to the substituents R ¹ , R ² and R
³ means that the total number of carbon atoms is 10 or more.

In the general formula (I), "C1-C28"
As a `` saturated or unsaturated aliphatic hydrocarbon group '', methyl, ethyl, n-propyl, n-butyl, n-pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl Linear saturated hydrocarbon groups such as, for example, hexadecyl, heptadecyl, octadecyl, nonadecyl, icosyl, henicosyl, docosyl, tricosyl, tetracosyl, pentacosyl, hexacosyl, heptacosyl, octacosyl;

Iso-propyl, iso-butyl, sec-butyl,
tert-butyl, iso-pentyl, tert-pentyl, neo-pentyl and the like; methylhexyl, methylheptyl, methyloctyl, ethyloctyl, dimethyloctyl, methylnonyl, ethylnonyl, ethylnonyl, methyldecyl,
Ethyl decyl, dimethyl decyl, methyl undecyl, ethyl undecyl, dimethyl undecyl, methyl dodecyl, ethyl dodecyl, dimethyl dodecyl, methyl tridecyl, ethyl tridecyl, dimethyl tridecyl, methyl tetradecyl, ethyl tetradecyl, dimethyl tetradecyl, Methylpentadecyl, ethylpentadecyl, dimethylpentadecyl, methylhexadecyl, ethylhexadecyl, dimethylhexadecyl, methylheptadecyl,
Ethyl heptadecyl, dimethyl heptadecyl, methyl octadecyl, ethyl octadecyl, dimethyl octadecyl, methyl nonadecyl, ethyl nonadecyl, dimethyl nonadecyl, methyl icosyl, ethyl icosyl, dimethyl icosyl, methyl henicosyl, ethyl henicosyl, dimethyl henicosyl, methyl docosyl, ethyl docosyl, dimethyl docosyl, Methyltricosyl, ethyltricosyl, dimethyltricosyl, methyltetracosyl, ethyltetracosyl, dimethyltetracosyl, methylpentacosyl, ethylpentacosyl, dimethylpentacosyl, methylhexacosyl, ethylhexacosyl Branched, saturated hydrocarbon groups such as dimethyl, dimethylhexacosyl and methylheptacosyl;

Vinyl, allyl, iso-propenyl, butenyl, pentenyl, hexenyl, pepsenyl, octenyl, nonenyl, decenyl, undecenyl, dodecenyl,
Tridecenyl, tetradecenyl, pentadecenyl, hexadecenyl, heptadecenyl, octadecenyl (oleyl = 9-cis-octadecenyl), nonadecenyl, icosenyl, henicosenyl, docosenyl, tricosenyl, tetracosenyl, pentacosenyl, hexacosenyl, heptacocenyl, octacothenyl, octacothenyl, etc. Hexynyl, heptynyl, octynyl, noninyl, decynyl, undecynyl, dodecynyl, tridecynyl, tetradecynyl, pentadecynyl,
Hexadecynyl, heptadecynyl, octadecynyl, nonadecinyl, icosinyl, henicosinyl, docosynyl,
Tricosynyl, tetracosynyl, pentacosynyl, hexacosynyl, heptacosynyl, octacosynyl and the like; butazinyl, pentazinyl, hexazinyl, heptazinyl,
Octazinyl, nonazinyl, decadinyl, undecadinyl, dodecadinyl, tridecazinyl, tetradecadinyl, pentadecadinyl, hexadecadinyl, heptadecazinyl, octadecadinyl, nonadecadinyl, icosazinyl, henicosazinyl, docosadinyl, pentasadinyl, icosazinyl, hexosadicinyl, hexosadinyl, icosazinyl, hexosadinyl Group;

