JPH06219915A - Controlling agent against underwater pest - Google Patents

Abstract

PURPOSE:To obtain a controlling agent against underwater pests, having low toxicity, residual properties, etc., and capable of manifesting effects thereof for a long period without adversely affecting an ecosystem or a working environment. CONSTITUTION:This controlling agent against underwater pests comprises one or two or more of halogen-containing phosphate compounds of formula I [R1 is alkyl; R2 is H or alkyl; R is halogenated alkyl; m and n are 1 or 2, with the proviso that (m+n) is 3], e.g. compounds of formulas II and III as an active ingredient. The controlling agent is usually prepared as a coating composition or an antifouling solution, etc., for fishing nets, etc., for use. In the process, the compound of formula I is used in an amount within the range of preferably 0.5-90wt.%, especially preferably 5-80wt.%.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an underwater pest control agent for the purpose of preventing damages caused by the attachment and reproduction of pests in seawater or industrial water systems, and more specifically, ships, fishing nets, buoys, and seawater guides. The present invention provides an underwater pest control agent used for preventing adhesion of underwater pests on the surface of underwater structures such as pipes.

[0002]

BACKGROUND OF THE INVENTION Problems to be Solved by the Invention Underwater structures such as ships, harbor facilities, buoys, pipelines, bridges, offshore oilfield drilling facilities, waterway pipes for power plants or seaside plants, fishnets and aquaculture. Large adherent flora and fauna such as barnacles, mussels, and sea urchins and microscopic organisms such as diatoms and bacteria adhere to rafts, causing structure corrosion, increasing seawater friction resistance of ships, and massive death of seafood due to clogging of fishnets. Damage such as sedimentation and reduced work efficiency due to increased weight will occur. In addition, in industrial water systems such as cooling water that uses natural water such as river water and lake water, and in circulating type cooling devices that use medium and tap water, bacteria, diatoms, cyanobacteria, blue-green algae, etc. abnormally propagate and water quality It causes problems such as deterioration of cooling efficiency due to deterioration and adhesion to vessel walls, blockage of water pipes, and reduction of flow rate.

In order to prevent such damage from pests in water, inorganic heavy metal compounds such as cuprous oxide, copper rhodanide and mercury oxide, or tributyltin oxide,
It has been practiced to use an antifouling agent containing an organometallic compound such as triphenyltin oxide and tributyltin (meth) acrylate polymer.

However, these conventionally used compounds are extremely toxic, and not only require special handling, but also cause malformation due to accumulation in fish bodies and environmental pollution. It has been desired to use an antifouling agent containing no organic metal.

As antifouling agents containing neither heavy metals nor organic metals, alkylphenols (JP-A-3-12830) are used.
No. 2) or dichloro-N-phenylmaleimides (Japanese Examined Patent Publication No. 24242/1990), but these compounds are not sufficient in their effects, and in a short period of time. At present, it is not practical because the effect is lost.

[0006] Therefore, there are problems in safety and hygiene and the environment, that is, toxicity and persistence are low, which does not adversely affect the ecosystem and working environment, and which can exert its effect for a long period of time. There is a need for agents, and it is an object of the present invention to provide such pest control agents in water.

[0007]

Means for Solving the Problems The inventors of the present invention have conducted extensive studies in order to achieve the above object, and as a result, by using an aquatic pest controlling agent containing a halogen-containing phosphate compound, the above object was achieved. I was found to be done.

That is, the present invention provides an aquatic pest control agent containing, as an active ingredient, one or more compounds represented by the following general formula (I).

[0009]

[Chemical 2]

The present invention having the above-mentioned gist will be described below in more detail.

In the compound represented by the general formula (I), examples of the alkyl group represented by R ₁ and R ₂ include, for example, methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl and tert-butyl. , Amyl, hexyl, heptyl, octyl, isooctyl, 2-ethylhexyl, secondary octyl, tertiary octyl, nonyl, isononyl, tertiary nonyl, decyl, isodecyl, dodecyl, tridecyl, isotridecyl, tetradecyl, hexadecyl, octadecyl, eicosyl, docosyl , Straight chain or branched alkyl groups such as tetracosyl and triacontyl, and examples of the halogenated alkyl group represented by R include 2-chloroethyl and 1-chloro-2.
-Propyl, 3-chloro-1-propyl, 1,3-dichloro-2-propyl, 4-chloro-1-butyl, 2,2
-Bis (chloromethyl) -1-propyl, 3-chloro-
2,2-Dimethyl-1-propyl, 6-chloro-1-hexyl, 10-chloro-1-decyl, 2-bromoethyl, 1-bromo-2-propyl, 3-bromo-1-propyl, 1,3- Dibromo-2-propyl, 2,3-dibromopropyl, 1,4-dibromo-2-butyl, 3-bromo-2-methyl-1-propyl, 3-bromo-2,2
-Dimethyl-1-propyl, 6-bromo-1-hexyl, 7-bromo-1-heptyl, 8-bromo-1-octyl, 9-bromo-1-nonyl, 10-bromo-1-decyl, 11-bromo -1-undecyl, 12-bromo-
Examples include 1-dodecyl and perfluoroethyl.

