JP2703530B2 - Antifouling agent for fishing net - Google Patents

Description

Description: BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to the use of aquatic fouling organisms for aquaculture or stationary fishing nets, and for aquatic contaminants such as aquatic materials used therefor. The present invention relates to an antifouling agent for fishing nets having low pollution and containing no heavy metal for preventing adhesion, and having a practical effect. 2. Description of the Related Art Fishing nets for aquaculture or fixed nets and ropes used for the nets are required to be kept in the sea for a long time.
Marine algae and marine fouling organisms such as barnacles, serpula, bryozoans, and mollusks are heavily attached, hindering the economical operation of fishing nets, and requiring a great deal of labor and cost to maintain them. Is the current situation. On the other hand, a series of organotin compounds have a function of preventing fouling organisms and have been widely used in the past, but these organotin compounds are highly toxic, so that products containing them are unprepared. However, there is a drawback that the handling may be hindered, and furthermore, it is not preferable in terms of environmental pollution countermeasures. Therefore, low-pollution underwater antifouling agents containing no heavy metals have been studied. For example,
No. 17764 discloses an aquatic organism repellent mainly containing N-arylmaleimides.
Japanese Patent No. 170004 discloses that by using an N-arylmaleimide and tetrachloroisophthalonitrile in combination, an improved underwater biological repellent is provided. 56-81
No. 505 and Japanese Unexamined Patent Publication No. Sho 56-118006 each disclose tetrachloroisophthalonitrile, a dialkyl sulfide compound or a tetraalkyl thiuram disulfide compound, and an antifouling agent and a fishing net using these three in combination. An antifouling solution is disclosed. DISCLOSURE OF THE INVENTION [0004] The present invention is not practical because any of the conventional compounds alone has a weak effect of preventing adhesion to water-fouling organisms and is not practical. Does not show a broad antifouling effect against fouling organisms, and some are being put into practical use.However, it is necessary to obtain a practically effective antifouling agent for fishing nets with low pollution and low fish toxicity. It is an object. [0005] The present inventors have developed a low toxicity and practically effective antifouling agent for fishing nets, excluding these drawbacks of the conventional antifouling agent for fishing nets. As a result of intensive research, the fish net antifouling agent of the present invention has been completed.
That is, the first invention of the present invention provides a compound represented by the following general formula (i): (Wherein X ¹ and X ² are the same or different and each represents a hydrogen atom or a halogen atom, n is an integer of 1 to 3,
The n Ys are the same or different and represent a halogen atom or a lower alkyl group. )) (Hereinafter, referred to as one or more compounds)
Compound group (I)) and a compound represented by the general formula (ii): (Wherein, R ¹ represents an alkyl group having 1 to 20 carbon atoms, and m represents an integer of 2 to 10) (hereinafter, also referred to as compound group (II)). ) As an active ingredient. The second invention relates to an antifouling agent for fishing nets, comprising a first active ingredient, that is, a compound group (I), a compound group (II), and further, tetrachloroisophthalonitrile as an active ingredient. . DETAILED DESCRIPTION OF THE INVENTION According to the study of the present inventors, the compound group (I), the compound group (II) or tetrachloroisophthalonitrile alone has an effect of preventing adhesion of deposits. Although it is weak and its effect is not practical, as in the present invention, compound group (I) and compound group (II) are blended, or compound group (I), compound group (II), In addition, when tetrachloroisophthalonitrile is blended, it has an unexpectedly excellent and long-lasting synergistic effect, shows a balanced practical effect, and has a low toxicity and a high safety of fishing nets. It has been found that it can be a pollutant. Therefore, the present invention will be described in more detail. As the compounds of the compound group (I) of the present invention,
-(2- (or 3- or 4-) chlorophenyl)
Maleimide, N- (4-iodophenyl) maleimide,
N- (4-fluorophenyl) maleimide, N- (2,
3- (or 2,4-, 2,5-, 2,6- or 3,5-) chlorophenyl) maleimide, N- (2,
4,6-trichlorophenyl) maleimide, N-2-
(Or 3- or 4-) tolylmaleimide, N-
(2- (or 3- or 4-) ethylphenyl) maleimide, N-2,3- (or 2,4-, 2,5-,
2,6- or 3,5-) xylylmaleimide, N-
(2,3- (or 2,4-, 2,5-, 2,6- or 3,5-) ethylphenyl) maleimide, N- (2
-Methyl-3- (or 4-, 5- or 6-ethylphenyl) maleimide, 2-chloro-N-phenylmaleimide, 2-bromo-N-phenylmaleimide, 2-
Chloro-N- (2- (or 3- or 4-) chlorophenyl) maleimide, 2-chloro-N- (4-iodophenyl) maleimide, 2-chloro-N- (2,3-
(Or 2,4-, 2,5-, 2,6- or 3,5
-) Chlorophenyl) maleimide, 2-chloro-N-
(2,4,6-trichlorophenyl) maleimide, 2-
Chloro-N-2- (or 3- or 4-) tolylmaleimide, 2-chloro-N- (2- (or 3- or 4-) ethylphenyl) maleimide, 2-chloro-N
-2,3- (or 2,4-, 2,5-, 2,6- or 3,5-) xylylmaleimide, 2-chloro-N-
(2-methyl-3- (or 4-, 5- or 6-)
Ethylphenyl) maleimide, 2,3-dichloro-N-
Phenylmaleimide, 2,3-dibromo-N-phenylmaleimide, 2,3-dichloro-N- (2- (or 3
-Or 4-) chlorophenyl) maleimide, 2,3
-Dichloro-N- (4-iodophenyl) maleimide,
2,3-dichloro-N- (2,3- (or 2,4-,
2,5-, 2,6- or 3,5-) chlorophenyl) maleimide, 2,3-dichloro-N- (2,4,6
-Trichlorophenyl) maleimide, 2,3-dichloro-N-2- (or 3- or 4-) tolylmaleimide, 2,3-dichloro-N- (2- (or 3- or 4-) ethylphenyl) maleimide , 2,3-dichloro-N-2,3- (or 2,4-, 2,5-, 2,6