Methyl pentenyl, ethyl pentenyl, dimethyl pentenyl, methyl hexenyl, ethyl hexenyl, dimethyl hexenyl, methyl peptenyl, ethyl pepsenyl, dimethyl pepenyl, methyl octenyl, ethyl octenyl, dimethyl octenyl, methyl nonenyl, ethyl nonenyl, dimethyl nonenyl, methyl decenyl, ethyl decenyl Dimethyl undecenyl, methyl undecenyl, ethyl undecenyl, dimethyl undecenyl,
Methyl dodecenyl, ethyl dodecenyl, dimethyl dodecenyl, methyl tridecenyl, ethyl tridecenyl, dimethyl tridecenyl, methyl tetradecenyl, ethyl tetradecenyl, dimethyl tetradecenyl, methyl pentadecenyl, ethyl pentadecenyl, dimethyl Pentadecenyl, methyl hexadecenyl, ethyl hexadecenyl, dimethyl hexadecenyl, methyl heptadecenyl, ethyl heptadecenyl, dimethyl heptadecenyl, methyl octadecenyl, ethyl octadecenyl, dimethyl octadecenyl, methyl Nonadecenyl, ethyl nonadecenyl, dimethyl nonadecenyl, methyl icosenyl, ethyl icosenyl, dimethyl icosenyl, methyl henicosenyl, ethyl henicosenyl, dimethyl henicosenyl, methyl docosenyl, ethyl doco Cycloalkenyl, dimethyl DoCoMo cell sulfonyl, methyl Trichoderma cell sulfonyl, ethyl Trichoderma cell sulfonyl, dimethyl Trichoderma cell sulfonyl, methyl-tetracosenoylamino sulfonyl, ethyl tetracosenoylamino alkenyl,
Dimethyltetracosenyl, methylpentacosenyl, ethylpentacosenyl, dimethylpentacosenyl, methylhexacosenyl, ethylhexacosenyl, hexacosenyldimethyl, methylheptacosenyl and the like;

Methylpentynyl, ethylpentynyl, dimethylpentynyl, methylhexynyl, ethylhexynyl, dimethylhexynyl, methylheptynyl, ethylheptynyl, dimethylheptynyl, methyloctynyl, ethyloctynyl, dimethyloctynyl, methylnoninyl, ethylnoninyl, dimethylnoninyl, Methyldecynyl, ethyldecynyl, dimethyldecynyl, methylundecinyl, ethylundecinyl, dimethylundecinyl,
Methyl dodecinyl, ethyl dodecynyl, dimethyl dodecynyl, methyl tridecynyl, ethyl tridecynyl, dimethyl tridecynyl, methyl tetradecynyl, ethyl tetradecynyl, dimethyl tetradecynyl, methyl pentadecynyl, ethyl pentadecynyl, dimethyl pentadecynyl , Methyl hexadecynyl, ethyl hexadecynyl, dimethyl hexadecynyl, methyl heptadecynyl, ethyl heptadecynyl, dimethyl heptadecynyl, methyl octadecynyl, ethyl octadecynyl, dimethyl octadecynyl, methyl nonadecynyl , Ethyl nonadecynyl, dimethyl nonadecinyl, methyl icosinyl, ethyl icosinyl, dimethyl icosinyl, methyl henicosinyl, ethyl henikosinyl, dimethyl henosynyl, methyl docosinyl, ethyl docosyl Cycloalkenyl, dimethyl de waist sulfonyl, methyl Trichoderma shea sulfonyl, ethyl Trichoderma shea cycloalkenyl, dimethyl Trichoderma shea sulfonyl, methyl tetracosyl sulfonyl, ethyl tetracosyl alkenyl,
Branched unsaturated hydrocarbon groups such as dimethyltetracosynyl, methylpentacosynyl, ethylpentacosynyl, dimethylpentacosynyl, methylhexacosynyl, ethylhexacosynyl, dimethylhexacosynyl, and methylheptacosynyl;

Examples include coconut alkyl, tallow alkyl, hardened tallow alkyl, soybean alkyl, coconut alkyl, oleoalkyl and the like.

Here, coconut alkyl, tallow alkyl, hardened tallow alkyl, soybean alkyl, coconut alkyl, and oleoalkyl are produced from coconut oil or coconut fat, tallow, soybean oil, coconut oil, or oleostock by known means. It is an alkyl group constituting a higher aliphatic secondary or tertiary amine. In addition, these alkyl groups may include a plurality of types of linear or branched saturated or unsaturated aliphatic hydrocarbon groups having an arbitrary value between 8 and 28 carbon atoms.

