JPH07233003A - Aquatic rest-controlling agent - Google Patents

Abstract

PURPOSE:To obtain an aquatic pest-controlling agent few in problems in terms of safety and health and environment, i.e., low in toxicity and persistence, having no adverse effects on the ecological system and workplace environment, and presenting aquatic pest-controlling activity for a long period. CONSTITUTION:This agent contains, as active ingredient, at least one kind of thiol carboxylate compound of the formula (R1 is an alkyl or an aryl; R2 and R3 each is H, an alkyl or a halogen; X is a halogen, thiocyanate or N)2). This compound, in the form of a highly concentrated solution (e.g. 80wt.% or so), can be impregnated in or applied to fishnets, etc.; or, as an antifouling agent through blending in a coating, it can also be applied to ships or underwater structures, and, by combined use of conventional antifouling agents, longer-term antifouling effect can be expected. The compound of the formula can be obtained by reaction between chloroacetyl chloride and an alkyl or allyl mercaptan in the presence of a hydrochloric acid scavenger.

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 due to the attachment and reproduction of pests in seawater or industrial water systems, and more specifically, ships,
The present invention relates to an underwater pest control agent used for preventing adhesion of underwater pests on the surface of underwater structures such as fishing nets, buoys, and seawater guide pipes.

[0002]

BACKGROUND OF THE INVENTION Underwater structures, such as ships, port facilities, buoys, pipelines, bridges, offshore oilfield drilling facilities, waterway pipes for power plants or coastal plants, fishing nets and rafts for aquaculture. Large adherent flora and fauna such as barnacles, mussels, and sea urchins and microscopic organisms such as diatoms and bacteria adhere to these, and corrosion of structures, increase in seawater friction resistance of ships, massive hay death of seafood due to clogging of fishing nets, 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, triphenyltin oxide, and tributyltin (meth) acrylate polymerization. Antifouling agents containing organometallic compounds such as materials are used.

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 the antifouling agent containing neither heavy metal nor organic metal, for example, a metal salt of dithiocarbamic acid (for example, JP-B-52-13976), a thiourea compound (JP-A-60-42471), a thiuram disulfide compound ( Various compounds containing a sulfur atom, such as JP-A-52-121638), have been proposed, but their effects were insufficient. Further, an alkylphenol compound (for example, JP-A-3-128302) or an N-phenylmaleimide compound (for example, JP-B-2-24242) is used in combination with another compound having a controlling action as an antifouling agent for fishing nets. However, those compounds have no bioactive effect.

[0006] Therefore, the object of the present invention is to prevent health and hygiene and environmental problems, that is, toxicity and persistence are low, have no adverse effect on the ecosystem and working environment, and control pests in water. An object is to provide an aquatic pest control agent that can exert its effects for a long period of time.

[0007]

As a result of intensive studies, the present inventors have found that an aquatic pesticide containing a specific compound can achieve the above object, and Reached

That is, the present invention provides an aquatic pest containing, as an active ingredient, one or more compounds represented by the general formula (I) of the following [Chemical formula 2] (the same as the above-mentioned [Chemical formula 1]). A control agent is provided.

[0009]

[Chemical 2]

The aquatic pest control agent of the present invention will be described in detail below.

The aquatic pest control agent of the present invention contains, as an active ingredient, one or more compounds represented by the above general formula (I). In the compound represented by the general formula (I), examples of the alkyl group represented by R ₁ , R ₂ and R ₃ include methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl and tert-butyl. , Amyl, hexyl, heptyl, octyl, isooctyl,
2-Ethylhexyl, tertiary octyl, nonyl, isononyl, tertiary nonyl, decyl, isodecyl, dodecyl, tridecyl, isotridecyl, tetradecyl, hexadecyl, octadecyl, eicosyl, docosyl, tetracosyl, triacontyl, and other linear or branched alkyl groups. Examples of the aryl group represented by R ₁ include an aromatic group which may have a substituent such as phenyl, tolyl, xylyl and naphthyl.

Examples of the halogen atom represented by R ₂ , R ₃ and X include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom.

Therefore, as the compound represented by the above general formula (I), for example, compounds represented by the following [Chemical Formula 3] to [Chemical Formula 13]
Examples include No. 1 to No. 11.

[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]

A part of the compound represented by the above general formula (I), that is, the thiol carboxylate compound is a known compound. As a method for producing the compound, for example, chloroacetic acid chloride and alkyl or aryl mercaptan are captured by hydrochloric acid. A thiolcarboxylate can be easily synthesized by reacting in the presence of an agent, and a method of introducing a thiocyanato group by reacting this thiolcarboxylate with ammonium thiocyanate can be mentioned.

The synthesis examples of the thiolcarboxylate compound represented by the above general formula (I) used in the present invention are shown below, but the method for producing the compound is not limited to these synthesis examples.

