JPH07133207A - Antifoulant for fishnet - Google Patents

Abstract

PURPOSE:To provide an antifoulant for fishnet, composed essentially of triphenylboronpyridine, excellent in prevention of fouling due to various kinds of marine fouling organisms, especially due to a Hydrozoa or an Obelia, adhesion to a fishnet and workability and reduced in environmental pollution. CONSTITUTION:This antifoulant for fishnet is composed essentially of triphenylboronpyridine of the formula or triphenylboronpyridine of the formula and a silicone oil. Triphenylboronpyridine of the formula has merits such as high safety and low environmental pollution. In addition, if a silicone oil is used in combination with triphenylboronpyridine of the formula, the antifouling effect is remarkably improved and maintained for a long period. The antifouling effect especially against, e.g. a large-sized organism such as a barnacle, a Serpula, a sea-squirt or a moss worms or an alga is improved. In addition thereto, the antifouling effect against a Hydrozoa or an Obelia is also improved and further, the effect on slime is remarkably improved.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention prevents aquatic fouling organisms from adhering to a fishing net for aquaculture or stationary and fishing net accessories such as floats and ropes used therefor, and is effective for a long time. The present invention relates to a low pollution pollution anti-fouling agent for fishing net equipment.

[0002]

[Prior art]

Since fishing nets for aquaculture or stationary are stored in the sea for a long period of time, marine fouling organisms such as seaweeds, barnacles, serpra, bryozoans and molluscs are strongly attached to the nets.
The current situation is that they impede the economical operation of these and maintain them with great effort and expense. Although various studies and proposals have been made as measures against this, conventionally, organotin polymers including organotin have been widely used. However, tin compounds are designated as Class 1 Specified Chemical Substances and Class 2 Specified Chemical Substances because of their high toxicity to the environment, especially their accumulation in the environment, and their use as a fishing net antifouling agent has been prohibited. . Therefore, a fishing net antifouling agent containing cuprous oxide as an active ingredient has come to be used as a non-tin antifouling agent, but cuprous oxide is eluted in seawater and remains as a copper ion or a copper compound. Therefore, it may have an unfavorable effect on the environment. Further, cuprous oxide has a drawback that it is extremely difficult to prepare a formulation having practical and good workability because it has a large specific gravity and causes sedimentation. That is,
Since settling will occur in the storage container, it is necessary to perform painting work while stirring again. Furthermore, when coating fishing net antifouling agents, most of them are dip-coated, and if sedimentation occurs during the coating operation, the active ingredients cannot be evenly applied, resulting in poor antifouling performance. It has drawbacks. Therefore, it is necessary to take measures such as increasing the viscosity of the paint in order to reduce the sedimentation. The fishing net is made of a material such as polyethylene and polyester, and since it is relatively difficult to apply the paint, the fishing net is made to have adhesiveness by impregnating the stitches. However, when the paint viscosity is increased,
As a result, the penetration into the net is reduced, resulting in poor adhesion.

For these reasons, the advent of a low-pollution fishing net antifouling agent that does not contain heavy metals is desired, and various organic agents have been proposed. In particular, many compounds are dissolved in a solvent or resin to make the coating film flexible due to its suitability as a fishing net antifouling agent, for example, many compounds such as tetraethylthiuram disulfide, tetrachloroisophthalonitrile, and dimethylphenyldichloromaleimide. A compound that has been used but is satisfactory in terms of coating film physical properties and antifouling properties has not yet been found. There are also examples of using tetravalent boron compounds of tetraarylboron derivatives as ship bottom antifouling paints (JP-A-51-62831, JP-A-60-248780, JP-A-61). -4776
Issue). However, these compounds are inferior in the antifouling property of hydroids and the antifouling property of Oberias, and cannot be applied to fishing nets.