The term "saturated or unsaturated aliphatic hydrocarbon group having 1 to 28 carbon atoms substituted by one hydroxyl group" means that any one hydrogen atom of the aliphatic hydrocarbon group is a hydroxyl group. In particular, those in which the parent aliphatic hydrocarbon group is a linear saturated hydrocarbon group and the β-position of which is substituted with a hydroxyl group are preferred. Specifically, hydroxymethyl,
β-hydroxyethyl, β-hydroxy-n-propyl,
β-hydroxy-n-butyl, β-hydroxy-n-pentyl, β-hydroxyhexyl, β-hydroxyheptyl, β-hydroxyoctyl, β-hydroxynonyl,
β-hydroxydecyl, β-hydroxyundecyl, β
-Hydroxydodecyl, β-hydroxytridecyl, β
-Hydroxytetradecyl, β-hydroxypentadecyl, β-hydroxyhexadecyl, β-hydroxyheptadecyl, β-hydroxyoctadecyl, β-hydroxynonadecyl, β-hydroxyicosyl, β-hydroxyhenicosyl, β-hydroxy Docosyl, β-hydroxytricosyl, β-hydroxytetracosyl, β-hydroxypentacosyl, β-hydroxyhexacosyl, β
-Hydroxyheptacosyl, β-hydroxyoctacosyl and the like.

Further, "a saturated or unsaturated aliphatic hydrocarbon group having 1 to 28 carbon atoms and substituted by one alkoxy group"
Is preferably an "alkoxy lower alkyl group having 8 to 28 carbon atoms". Here, “lower” means having 1 to 3 carbon atoms. Specifically, octyloxymethyl, nonyloxymethyl, decyloxymethyl, undecyloxymethyl, dodecyloxymethyl, tridecyloxymethyl, tetradecyloxymethyl, pentadecyloxymethyl, hexadecyloxymethyl, heptadecyloxymethyl , Octadecyloxymethyl, nonadecyloxymethyl, icosyloxymethyl, henicosyloxymethyl, docosyloxymethyl, tricosyloxymethyl,
Tetracosyloxymethyl, pentacosyloxymethyl, hexacosyloxymethyl, heptacosyloxymethyl and the like; octyloxyethyl, nonyloxyethyl,
Decyloxyethyl, undecyloxyethyl, dodecyloxyethyl, tridecyloxyethyl, tetradecyloxyethyl, pentadecyloxyethyl, hexadecyloxyethyl, heptadecyloxyethyl, octadecyloxyethyl, nonadecyloxyethyl, icosyloxy Ethyl, henicosyloxyethyl, docosyloxyethyl, tricosyloxyethyl, tetracosyloxyethyl, pentacosyloxyethyl, hexacosyloxyethyl, etc .; octyloxypropyl, nonyloxypropyl, decyloxypropyl, Decyloxypropyl, dodecyloxypropyl, tridecyloxypropyl, tetradecyloxypropyl, pentadecyloxypropyl, hexadecyloxypropyl, heptadecyloxypro Le, octadecyloxy propyl,
Nonadecyloxypropyl, icosyloxypropyl,
Henicosyloxypropyl, docosyloxypropyl,
Tricosyloxypropyl, tetracosyloxypropyl, pentacosyloxypropyl and the like;

Octenyloxymethyl, nonenyloxymethyl, decenyloxymethyl, undecenyloxymethyl, dodecenyloxymethyl, tridecenyloxymethyl, tetradecenyloxymethyl, pentadecenyloxymethyl, hexadecenyloxymethyl Nyloxymethyl, heptadecenyloxymethyl, octadecenyloxymethyl, nonadecenyloxymethyl, icosenyloxymethyl, henicocenyloxymethyl, docosenyloxymethyl, tricosenyloxymethyl, tetracosenyloxy Methyl,
Pentacosenyloxymethyl, hexacosenyloxymethyl, heptacosenyloxymethyl, etc .; octenyloxyethyl, nonenyloxyethyl, decenyloxyethyl, undecenyloxyethyl, dodecenyloxyethyl, tridecenyloxy Ethyl, tetradecenyloxyethyl, pentadecenyloxyethyl, hexadecenyloxyethyl, heptadecenyloxyethyl, octadecenyloxyethyl, nonadecenyloxyethyl, icosenyloxyethyl, henicocenyloxyethyl, Docosenyloxyethyl, tricosenyloxyethyl, tetracosenyloxyethyl, pentacosenyloxyethyl, hexacosenyloxyethyl, etc .; octenyloxypropyl, nonenyloxypropyl, decenyloxypropyl, undecenyl Propyl, de Deke oxy propyl, tri Deke oxy propyl, tetra Deke oxy propyl, penta Deke oxy propyl,
Hexadecenyloxypropyl, heptadecenyloxypropyl, octadecenyloxypropyl, nonadecenyloxypropyl, icosenyloxypropyl, henicocenyloxypropyl, docosenyloxypropyl, tricosenyloxypropyl, tetracosenyl Nyloxypropyl, pentacosenyloxypropyl and the like;