Synthesis Example 1 Synthesis of Compound No. 1 2.26 g (20 mm of octyl mercaptan in a flask)
ol), 2.0 g of triethylamine and 20 g of toluene
Was charged and stirred while cooling. Chloroacetic acid chloride (2.93 g, 20 mmol) was slowly added dropwise while paying attention to the heat generated by hydrochloric acid, and after completion, the temperature was returned to room temperature.

It was confirmed by gas chromatography that the unreacted material had disappeared, and after washing with water and drying, the solvent was removed. A fraction (purified product) at 116 ° C. and 3 mmHg was taken out by a vacuum distillation method.

As a result of measuring the IR spectrum of the purified product,
Carbonyl-based absorption at 1680 cm ^-1 , 740 cm
^-1 shows absorption based on C-Cl, and H ¹ -NM
From R 4.1ppm (s, 2H), 2.9ppm
Since absorption was observed at (t, 2H) and 1.9 to 0.8 ppm (m, 15H), it was confirmed that this purified product was the target product.

[Synthesis Example 2] Synthesis of compound No. 10 13.76 g (55 mmo) of monochloroacetic acid decylthioester synthesized in the same manner as in Synthesis Example 1 using decyl mercaptan in place of octyl mercaptan in Synthesis Example 1
l) and ammonium thiocyanate 4.57 g (60 m
mol) in 20 ml of acetone and reflux under acetone for 5
Reacted for hours. The formed ammonium chloride was filtered off, and after deacetone, the residue was dissolved in toluene, washed with water, dehydrated, and then desolvated to obtain a crude product. 158 by vacuum distillation
A fraction (purified product) having a temperature of ˜160 ° C. and 0.3 mmHg was taken out.

As a result of measuring the IR spectrum of the purified product,
Absorption based on -SCN at 2160 cm ^-1 , 1680 cm
^-1 shows absorption based on C = O, and H ¹ -NMR
From 3.7 ppm (s, 2H), 2.8 ppm (t,
2H), absorption was observed at 1.7 to 0.4 ppm (m, 19H), confirming that this purified product was the target product.

Further, the thiolcarboxylate compound represented by the above general formula (I) is a high concentration liquid, for example, 80
It can be used as a solution of about wt% and can be dipped and applied with fishing nets, etc., or can be blended in paint and applied as antifouling paint to ships and underwater structures, as a paint composition or antifouling liquid for fishing nets. Used.

The content of the thiol carboxylate compound is appropriately selected in consideration of the purpose of use, antifouling period, etc., but is usually 0.5 to 90% by weight, preferably 5 to 80%.
% By weight. If the content is less than 0.5% by weight, a sufficient antifouling effect does not appear, and if it exceeds 90% by weight, no further effect tends to be expected.

The components used for preparing the above-mentioned paint or antifouling liquid are not particularly limited, and the components conventionally used for preparing these paints or antifouling liquids can be used as they are. Examples of the components include vinyl chloride resins, chlorinated rubber resins, chlorinated polyethylene resins, chlorinated polypropylene resins, acrylic resins, styrene-butadiene resins, polyester resins as resin vehicles used as organic solvent-based paints,
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 also used as an aqueous paint. As the vehicle, acrylic emulsion resin, epoxy emulsion resin, vinyl acetate resin or the like can be used.

The aquatic pest control agent of the present invention comprises a conventionally used metal-containing antifouling agent, nitrogen-containing antifouling agent, sulfur-containing antifouling agent, oxygen-containing antifouling agent and phosphorus-containing antifouling agent. By using one or more antifouling agents selected from the group in combination, the antifouling effect can be exerted for a longer period of time.

Examples of the metal-containing antifouling agent include copper-based metal powder such as copper powder and copper-nickel alloy powder; cuprous oxide, cuprous thiocyanate, basic copper carbonate, copper pyrophosphate, naphthene. Copper compounds such as copper acid, copper abietic acid, and copper oxyquinoline; zinc dimethyldithiocarbamate, zinc diethyldithiocarbamate, zinc dibutyldithiocarbamate, zinc ethylphenyldithiocarbamate,
Zinc ethylenebisdithiocarbamate, zinc propylenebisdithiocarbamate, zinc bis (dimethyldithiocarbamoyl) zinc ethylenebisdithiocarbamate, manganese ethylenebisdithiocarbamate, nickel dimethyldithiocarbamate, nickel dibutyldithiocarbamate, copper dimethyldithiocarbamate, iron dimethyldithiocarbamate, etc. And the dithiocarbamate-based compound.

Examples of the nitrogen-containing antifouling agent include 2
-(4-thiazolyl) benzimidazole, methyl-1
-(Ω-cyanopentylcarbamoyl) -2-benzimidazole, 2-mercaptobenzimidazole zinc,
Benzimidazole compounds such as 2-thiocyanomethylthiobenzimidazole; Nitrile compounds such as tetrachloroisophthalonitrile and 5-chloro-2,4-difluoro-6-methoxyisophthalonitrile; 1-
[2- (2,4-dichlorophenyl) -4-propyl-
1,3-dioxolanyl-2-methyl 1-1H-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; N-trichloromethylthiotetrahydrophthalimide, N-1,
1,2,2-tetrachloroethylthiootetrahydrophthalimide, N-trichloromethylthiophthalimide,
Phthalimide compounds such as N-fluorodichloromethylthiophthalimide; N- (2-chlorophenyl) maleimide, N- (4-fluorophenyl) maleimide, N
-(3,5-Dichlorophenyl) maleimide, N-
(2,4,6-Trichlorophenyl) maleimide, N-4
And maleimide compounds such as tolylmaleimide and N-2,4-xylylmaleimide.