-Or 3,5-) xylylmaleimide, 2,3-dichloro-N- (2-ethyl-3- (or 4-, 5- or 6-) methylphenyl) maleimide, and the like. It is not limited. The compounds of the compound group (II) of the present invention include diethylpentasulfide, diethylhexasulfide, dipropyltetrasulfide, diisopropyltrisulfide, ditertiarybutyldisulfide. Dibutyl tetrasulfide, ditertiary butyl tetrasulfide, diamyl tetrasulfide, dihexyl pentasulfide, dioctyl tetrasulfide, ditertiary nonyl pentasulfide, ditertiary Dodecyl pentasulfide, ditetradecyl tetrasulfide, dihexyl tetrasulfide, dinonadecyl tetrasulfide, dimethyl octasulfide, ditertiary butyl decasulfide, etc. It is not limited to these. [0013] The solvent used in the present invention includes:
Acetone, xylene, solvent naphtha, diethylbenzene, pseudocumene, mesitylene, triethylbenzene and the like can be mentioned, with preference given to xylene, solvent naphtha and pseudocumene. The mixing ratio of the compound group (I) and the compound group (II) or the compound group (I), the compound group (II) and the tetrachloroisophthalonitrile of the present invention depends on the required antifouling performance and use environment conditions. Can be arbitrarily changed according to the conditions, and is not particularly limited. Also, the total amount of these is usually 100
The amount is 3 to 30 parts, preferably 8 to 20 parts per part. The antifouling agent for fishing nets of the present invention can be easily produced. That is, the compound group (I) and the compound group (I
I) or a compound group (I), a compound group (II) and tetrachloroisophthalonitrile, and a resin such as a natural resin, oily, synthetic resin, or synthetic rubber for general paint;
It may be mixed and dissolved with a solvent such as xylene, solvent naphtha, pseudocumene, and various additives such as a coloring agent and a plasticizer as needed. Suitable resins are various acrylics,
Examples thereof include polybutene, rosin, cumarone, vinyl chloride, rubber chloride, various alkyds, ethylene, and vinyl acetate copolymer resins. Further, known effective, safe and soluble active ingredients may be blended, and a more balanced effect on various fouling organisms can be expected. Small amounts are also possible. The following examples illustrate the formulation of the antifouling agent for fishing nets of the present invention, but the present invention is not limited by these examples. In the examples, "%" indicating the blending amount is used.
Represents "% by weight". Example 1 2,3-dichloro-N- (2-ethyl-5% 6-methylphenyl) maleimide ditertiary nonyl pentasulfide 10% acrylic resin (50% xylene solution) 22% xylene 53% acetone 10% Example 2 2,3-dichloro-N- (2,6-5% diethylphenyl) maleimide ditertiary nonylpentasulfide 10% acrylic resin (50% xylene solution) 22% xylene 48% acetone 10% toluene 5% Example 3 2,3-dichloro-N- (2-ethyl-5% 6-methylphenyl) maleimide tertiary nonyl pentasulfide 5%・ 5% tetrachloroisophthalonitrile ・ 22% acrylic resin (50% xylene solution) ・ 1% polybutene ・ 42% xylene ・ 20% acetone Example 4 2,3-dichloro-N- (2,6-5% diethylphenyl) maleimide ditertiary nonylpentasulfide 5% tetrachloroisophthalonitrile 5% acrylic resin (50% xylene solution 22% Polybutene 1% Xylene 42% Acetone 20% The effect of the antifouling agent for fishing nets of the present invention will be described by the following experimental examples using the formulation of the above example. In addition,
The comparative formula is as follows. Comparative Example 1 2,3-dichloro-N- (2-ethyl-15% 6-methylphenyl) maleimide acrylic resin (50% xylene solution) 22% xylene 63% Comparative Example 2 2,3-dichloro- N- (2,6-15% diethylphenyl) maleimide acrylic resin (50% xylene solution) 22% xylene 63% Comparative Example 3 N- (2,4,6-trichloro 15% phenyl) maleimide acrylic resin (50% xylene solution) 22% xylene 63% Comparative Example 4 2,3-dichloro-N- (2-ethyl-5% 6-methylphenyl) maleimide / 2,3-dichloro-N- (2,6 -10% diethylphenyl) maleimide / acrylic resin (50% xylene solution) 22% xylene 63% Experimental Example The antifouling solution for fishing nets of the examples of the present invention and the comparative examples. To, each polyethylene nodule network (Section 6, 400 denier / 60
After dip coating and air-drying the book, it was immersed and held at about 1 m below the sea surface in Kii Tanabe Bay, Wakayama Prefecture from early August 1985,
The state of fouling organisms attached to the net was investigated and evaluated according to the following criteria. Rating Adhesion condition 1: No attachment 2: Less than 1% of attachment 3: Less than 5% of attachment 4: Less than 5 to 10% of attachment 5: 10 to 20% of attachment 6: 20 to 50% of attachment 7: Attached Kimono 50% or more In the experiment, if the amount of deposit on the net became 50% or more, the experiment was stopped at that time. Usually, a net having less than 10% of attached matter can be practically used. The results are shown below. [0018] Industrial Applicability Examples 1 and 2 are directed to a fishing net antifouling agent containing a mixture consisting of the compound group (I) and the compound group (II) as an active ingredient. No. 4 relates to an antifouling agent for fishing nets containing, as an active ingredient, a mixture comprising the compound group (I), the compound group (II) and tetrachloroisophthalonitrile. These antifouling agents for fishing nets are extremely excellent and exhibit a synergistic effect of preventing adhesion, exhibit a well-balanced practical effect, and have low toxicity and high safety. It turned out that it could be provided. Therefore, the antifouling agent for fishing nets of the present invention which comprises the compound group (I) and the compound group (II) or the compound group (I), the compound group (II) and tetrachloroisophthalonitrile is compounded. It has been found that it is possible to provide a highly safe and highly safe fishing net antifouling agent which exhibits an extremely excellent and long-lasting synergistic effect of preventing adhesion, exhibits a balanced practical effect, and has low toxicity.