Some of the compounds represented by the above general formula (I) are known compounds, for example, phosphorus oxychloride,
Method of reacting phosphorus pentachloride, phosphorus pentaoxide or triphenyl phosphate with alkylphenol and halogenated alcohol simultaneously or sequentially, or reacting mono- or diaryl phosphite di- or monohalide with olefin oxide such as ethylene oxide or propylene oxide It can be easily manufactured by the method.

Examples of the compound represented by the above general formula (I) used in the present invention include the following compounds.

[0014]

[Chemical 3]

[0015]

[Chemical 4]

[0016]

[Chemical 5]

[0017]

[Chemical 6]

[0018]

[Chemical 7]

[0019]

[Chemical 8]

[0020]

[Chemical 9]

[0021]

[Chemical 10]

[0022]

[Chemical 11]

[0023]

[Chemical 12]

[0024]

[Chemical 13]

[0025]

[Chemical 14]

[0026]

[Chemical 15]

The present invention relates to an aquatic pest control agent containing one or more compounds represented by the general formula (I) as an active ingredient, which is one of conventionally used antifouling agents or It is also possible to use it in combination with two or more kinds, and in some cases, it is possible to exert the effect for a longer period of time.

Examples of the antifouling agent which can be used in combination with the halogen-containing phosphate compound of the present invention include tetramethylthiuram disulfide, tetraethylthiuram disulfide, tetra-n-propylthiuram disulfide, tetraisopropylthiuram disulfide, Tetra-n-butyl thiuram disulfide, tetraisoptyl thiuram disulfide, N, N'-ethylenebisthiocarbamoyl sulfide, N, N'-propylenebisthiocarbamoyl sulfide, N, N '
-Thiuram compounds such as butylene bisthiocarbamoyl sulfide; copper metal powders such as copper powder and copper-nickel alloy powder; cuprous oxide, cuprous thiocyanate, basic copper carbonate, copper pyrophosphate, copper naphthenate Copper compounds such as copper abietic acid and copper oxyquinoline; zinc dimethyldithiocarbamate, zinc diethyldithiocarbamate, zinc dibutyldithiocarbamate, zinc ethylphenyldithiocarbamate, zinc ethylenebisdithiocarbamate,
Zinc propylene bisdithiocarbamate, zinc bis (dimethyldithiocarbamoyl) ethylenebisdithiocarbamate, manganese ethylenebisdithiocarbamate, nickel dimethyldithiocarbamate, nickel dibutyldithiocarbamate, copper dimethyldithiocarbamate,
Dithiocarbamate compounds such as iron dimethyldithiocarbamate; 2- (4-thiazolyl) benzimidazo-
Methyl-1- (ω-cyanopentylcarbamoyl)
Benzimidazole compounds such as 2-benzimidazole, 2-mercaptobenzimidazole zinc, 2-thiocyanomethylthiobenzimidazole; 2-mercaptobenzothiazole, 2- (thiocyanomethylthio) )
Benzothiazole, 2- (thiocyanomethylsulfonyl) benzothiazole, 2-thiocyanoethylthio-4
-Chlorobenzothiazole, 2-thiocyanopropylthio-5,7-dichlorobenzothiazole, 2-thiocyanomethylthio-4,5,6,7-tetrachlorobenzothiazole and other benzothiazols -Type compounds; nitrile-type compounds such as tetrachloroisophthalonitrile and 5-chloro-2,4-difluoro-6-methoxyisophthalonitrile; 4,5-dichloro-2-n-octyl-4-isothiazoline-3 -One, 2-n-octyl-4-isothiazolin-3-one, 1,2-benzisothiazolin-3-one and other isothiazoline compounds; 1- [2-
(2,4-Dichlorophenyl) -4-propyl-1,3
-Dioxolanyl-2-methyl-1-1 (H) -1,
2,4-triazole, 4,4-dimethyl-2- (1,
2,4-triazol-1-yl) -1- (4-trifluoromethyl-2-chlorophenyl) -1-pentene-
Triazole compounds such as 2-ol; 2, 3, 5,
6-Tetrachloro-4- (methylsulfonyl) pyridine, 2,3,6-trichloro-4-propylsulfonylpyridine, 2,6-dichloro-3,5-dicyano-4-
Pyridine compounds such as phenylpyridine; 2,4-dichloro-6- (α-chloroanilino) -s-triazine,
2-chloro-4-methylamino-6-isopropylamino-s-triazine, 2-chloro-4,6-bis (ethylamino) -s-triazine, 2-chloro-4,6-bis (isopropylamino)- s-triazine, 2-methylthio-4,6-bis (ethylamino) -s-triazine, 2-methylthio-4-ethylamino-6-isopropylamino-s-triazine, 2-methylthio-4-t