[0005]

SUMMARY OF THE INVENTION The present invention has been made in view of the situation of the above-mentioned prior art, does not contain organic tin or heavy metal having high environmental persistence, is excellent in low pollution and has antifouling property. The object is to provide a fishing net antifouling agent which is excellent, and is particularly excellent in the antifouling property of hydro worms and the antifouling property of obelia which cannot be reached by the conventional techniques, and has good workability.

[0006]

Means for Solving the Problems As a result of intensive studies to solve the above problems, the present inventors have found that a fishing net antifouling agent containing triphenylboron pyridine represented by the formula (1) as an essential component However, it has an excellent antifouling property against various marine fouling organisms, and in particular, it has an excellent antifouling effect on hydrozoa and obelia that could not be achieved by conventional techniques, and has good adhesion to fishing nets. No sedimentation was observed, and it was found that the workability was good, and the present invention was completed. That is, the present invention provides a fishing net antifouling agent, which comprises triphenylboron pyridine represented by the formula (1) of Chemical formula 3 as an essential component.

[0007]

[Chemical 3]

Furthermore, the present invention provides a fishing net antifouling agent, which comprises triphenylboron pyridine represented by the formula (1) and silicone oil as essential components. Hereinafter, the present invention will be described in detail.

The fishing net device of the present invention means a fishing net and a fishing net accessory such as a float or rope used for the fishing net. The fishing net to which the anti-fouling agent of the present invention is applied is not particularly limited and is a fishing net made of various materials such as polyethylene and polyester.

The fishing net antifouling agent of the present invention contains triphenylboron pyridine of the above formula (1) as an essential component. Triphenylboron pyridine has advantages such as high safety and low environmental pollution. Therefore, when used as a fishing net antifouling agent, most of the toxic aspects of the above-mentioned known organometallic compounds are solved, so there is almost no toxicity or skin irritation which is a problem during painting, and fish There is no problem in toxicity. Also, in terms of antifouling properties, it shows a broad spectrum for adherent organisms, and is often seen in aquaculture areas, cuprous oxide and tin compounds for large organisms such as barnacles, cerpra, ascidians, bryozoans and algae. Shows a strong effect equal to or higher than. Further, it can be mentioned as a feature that it exerts a surprising antifouling effect on Cudrum Hydro and Oberias, which did not show antifouling effect on cuprous oxide and organic tin in a fixed net. Triphenylboron pyridine used in the fishing net antifouling agent of the present invention has a specific gravity of 1.1 and is very small compared to the specific gravity of 5.9 of cuprous oxide. The viscosity does not cause sedimentation and the workability is very good.

In the present invention, when triphenylboron pyridine is used in combination with silicone oil, the antifouling property is remarkably improved and can be maintained for a long time. That is, when silicone oil is used in combination with triphenylboron pyridine, the antifouling effect against large organisms such as barnacles, serpra, squirts, bryozoans and algae, which are often seen in cultured sea areas, is improved compared to the case where silicone oil is not used in combination. In addition, the antifouling effect on hydro and obelia, which is a problem in the fixed sea area, is improved, and the antifouling effect on slime is dramatically improved in addition to the above antifouling effect on large organisms. To do.

The silicone oil used in the present invention is
For example, polydimethylsiloxane, polymethylphenylsiloxane, methylphenylsiloxane-dimethylsiloxane copolymer, polyether modified polydimethylsiloxane, polyether modified polymethylalkylsiloxane,
Examples thereof include, but are not limited to, polyester-modified polydimethylsiloxane, fluorosilicone oil, amino-modified silicone oil, and other functional group-modified silicone oil. Among these silicone oils, preferred are polydimethylsiloxane, methylphenylsiloxane-dimethylsiloxane copolymer, and polyether-modified polydimethylsiloxane. These silicone oils may be used alone or in combination of two or more. The compounding ratio of triphenylboron pyridine and silicone oil is not particularly limited, but usually the weight ratio of triphenylboron pyridine to silicone oil is 1:99.
The range is from 9 to 999: 1, preferably from 1:99 to 9
It is in the range of 9: 1, particularly preferably 10:90 to 9
The range is 0:10.