Coconut alkyloxymethyl, tallow alkyloxymethyl, hardened tallow alkyloxymethyl, soybean alkyloxymethyl, coconut alkyloxymethyl,
Oleoalkyloxymethyl; palm alkyloxyethyl, tallow alkyloxyethyl, hardened tallow alkyloxyethyl, soybean alkyloxyethyl, coconut alkyloxyethyl, oleoalkyloxyethyl; cocoalkyloxypropyl, tallow alkyloxypropyl,
Hardened tallow alkyloxypropyl, soybean alkyloxypropyl, coconut alkyloxypropyl, oleoalkyloxypropyl and the like can be mentioned.

As the substituent R ^{1 in} the general formula (I), β-
A saturated or unsaturated aliphatic hydrocarbon group having 8 to 28 carbon atoms which may be substituted with a hydroxy group, or 8 to 2 carbon atoms;
Preferred are saturated or unsaturated alkoxy lower alkyl groups of 8; specifically, octyl, decyl, dodecyl, tetradecyl, hexadecyl, octadecyl, palm alkyl, tallow alkyl, hardened tallow alkyl, soy alkyl,
Coconut alkyl, oleoalkyl, oleyl, β-hydroxydodecyl, β-hydroxyhexadecyl, β-
Hydroxyoctadecyl, 3-dodecyloxyethyl,
3- (2-Ethylhexyloxy) propyl, 3-cocoalkyloxypropyl and tallowalkyloxypropyl are preferred.

The substituent R ² is preferably a saturated or unsaturated aliphatic hydrocarbon group having 1 to 28 carbon atoms which may be substituted with a β-hydroxy group. , Propyl, butyl, hexyl, octyl, decyl, dodecyl, tetradecyl, hexadecyl,
Octadecyl, coconut alkyl, tallow alkyl, hardened tallow alkyl, soy alkyl, coconut alkyl, oleoalkyl, oleyl, β-hydroxyhexadecyl, β-
Hydroxyoctadecyl is preferred.

Further, the substituent R ³ is preferably a hydrogen atom or a saturated or unsaturated aliphatic hydrocarbon group having 1 to 10 carbon atoms, and specifically, methyl, ethyl, propyl, butyl, hexyl, Octyl and decyl are preferred.

In the present invention, specific examples of the higher aliphatic secondary amine represented by the general formula (I) include dioctylamine, didodecylamine, dioctadecylamine, dioleylamine, dicocoalkylamine, and ditallowalkyl. Amine, di-soy alkylamine, dodecylmethylamine, hexadecylmethylamine, octadecylmethylamine, hexadecylbutylamine, tallowalkylmethylamine, hardened tallowalkylmethylamine, cocoalkylmethylamine, di (β-hydroxyhexadecyl) amine, Examples thereof include di (β-hydroxyoctadecyl) amine, and particularly preferred are dicocoalkylamine (DCA) and disoybean alkylamine (DSA).

In the present invention, specific examples of the higher aliphatic tertiary amine represented by the general formula (I) include octyldimethylamine, dodecyldimethylamine, hexadecyldimethylamine, octadecyldimethylamine, cocoalkyldimethylamine, Tallow alkyl dimethylamine,
Hardened tallow alkyldimethylamine, didodecylmethylamine, dioctadecylmethylamine, ditallowalkylmethylamine, dicocoalkylmethylamine, dodecyltetradecylmethylamine, dodecyloctadecylmethylamine, tetradecylhexadecylmethylamine, dodecylmethylpropylamine , Tallow alkylethylpropylamine, tallowalkyldiethylamine, tallowalkyldipropylamine, tallowalkyldibutylamine, cocoalkyldihexylamine, trioctylamine, tridecylamine, β-hydroxydodecyldimethylamine, β-hydroxyhexadecyldimethylamine, β-
Hydroxyoctadecyldimethylamine, di (β-hydroxyhexadecyl) methylamine, di (β-hydroxyoctadecyl) methylamine and the like, dodecyldimethylamine (DDDA), hexadecyldimethylamine (HDDA), hardened tallow alkyldimethylamine (HTDA) is particularly preferred.