Triazine compounds such as -butylamino-6-cyclopropylamino-s-triazine; 3- (3,4-dichlorophenyl) -1,1-dimethylurea, 3- (3,4
-Dichlorophenyl) -1-methoxy-1-methylurea, 1- (α, α'-dimethylbenzyl) -3-methyl-3-phenylurea, 1- (2-methylcyclophenyl) -3-phenylurea, etc. Urea compounds; quinone compounds such as 2-amino-3-chloro-1,4-naphthoquinone and 2,3-dicyano-1,4-dithiaanthraquinone; N-trichloromethylthiotetrahydrophthalimide, N-1,1, 2,2-Tetrachloroethylthiootetrahydrophthalimide, N-trichloromethylthiophthalimide, N-fluorodichloromethylthiophthalimide, N, N-dimethyl-N'-phenyl-N'-
(Fluorodichloromethylthio) sulfurylamide, trichloromethylthiomethanesulfone-p-chloroanilide, N- (1,1,2,2, -tetrachloro-2-fluoroethylthio) methanesulfonanilide, N-fluorodichloromethylthio-N -3-Chlorophenyl-N '
-Dimethylurea, N-fluorodichloromethylthio-N
-3,4-dichlorophenyl-N'-methylurea, N-
Fluorodichloromethylthio-N-trissulfonyl-
N-haloalkylthio compounds such as N-methylamine; N- (2-chlorophenyl) maleimide, N- (4
-Fluorophenyl) maleimide, N- (3,5-dichlorophenyl) maleimide, N- (2,4,6-trichlorophenyl) maleimide, N-4-tolylmaleimide,
Maleimide compounds such as N-2,4-xylylmaleimide; 3,5-dimethyl-tetrahydro-1,3,5
2 (H) -thiadiazin-2-one, 3,3′-ethylenebis (tetrahydro-4,6-dimethyl-2H-1,
3,5-thiadiazin-2-one, 3,5-dimethyl-
2-thiotetrahydro-1,3,5-thiadiazine,
Thiadiazine compounds such as 3,5-dibenzyltetrahydro-1,3,5-thiadiazine-2-thione; methyl thiocyanate, chloromethyl thiocyanate, ethyl thiocyanate, methylenebisthiocyanate, chloromethylenebisthiocyanate, ethylenebisthiocyanate , Chloroethylene bis-thiocyanate, isobornyl thiocyanate, methyl isothiocyanate, allyl isothiocyanate, phenyl isothiocyanate,
Thiocyan compounds such as benzyl isothiocyanate;
Alkylphenol compounds such as caprylphenol and nonylphenol; tris (octylphenyl) phosphite, tris (nonylphenyl) phosphite, tris (dinonylphenyl) phosphite, tris (mono,
Alkylphenyl phosphite compounds such as di-mixed nonylphenyl) phosphite; alkyls such as tris (octylphenyl) phosphate, tris (nonylphenyl) phosphate, tris (dinonylphenyl) phosphate, tris (mono, di-mixed nonylphenyl) phosphate Examples thereof include phenyl phosphate compounds.

The underwater pest control agent according to the present invention is
It is usually prepared and used as a coating composition or an antifouling agent liquid for fishnets and the like. In this case, the halogen-containing phosphate compound content is preferably 0.5 to 90% by weight, more preferably 5 to 80% by weight, and is appropriately selected in consideration of the purpose of use, antifouling period and the like. For example, a solution of about 80% by weight can be dipped and applied in a fish net or the like, or can be mixed in a paint and applied as antifouling paint to a ship or an underwater structure.

The components used for preparing the above coating composition or antifouling agent liquid are not particularly limited, and the components conventionally used for preparing these coating materials or antifouling agent liquid may be used as they are. it can. For example, as a resin vehicle used as an organic solvent-based paint, vinyl chloride resin, chlorinated rubber resin, chlorinated polyethylene resin, chlorinated polypropylene resin, acrylic resin, styrene-butadiene resin, polyester resin, epoxy resin, polyamide resin , Petroleum-based resin, silicone resin, silicone rubber-based resin, wax, paraffin, rosin ester, rosin-based resin, etc. can be used alone or in combination, and acrylic resin is used as a resin vehicle used as an aqueous paint. Resins, epoxy emulsion resins, vinyl acetate resins and the like can be used.