Continuation of front page    (56) References JP-A-53-9320 (JP, A)                 JP-A-59-170004 (JP, A)                 JP-A-56-34604 (JP, A)                 JP-A-56-118006 (JP, A)                 Tokiko Sho 60-17764 (JP, B2)

Claims (1)

(57) [Claims] General formula (i) (Wherein X ¹ and X ² are the same or different and represent a hydrogen atom or a halogen atom, n is an integer of 1 to 3, and n Ys are the same or different and represent a halogen atom or a lower alkyl group). One or more compounds represented by the general formula (ii): (Wherein, R ¹ represents an alkyl group having 1 to 20 carbon atoms, and m represents an integer of 2 to 10). A mixture comprising at least one compound represented by the formula: Antifouling agent for fishing nets. 2. General formula (i) (Wherein X ¹ and X ² are the same or different and represent a hydrogen atom or a halogen atom, n is an integer of 1 to 3, and n Ys are the same or different and represent a halogen atom or a lower alkyl group). One or more compounds represented by the general formula (ii): (Wherein, R ¹ represents an alkyl group having 1 to 20 carbon atoms, and m represents an integer of 2 to 10). A mixture comprising at least one compound represented by the formula: and tetrachloroisophthalonitrile is effective. An antifouling agent for fishing nets, which is contained as an ingredient.