The fishing net antifouling agent of the present invention usually contains a resin vehicle. The resin vehicle is not particularly limited and various resin vehicles can be used, and examples thereof include polyester resin, acrylic resin, epoxy resin, rosin, rosin ester, rosin-based soap, vinyl chloride-based resin, chlorinated rubber-based resin, and chlorine. Polyethylene resin, chlorinated polypropylene resin, styrene-butadiene resin, polyamide resin, petroleum resin, oil resin and the like.
These resin vehicles may be used alone, or
You may use it in combination of 2 or more type. The molecular weight of the resin vehicle is usually 1,000,000 or less in terms of weight average molecular weight,
The range of 200 to 200,000 is particularly preferable.

In addition, the fishing net antifouling agent of the present invention usually contains a solvent. The solvent is not particularly limited and various solvents can be used, for example, aromatic hydrocarbon solvents such as benzene, toluene, xylene and trimethylbenzene, alcohol solvents such as ethanol, isopropanol and n-butanol, and acetone. Examples thereof include ketone solvents such as diethyl ketone and methyl isobutyl ketone. These solvents may be used alone or in combination of two or more.

The amount of triphenylboron pyridine contained in the anti-fouling agent for fishing nets of the present invention is not particularly limited, but when a resin vehicle and a solvent are contained,
The amount is usually 0.01 to 99% by weight, preferably 0.1 to 70% by weight, based on the total amount of triphenylboron pyridine, resin vehicle and solvent. 0.
If it is less than 01% by weight, the antifouling property may deteriorate,
If it exceeds 99% by weight, the physical properties as an antifouling agent for fishing nets are insufficient. When triphenylboron pyridine and silicone oil are used in combination, the total compounding amount of these compounds is not particularly limited, but relative to the total amount of triphenylboron pyridine, silicone oil, resin vehicle and solvent. The range is usually 0.1 to 99% by weight, preferably 0.1 to 70% by weight, and particularly preferably 0.1 to 50% by weight. 0.1
If it is less than 10% by weight, the antifouling property may deteriorate.
If it exceeds 9% by weight, the physical properties as an antifouling agent for fishing nets are insufficient.

Other chemicals may be added to the fishing net antifouling agent of the present invention. Examples of these agents include dithiocarbamate agents, carbamate agents, maleimide agents, isothiazolone agents, and other agents such as tetrachloroisophthalonitrile. Also,
A plasticizer such as ditertiary nonyl polysulfide, polybutene, liquid paraffin, or tricresyl phosphate can be added to the fishing net antifouling agent of the present invention. Furthermore, the fishing net antifouling agent of the present invention includes pigments and other additives such as polyamide phosphoric acid type, polyamide type,
An unsaturated polycarboxylic acid-based dispersant, a defoaming agent, an anti-sagging agent, or the like can be added. In the anti-fouling agent for fishing nets of the present invention, other chemicals, plasticizers, pigments and other additives can be contained in any mixing ratio.

The fishing net antifouling agent of the present invention can be produced by mixing the above components, and if necessary, adding various additives and mixing them. The method of mixing each component and the method of adding various additives are not particularly limited, and various methods can be used, and the mixing order and the addition order can also be performed in various mixing orders and addition orders.

The present invention also provides a method for antifouling fishing net equipment, which prevents the adhesion of aquatic fouling organisms and exerts excellent antifouling property by applying the antifouling agent for fishing net equipment of the present invention to the fishing net equipment. You can do that. As a method for applying the fishing net antifouling agent to the fishing net, various coating methods such as dip coating and spray coating can be applied, but dip coating is preferable.

[0019]

EXAMPLES Next, the present invention will be described more specifically by way of Examples and Comparative Examples. The present invention is not limited to these examples. In addition, the evaluation test of the fishing net antifouling agents of Examples and Comparative Examples was performed by the following method.