In addition to the halogen-containing phosphate compound of the present invention, a plasticizer, a coloring pigment, a filler, a solvent and the like which are usually used can be contained in an optional ratio.

[0032]

EXAMPLES The present invention will be described in more detail with reference to examples below, but the present invention is not limited to the following examples.

Example 1 Chlorinated rubber having a chlorine content of 65% (CR-2 manufactured by Asahi Denka Kogyo Co., Ltd.
20 parts by weight of the sample compound was added to 100 parts by weight of the 30% xylene solution of 0), sufficiently stirred, then coated on a hard vinyl chloride plate, and dried for 24 hours to obtain a test piece.

The test piece was immersed in a test raft in Yokosuka City, Kanagawa Prefecture, at a depth of 1 m in the sea, and the degree of fouling by adherent organisms was observed over time to measure the ratio of the adhered area to the painted area. The results were evaluated according to the following criteria on a four-point scale. The results are shown in Table 1. A: No adhesion was observed. B: Adhesion was recognized in a portion of 50% or less. C: Adhesion was recognized in 50% or more. D: It adhered to the entire surface and the coated surface was completely covered.

[0035]

[Table 1]

Example 2 [Composition] wt% Sample compound (Table 2) 10 Acrylic resin (50% xylene solution) * 1 20 Chlorinated paraffin * 2 1 Xylene 69 * 1: NT-100 * 2 manufactured by Nitto Kasei : Asahi Denka Kogyo Adeka Sizer E-430

The above mixture was thoroughly mixed with a high speed homomixer to prepare an antifouling agent for fishnets. Using this antifouling agent for fish nets, polyethylene test net (60 knotless twisted nodes 20 cm
(30 cm) was dyed with a dyeing net and air-dried for 2 days, and then the degree of fouling by attached organisms was examined in the same manner as in Example 1. The results are shown in Table 2.

[0038]

[Table 2]

From the results of each of the above examples, when alkylphenol was used as a pest control agent in water, the effect was lost in a short period of time, whereas when the halogen-containing phosphate compound of the present invention was used. It is clear that the effect lasts for a long time.

Further, the halogen-containing phosphate compound of the present invention is considered not to have properties such as toxicity and teratogenicity which adversely affect the ecosystem, and is extremely useful as an aquatic pest control agent which does not cause environmental pollution. It is clear that

[0041]

INDUSTRIAL APPLICABILITY The aquatic pest control agent of the present invention has low safety and hygiene and environmental problems, that is, low toxicity and persistence, and does not adversely affect the ecosystem and working environment. The effect can be exerted for a long period of time.

─────────────────────────────────────────────────── ───

[Procedure amendment]

[Submission date] February 9, 1993

[Procedure Amendment 1]

[Document name to be amended] Statement

[Name of item to be corrected] 0002

[Correction method] Change

[Correction content]

[0002]

BACKGROUND challenges technology and invention is to provide a underwater structures, for example, ships, port facilities, buoys, pipelines,
Large adherent plants and animals such as barnacles, mussels, and sea bream, and microscopic organisms such as diatoms and bacteria adhere to bridges, offshore oilfield drilling facilities, waterway pipes of power plants or waterfront plants, fishnets and rafts for aquaculture. Corrosion, increased seawater friction resistance of ships, large-scale death of seafood due to clogging of fishnets, sedimentation due to increased weight, and reduced work efficiency. In addition, in industrial water systems such as cooling water that uses natural water such as river water and lake water, and in circulating type cooling devices that use medium and tap water, bacteria, diatoms, cyanobacteria, blue-green algae, etc. abnormally propagate and water quality It causes problems such as deterioration of cooling efficiency due to deterioration and adhesion to vessel walls, blockage of water pipes, and reduction of flow rate.

[Procedure Amendment 2]

[Document name to be amended] Statement

[Correction target item name] 0006

[Correction method] Change

[Correction content]

[0006] Therefore, the object of the present invention is to prevent health and hygiene and environmental problems, that is, toxicity and persistence are low, which does not adversely affect the ecosystem and working environment, and the effect is long-term. An object is to provide an aquatic pest control agent that can exert its effect. .

[Procedure Amendment 2]

[Document name to be amended] Statement

[Correction target item name] 0007

[Correction method] Change

[Correction content]

[0007]

Means for Solving the Problems As a result of intensive studies conducted by the present inventors in order to achieve the above object, the above object was achieved by using an aquatic pest control agent containing a halogen-containing phosphate compound. I found that.

Claims (1)

[Claims] 1. An aquatic pest control agent comprising, as an active ingredient, one or more compounds represented by the following general formula (I). [Chemical 1]