In the present invention, salts of the above-mentioned higher aliphatic secondary or tertiary amines can also be used. Examples of such addition salts include inorganic acids such as hydrochloric acid, hydrobromic acid, nitric acid, sulfuric acid, and phosphoric acid; and organic acids such as formic acid, acetic acid, oleic acid, naphthenic acid, adipic acid, lactic acid, citric acid, and benzoic acid. Or an anionic residue such as saccharin, among which acetic acid and hydrochloric acid are particularly preferred. These higher aliphatic secondary or tertiary amines or salts thereof may be used alone or in combination of two or more.
More than one species can be used in combination.

Accordingly, the combination of triphenylborane or an alkali metal hydroxide adduct thereof with a higher aliphatic secondary or tertiary amine or a salt thereof in the present invention includes, for example, triphenylborane (TPB) and D
CA, TPB and DSA, TPB and DDDA, TPB and H
DDA, TPB, HTDA, etc .; sodium hydroxide adduct of triphenylborane (TPB-Na), DCA, TP
B-Na and DSA, TPB-Na and DDDA, TPB-
Na and HDDA, TPB-Na and HTDA, etc .; potassium hydroxide adduct of triphenylborane (TPB-K) and D
CA, TPB-K and DSA, TPB-K and DDDA, T
PB-K and HDDA, TPB-K and HTDA, etc .;

Triphenylborane (TPB) and acetate of DCA, acetate of TPB and DSA, acetate of TPB and DDDA, acetate of TPB and HDDA, TPB and HTDA
Acetate and the like; sodium hydroxide adduct of triphenylborane (TPB-Na) and acetate of DCA, acetate of TPB-Na and DSA, acetate of TPB-Na and DDDA, T
Acetate of PB-Na and HDDA, TPB-Na and HTD
A acetate, etc .; potassium hydroxide adduct of triphenylborane (TPB-K) and acetate of DCA, TPB-K and DS
A acetate, TPB-K and DDDA acetate, TPB-
Acetates of K and HDDA, TPB-K and HTDA acetate, and the like.

Triphenylborane (TPB) and DCA hydrochloride, TPB and DSA hydrochloride, TPB and DDDA hydrochloride, TPB and HDDA hydrochloride, TPB and HTDA
Hydrochloride and the like; sodium hydroxide adduct (TPB-Na) of triphenylborane and DCA, hydrochloride of TPB-Na and DSA, hydrochloride of TPB-Na and DDDA, T
Hydrochloride of PB-Na and HDDA, TPB-Na and HTD
A hydrochloride, etc .; potassium hydroxide adduct of triphenylborane (TPB-K) and hydrochloride of DCA, TPB-K and DS
A hydrochloride, TPB-K and DDDA hydrochloride, TPB-
K and hydrochloride of HDDA, TPB-K and HTDA hydrochloride, and the like.

The active ingredient of the present invention comprises triphenylborane or an alkali metal hydroxide adduct thereof (component A) and a higher aliphatic secondary or tertiary amine or a salt thereof (component B). The ratio is 1: 0.
It is 1 to 10, preferably 1: 0.2 to 8, more preferably 1: 0.8 to 3. When each component is in the above range, it is preferable because a so-called synergistic antifouling effect can be exerted on a wide range of attached organisms without impairing the antifouling effect of each active ingredient.

For example, when a sodium hydroxide adduct of triphenylborane is used, since the adduct is water-soluble, when formulated as an antifouling agent for fishing nets or an antifouling paint, an aqueous solution of the adduct is used. And a higher aliphatic secondary or tertiary amine or a salt thereof, at room temperature or at a temperature higher than the melting point of the amine or a salt thereof, and the mixture is stirred for several hours. What is obtained by filtering the oil layer portion or extracting it with an organic solvent such as toluene or xylene may be isolated as necessary for the preparation and used as an antifouling active ingredient.

The marine antifouling agent for marine fouling of the present invention is usually
It is prepared in the form of a solution by dissolving in a suitable solvent for improving the coating workability. Examples of the solvent include methyl alcohol, ethyl alcohol, butyl alcohol, xylene, toluene, cyclohexane, acetone, methyl isobutyl ketone, ethylene glycol monoethyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene carbonate, butyl acetate, and dimethyl acetate. Examples thereof include formamide, kerosene, and naphtha. In addition to these, various solvents used in the field of coatings can be used, and a small amount of water may be contained. These solvents may be used as a mixture of two or more kinds. Among them, xylene and propylene glycol monomethyl ether are preferred.