Antifouling test The fishing net antifouling agents of Examples and Comparative Examples were dip-coated on a fishing net, fixed on an iron frame of 40 cm x 60 cm, and allowed to stand at a water depth of 10 m from the net of the fixed net of Akkeshi Town, Akkeshi District, Hokkaido. Immersion was carried out, and the attached species and the attached area were visually observed.

Sedimentation Test Cold cycle of the anti-fouling agents for fishing nets of Examples and Comparative Examples (40
C. × 12 hours, −20 ° C. × 12 hours) The sedimentation property after 1 week was measured.

Adhesion test After the anti-fouling agents for fishing nets of Examples and Comparative Examples were applied to polyethylene plates and dried at room temperature for 3 days, an attachment having a diameter of 3 mm was adhered to the coating film with an instant adhesive to remove the peeling force. It was measured with a dyno meter (manufactured by BYK).

Example 1 5 parts by weight of triphenylboron pyridine, polyester resin (lauric acid / isophthalic acid / trimellitic anhydride /
Adipic acid / 1,5-pentanediol / trimethylolpropane = 20/25/10 / 8.4 / 28.9 /
7.7, weight average molecular weight: 1900) 10 parts by weight and xylene 85 parts by weight were uniformly stirred to prepare a fishing net antifouling agent.

Example 2 10 parts by weight of triphenylboron pyridine, acrylic resin (methyl methacrylate / positive butyl methacrylate = 60 /
40, weight average molecular weight: 20,000) 5 parts by weight, polybutene (polybutene 06N (manufactured by NOF Corporation)) 10
By weight, 75 parts by weight of toluene were uniformly stirred to prepare a fishing net antifouling agent.

Example 3 1 part by weight of triphenylboron pyridine, 5 parts by weight of tetraethylthiuram disulfide, 2 parts by weight of liquid paraffin (Moresco White P350P (manufactured by Matsumura Petrochemical Laboratory)), epoxy resin (epoki 834 (Mitsui Toatsu pressure) Chemical Co., Ltd.)) 3 parts by weight and 89 parts by weight of xylene were uniformly stirred to prepare a fishing net antifouling agent.

Example 4 10 parts by weight of triphenylboron pyridine, 2 parts by weight of tetrachloroisophthalonitrile, 30 parts by weight of polybutene (polybutene 200N (manufactured by NOF Corporation)) and 58 parts by weight of xylene were uniformly stirred to obtain a fishing net. An ingredient antifouling agent was prepared.

Example 5 1 part by weight of triphenylboron pyridine, 4,5-dichloro-2-n-octyl-3 (2H) -isothiazolone 4
By weight, 10 parts by weight of rosin, 20 parts by weight of xylene and 65 parts by weight of isopropanol were uniformly stirred to prepare a fishing net antifouling agent.

Comparative Example 1 A fishing net antifouling agent was prepared by uniformly stirring 25 parts by weight of cuprous oxide, 20 parts by weight of rosin, 1 part by weight of polyamide wax, and 54 parts by weight of xylene.

Comparative Example 2 A commercial product (organic nitrogen-sulfur-based fishing net antifouling agent) was prepared.

Comparative Example 3 5 parts by weight of tetraphenylboron pyridine salt, 10 rosin
By weight, 20 parts by weight of xylene and 65 parts by weight of isopropanol were uniformly stirred to prepare a fishing net antifouling agent. The results of the antifouling test of the fishing net antifouling agents of Examples 1 to 5 and Comparative Example are shown in Table 1, the results of the sedimentation test are shown in Table 2, and the results of the adhesion test are shown in Table 3.