Examples of the sulfur-containing antifouling agent include, for example, tetramethylthiuram disulphide, tetraethylthiuram disulphide, tetra-n-propylthiuram disulphide, tetraisopropylthiuram disulphide, tetra-n-butylthiuram disulphide, tetra. Isobutyl thiuram disulfide, N, N'-ethylenebisthiocarbamoyl sulfide, N, N'-
Propylene bisthiocarbamoyl sulfide, N,
Thiuram-based compounds such as N'-butylene bisthiocarbamoyl sulfide; 2-mercaptobenzothiazo-
2- (thiocyanomethylthio) benzothiazole,
2- (thiocyanomethylsulfonyl) benzothiazo-
2-thiocyanoethylthio-4-chlorobenzothiazole, 2-thiocyanopropylthio-5,7-dichlorobenzothiazole, 2-thiocyanomethylthio-4,
Benzothiazole compounds such as 5,6,7-tetrachlorobenzothiazole; 4,5-dichloro-2-n-octyl-4-isothiazolin-3-one, 2-n-octyl-4-isothiazoline Isothiazoline compounds such as -3-one and 1,2-benzisothiazolin-3-one; 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- Three
N-haloalkylthio compounds such as 4-dichlorophenyl-N′-methylurea and N-fluorodichloromethylthio-N-trissulfonyl-N-methylamine;
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, 3,5-dibenzyltetrahydro-1,3,5-thiadiazine-2-
Thiadiazine compounds such as thion; methyl thiocyanate, chloromethyl thiocyanate, ethyl thiocyanate,
Examples of thiocyan compounds such as methylenebisthiocyanate, chloromethylenebisthiocyanate, ethylenebisthiocyanate, chloroethylenebisthiocyanate, isobornylthiocyanate, methylisothiocyanate, allylisothiocyanate, phenylisothiocyanate and benzylisothiocyanate. .

As the oxygen-containing antifouling agent, for example, 2
-Amino-3-chloro-1,4-naphthoquinone, 2,3
Quinone compounds such as dicyano-1,4-dithiaanthraquinone; alkylphenol compounds such as caprylphenol and nonylphenol.

Examples of the phosphorus-containing antifouling agent include, for example, tris (octylphenyl) phosphite, tris (nonylphenyl) phosphite, tris (dinonylphenyl) phosphite, tris (mono, dimixed nonylphenyl) phosphite. Alkyl phenyl phosphate compounds such as phyto; alkyl phenyl phosphate compounds such as tris (octyl phenyl) phosphate, tris (nonyl phenyl) phosphate, tris (dinonyl phenyl) phosphate, tris (mono and di mixed nonyl phenyl) phosphate, etc. To be

Further, the aquatic pest control agent of the present invention comprises:
A plasticizer, a coloring pigment, a filler, a solvent and the like which are usually used can be blended in any proportion.

[0042]

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

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

This 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 attached organisms was observed over time (1 month, 3 months, and 6 months), The ratio of the adhered area to the coated area was measured, and evaluated according to the following four criteria from A to D according to the following criteria. The results are shown in [Table 1] below.

A: No adhesion is observed at all. 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.

[0046]

[Table 1]

Example 2 The following formulation [compounding] was thoroughly mixed with a high speed homomixer to prepare an antifouling agent for fishing nets. Using this antifouling agent for fishing nets, a polyethylene test net (60 knotless twisted knots 20
(cm × 30 cm) was dyed by dipping 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] below.

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

[0049]

[Table 2]

From the results of Examples 1 and 2 above, when cuprous oxide, nonylphenol, maleimide compound or the like was used as a component of the aquatic pest control agent (Comparative Example 1)
-1 to 1-4 and Comparative Examples 2-1 to 2-4) lose their effects in a short period of time, whereas the case of using the specific thiol carboxylate compound according to the present invention (Examples) In 1-1 to 1-9 and Examples 2-1 to 2-9), it is clear that the effect lasts for a long time.

Further, the specific thiolcarboxylate compound according to the present invention is considered to have no properties such as toxicity and teratogenicity, which adversely affect the ecosystem, and control pests in water which does not cause environmental pollution. It is apparent that it is extremely useful as a component of the agent.

[0052]

INDUSTRIAL APPLICABILITY The aquatic pest control agent of the present invention has low safety and health and environmental problems, that is, low toxicity and persistence.
It has no adverse effect on the ecosystem and working environment, and can exert the control effect of pests in water for a long time.

Claims (1)

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