In order to use the marine antifouling agent of the present invention as an antifouling agent for fishing nets, a film forming agent such as a natural resin, a synthetic resin, a plasticizer, and a solvent is appropriately selected and blended. It is formulated and used by operations such as dissolution, dispersion and kneading. Natural resins and synthetic resins used in the above formulations include rosin resin, coumarone resin, polybutene, vinyl chloride resin,
Butyral resin, acrylic resin, chlorinated rubber and the like can be mentioned. Examples of the plasticizer include liquid paraffin, nonylphenol, dioctyl phthalate, diadipate phthalate, trioctyl phosphate, and the like. Examples of the solvent include the solvents described above.

In this case, the mixing ratio of each component in the preparation is as follows:
5-35% by weight of antifouling active ingredient, 3-25% by weight of resin component,
The plasticizer is preferably 0 to 10% by weight, and the total solid concentration is preferably 10 to 60% by weight in view of film forming properties, film forming strength, and the like. When the content of the antifouling active ingredient is less than 5% by weight, a large amount of the antifouling composition is applied and applied in order to apply a required amount of the antifouling active ingredient, which is not preferable because cost and workability deteriorate. On the other hand, when the content is more than 35% by weight, the dissolution control of the antifouling active ingredient and the coating properties deteriorate, which is not preferable.

In order to improve the adhesion to the net or the stiffness of the net, dioctyl phthalate, dioctyl adipate, tricresyl phosphate, trioctyl phosphate, polybutene and the like may be blended. When these antifouling agents are applied to fishing nets, a usual method such as a dipping method is used.

In order to use the marine antifouling agent of the present invention as an antifouling paint, a pigment, a surfactant, a vehicle for preparing a coating film and the like are further added to the antifouling agent for fishing nets. I do. Examples of the pigment include talc, titanium white, graphite, navy blue, red iron oxide, phthalocyanine blue and the like.
As coating film adjustment vehicles, rosin resin, boil oil, chlorinated rubber, polybutene, vinyl chloride resin, acrylic resin,
Epoxy resins and the like can be mentioned.

In this case, the mixing ratio of each component in the preparation is
5-35% by weight of antifouling active ingredient, 3-25% by weight of resin component,
The plasticizer is preferably 0 to 10% by weight and the pigment is preferably 0 to 30% by weight, and the total solid concentration is preferably 25 to 90% by weight in view of film forming properties, film forming strength, and the like. The antifouling paint is useful for various seawater-based structures, and is preferably applied by a usual method, brush coating, a roller method, a spray method, or the like. The antifouling agent of the present invention applied to the antifouling object in this manner forms an antifouling film by drying, and exhibits a long-term antifouling effect.

Further, known antifouling components can be appropriately used in the marine-fouling organism antifouling agent of the present invention. In that case, as a known antifouling component, copper powder, cuprous oxide, copper rhodan, copper naphthenate, copper oleate, zinc dimethyldithiocarbamate, tetraethylthiuram disulfide,
Zinc pyrithione, 2,3-dichloro-N- (2 ′,
6'-diethylphenyl) maleimide, 4,5-dichloro-2-n-octylisothiazolin-3-one, 2-
Thiocyanomethylthiobenzothiazole, tetrachloroisophthalonitrile and the like can be mentioned.

Seawater antifouling systems in which the marine biofouling antifouling agent of the present invention can be effectively used include seawater cooling water systems such as steelworks and power plants, various pipes such as fishing nets, and facilities of aquaculture farms. (For example, fixed nets, aquaculture nets, etc.) Undersea structures such as ship bottoms, bridges and piers.

[0042]

The present invention will be illustrated by the following formulation examples and test examples, but the invention is not limited thereto.

Formulation Example 1 Under a nitrogen atmosphere, triphenylborane [a reagent manufactured by Aldrich, molecular weight 242.000] was placed in a 300 ml four-necked flask equipped with a mechanical stirrer, a condenser, a dropping funnel and a thermometer. 13)
18.5 g (7.6 mmol) and 21.5 g (7.8 mmol) of hexadecyldimethylamine (molecular weight 276)
And 60 g of xylene, and the mixture was stirred at room temperature for a while to obtain a pale yellow, transparent and uniform solution composition a. Table 1
Shows the compounding amount and the combination ratio of each compound.