[0031]

[Table 1]

[0032]

[Table 2]

[0033]

[Table 3]

Example 6 5 parts by weight of triphenylboron pyridine, polyester resin (lauric acid / isophthalic acid / trimellitic anhydride /
Adipic acid / 1,5-pentanediol / trimethylolpropane = 20/25/10 / 8.4 / 28.9 /
7.7, weight average molecular weight: 1900) 10 parts by weight, KF
5-100 parts by weight of 96-100 (polydimethylsiloxane manufactured by Shin-Etsu Chemical Co., Ltd.) and 80 parts by weight of xylene were uniformly stirred to prepare a fishing net antifouling agent.

Example 7 5 parts by weight of triphenylboron pyridine, polyester resin (lauric acid / isophthalic acid / trimellitic anhydride /
Adipic acid / 1,5-pentanediol / trimethylolpropane = 20/25/10 / 8.4 / 28.9 /
7.7, weight average molecular weight: 1900) 10 parts by weight, KF
A fishing net antifouling agent was prepared by uniformly stirring 5 parts by weight of 6016 (ether-modified silicone oil manufactured by Shin-Etsu Chemical Co., Ltd.) and 80 parts by weight of xylene.

Example 8 10 parts by weight of triphenylboron pyridine, acrylic resin (methyl methacrylate / positive butyl methacrylate = 60 /
40, weight average molecular weight: 20,000) 5 parts by weight, polybutene (polybutene 06N (manufactured by NOF Corporation)) 5 parts by weight, FQF501-1000 (Toshiba Silicone Co., Ltd. fluorosilicone oil) 5 parts by weight, toluene 75
The weight part was uniformly stirred to prepare a fishing net antifouling agent.

Example 9 10 parts by weight of triphenylboron pyridine, acrylic resin (methyl methacrylate / positive butyl methacrylate = 60 /
40, weight average molecular weight: 20,000) 5 parts by weight, polybutene (polybutene 06N (manufactured by NOF CORPORATION)) 5 parts by weight, KF50-100 (Shin-Etsu Chemical Co., Ltd. polymethylphenylsiloxane) 5 parts by weight, toluene 75 parts by weight The parts were uniformly stirred to prepare a fishing net antifouling agent.

Example 10 1 part by weight of triphenylboron pyridine, 4,5-dichloro-2-n-octyl-3 (2H) -isothiazolone 4
Parts by weight, 10 parts by weight of rosin, TSF4440 (silicone polyether copolymer manufactured by Toshiba Silicone Co., Ltd.) 2
0 parts by weight, xylene 20 parts by weight, isopropanol 45
The weight part was uniformly stirred to prepare a fishing net antifouling agent. The results of the antifouling test of the fishing net antifouling agents of Examples 6 to 10 and Comparative Example are shown in Table 4, and the results of the slime resistance evaluation are shown in Table 5.
The results of the sedimentation test are shown in Table 6, and the results of the adhesion test are shown in Table 7.

[0039]

[Table 4]

[0040]

[Table 5]

The numbers in the table indicate the following states. 3: There is no adhesion of slime. 2: There is adhesion of thin slime. 1: There is adhesion of thick slime. -: There are many attached organisms and it is impossible to observe slime.

[0042]

[Table 6]

[0043]

[Table 7]

[0044]

INDUSTRIAL APPLICABILITY The fishing net antifouling agent of the present invention is excellent in antifouling properties of various marine fouling organisms, and is particularly excellent in antifouling properties of hydro worms and obelia which cannot be achieved by the conventional techniques. It has excellent effects such as good effect, good adhesion to fishing nets, no sedimentation and good workability. Furthermore, when triphenylboron pyridine and silicone oil are used in combination, the antifouling effect on slime is dramatically improved in addition to the above effects.

 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Yoshihiro Honda 1-13-59 Koyodai, Kawanishi City, Hyogo Prefecture

Claims (2)

[Claims] 1. A fishing net antifouling agent comprising triphenylboron pyridine represented by the formula (1) as an essential component. [Chemical 1] 2. An antifouling agent for fishing nets, which comprises triphenylboron pyridine represented by the formula (1) and silicone oil as essential components. [Chemical 2]