The abbreviations of each compound in Table 1 are shown below. TPB: Triphenylborane PTPB: Pyridine-triphenylborane HDDA: Hexadecyldimethylamine DCA: Dicocoalkylamine DDDA: Dodecyldimethylamine DSA: Disoybean alkylamine HTDA: Hardened tallow alkyldimethylamine

Formulation Examples 2 to 5 and Comparative Formulation Examples 1 to 3 In the same manner as in Formulation Example 1, the components shown in Table 1 were dissolved in 60 g of xylene, and the blended compositions be to e and Comparative Formulation Examples were prepared. Blended compositions f to h were obtained. Formulation compositions f and g are:
The composition containing the active ingredient of the present invention as a single component as an antifouling active ingredient, and the composition h contain pyridine-triphenylborane. Table 1 shows the compounding amount and the combination ratio of each compound.

[0046]

[Table 1]

Test Example 1 [Test for confirming the efficacy as an antifouling agent for fishing nets] Each of the compounds shown in Table 2 was blended with each of the compositions obtained in Formulation Examples and Comparative Formulation Examples to obtain an antifouling agent for fishing nets. Formulated. A test net (polyethylene aquaculture net: 100, 4 nodes, 40 cm × 60 cm) was immersed in the obtained fishing net antifouling agent, the antifouling agent was attached to the net, and air-dried for 3 days. The test net with the fishing net antifouling agent was applied from the raft in the natural bay (Guraiura Bay, Mie Prefecture) for 3 months from May to July.
Hanging at a depth of 1.5m, Kanane Kanzashi, Barnacle,
The antifouling effect on marine organisms such as bivalves and bryozoans was observed. Table 3 shows the test results. In Table 3, the attached area (%) indicates the proportion of each attached organism, and the attached weight indicates the wet weight (g) of all attached organisms.

[0048]

[Table 2]

[0049]

[Table 3]

Test Example 2 [Effect Confirmation Test as Antifouling Paint] Each compound shown in Table 4 was blended with each of the blended compositions obtained in Formulation Examples and Comparative Formulation Examples, and formulated as antifouling paints. On a test plate (hard vinyl chloride, 7cm x 20cm)
The applied amount of the obtained antifouling paint is 1.5 to 2.0 kg / m ^2.
And dried in air for 3 days. A test plate coated with antifouling paint was applied for 12 months from May.
1.5 to 2 below sea level from a raft in Nature Bay (Guraura Bay, Mie Prefecture)
m at a depth of m, and the antifouling effect on marine-fouling organisms such as kanashi kanashi, barnacles, bivalves, and bryozoans was observed. Observations were made after 6 and 12 months. Table 5 shows the results.

[0051]

[Table 4]

[0052]

[Table 5]

Test Examples 1 and 2 show that the antifouling agent and antifouling paint for fishing nets comprising the composition of the present invention have a long antifouling effect over a long period of time. On the other hand, a fishing net antifouling agent and an antifouling paint comprising a composition containing the antifouling active ingredient of the present invention as a single component and a composition containing pyridine-triphenylborane as an active ingredient are dipped for a short time. And is contaminated by various marine organisms.

[0054]

The marine-fouling biofouling agent of the present invention comprises triphenylborane or an alkali metal hydroxide adduct thereof.
It is characterized by containing a specific higher aliphatic secondary or tertiary amine or a salt thereof as an antifouling active ingredient. Thus, a synergistic antifouling effect is exhibited, and the antifouling effect can be maintained.

Further, since the effective antifouling effect of each active ingredient can be exerted without impairing it, it is possible to extremely effectively prevent damage by marine organisms for fishing net antifouling agents and antifouling paints. , Barnacles, bivalves, bryozoans, etc., can be efficiently and long-term prevented.

Claims (2)

[Claims] 1. An antifouling marine fouling organism comprising triphenylborane or an alkali metal hydroxide adduct thereof and a higher aliphatic secondary or tertiary amine or a salt thereof as an antifouling active ingredient. Agent. 2. The method according to claim 1, wherein triphenylborane or an alkali metal hydroxide adduct thereof and a higher aliphatic secondary or tertiary amine or a salt thereof are mixed at a molar ratio of 1: 0.1 to 10. Item 7. The antifouling agent according to Item 1.