JPH0693214A - Antifouling coating for fishing net - Google Patents

Abstract

PURPOSE:To obtain an antifouling coating for fishing nets capable of sustaining high antifouling properties for a long period even without containing a toxic organotin compound. CONSTITUTION:The antifouling coating for fishing nets comprises (A) 100 pts.wt. resin component composed of 90-99.9wt.% water-insoluble acrylic resin having <20 deg.C glass transition temperature and 0.1-10wt.% at least one water-soluble resin selected from rosin and polyvinyl ethereal resins, (B) 3-10 pts.wt. surfactant and (C) 0.1-10 pts.wt. waxes.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an antifouling paint for fishing nets, which protects fishing nets used for aquaculture of fishes from the adhesion and fouling of marine organisms such as seaweeds and shellfish.

[0002]

[Prior art and its problems] If fish nets such as aquaculture nets and stationary nets are used without treatment, marine organisms will adhere and stain,
The distribution of seawater deteriorates, which adversely affects the growth of cultured fish and causes oxygen deficiency, making it impossible to perform the original function of the fishing net. Marine organisms attached to fishing nets include barnacles, oysters, mussels, hydroids, squirts, serpra,
Examples include animals and plants such as bryozoans, crackers, sea anemones, sea lions, and sea lions. In order to exert their original function as a fishing net, it is necessary to prevent them from adhering.

Conventionally, an organic tin compound has been used as an antifouling agent in order to prevent such marine organisms from adhering to and propagating on fishing nets.
There is a problem of residual / accumulation in the environment. As non-organotin-based antifouling agents, there are many copper compounds, organic nitrogen-sulfur compounds, etc., but even if a fishing net is treated with antifouling paints using these compounds as antifouling agents, the above-mentioned various marine organisms are It adheres to the surface, and the antifouling effect is not obtained sufficiently.

The present invention is intended to provide an antifouling paint for fishing nets, which can maintain a high antifouling property for a long period of time without containing an organotin compound.

[0005]

As a result of various studies to solve the above problems, the present inventors have found that a mixed resin of an acrylic resin having a low glass transition temperature and a small amount of a water-soluble resin is mixed with a surfactant. The inventors of the present invention have found that an antifouling paint mixed with waxes can exhibit a high antifouling property for a long period of time even if it does not contain an organotin compound.

That is, according to the present invention, (A) 90 to 99.9% by weight of a water-insoluble acrylic resin having a glass transition temperature of less than 20 ° C. and at least one water-soluble resin selected from rosin and polyvinyl ether resins. A fishing net characterized by containing (B) a surfactant 3 to 10 parts by weight and (C) waxes 0.1 to 10 parts by weight with respect to 100 parts by weight of a resin content of 1 to 10% by weight. Antifouling paint

[0007]

The water-insoluble acrylic resin in the component (A) of the coating composition of the present invention has a glass transition temperature of less than 20 ° C, preferably -1.
The molecular weight is not particularly limited as long as it is a water-insoluble acrylic resin of 0 to 10 ° C., but the number average molecular weight is usually 3,000 to 200,000, preferably 5,000.
~ 80,000 are used.

The acrylic resin contains 50% by weight or more of an ester of acrylic acid or methacrylic acid, and the monomer components are appropriately selected so that the solubility of the resulting resin is in the above range, and a known method such as solution radical is used. It is obtained by polymerization by a polymerization method or the like.

Examples of the monomer used in the above monomer component include methyl acrylate, ethyl acrylate, n-propyl acrylate, isopropyl acrylate, butyl acrylate (n-, i-, t-), hexyl acrylate, 2-ethylhexyl acrylate, n-octyl acrylate, decyl acrylate, lauryl acrylate, stearyl acrylate, cyclohexyl acrylate, methyl methacrylate, ethyl methacrylate, n-methacrylate
Propyl, isopropyl methacrylate, butyl methacrylate (n-, i-, t-), hexyl methacrylate, 2-ethylhexyl methacrylate, octyl methacrylate, decyl methacrylate, lauryl methacrylate, stearyl methacrylate, cyclohexyl methacrylate, etc. C1-18 alkyl or cycloalkyl esters of acrylic acid or methacrylic acid: methoxybutyl acrylate, methoxybutyl methacrylate, methoxyethyl acrylate, methoxyethyl methacrylate, ethoxybutyl acrylate, ethoxybutyl methacrylate, etc. C2-18 alkoxyalkyl ester of acrylic acid or methacrylic acid: N, N-dimethylaminoethyl acrylate, N, N-dimethylaminoethyl methacrylate, N, N- Ester of acrylic acid or methacrylic acid such as aminoalkyl ester of acrylic acid or methacrylic acid such as methylaminopropyl acrylate, N, N-dimethylaminopropyl methacrylate; acrylic acid, methacrylic acid, crotonic acid, itaconic acid, maleic acid, Carboxyl group-containing polymerizable unsaturated monomer such as fumaric acid; 2-hydroxyethyl acrylate, 2-
Hydroxyl group-containing polymerizable unsaturated monomers such as hydroxyethyl methacrylate, hydroxypropyl acrylate, hydroxypropyl methacrylate and hydroxybutyl acrylate; aromatic polymerizable unsaturated monomers such as styrene and vinyltoluene; vinyl acetate, vinyl propionate, butadiene, ethyl vinyl ether , Other polymerizable unsaturated monomers such as butyl vinyl ether and allyl ethyl ether.

When the glass transition temperature of the water-insoluble acrylic resin is 20 ° C. or higher, the flexibility of the coated net is poor and the handling work of the net is hindered.

The water-soluble resin in the component (A) of the coating composition of the present invention is at least one of rosin and polyvinyl ether resins, and includes slightly water-soluble resins and easily water-soluble resins. The polyvinyl ether resin is a homopolymer of vinyl alkyl ether or a copolymer containing 30% by weight or more of vinyl alkyl ether as a monomer component. The alkyl group of the vinyl alkyl ether generally has 1 to 4 carbon atoms, and the smaller the number of carbon atoms, the more likely it is to dissolve in water. Specific examples of the vinyl alkyl ether include vinyl methyl ether, vinyl ethyl ether, vinyl isobutyl ether and the like. The molecular weight of the polyvinyl ether-based resin is not particularly limited, but usually, the number average molecular weight is 3,0.
100 to 200,000 are used.

The blending amount of each resin in the component (A) is 90 to 99.9% by weight of the water-insoluble acrylic resin, preferably 95 to 98% by weight.
It is 10% by weight, preferably 2 to 5% by weight. If the amount of the water-soluble resin is less than 0.1% by weight, the antifouling property is insufficient. On the other hand, if it exceeds 10% by weight, the strength of the coating film in water is insufficient and an antifouling agent is added. In that case, the elution of the antifouling agent is promoted, so that the antifouling property cannot be exhibited for a long time.

As the surface active agent which is the component (B) in the coating composition of the present invention, a silicone type surface active agent can be mentioned, and particularly, an oxyalkylene group-containing organopolysiloxane of HLB 3 to 12 is preferable, and a commercially available product is
For example, SH-8400 (manufactured by Toray Silicone Co., Ltd.), KF-
353A (manufactured by Shin-Etsu Chemical Co., Ltd.) and the like.

The blending amount of the above-mentioned surfactant is 3 to 10 parts by weight with respect to 100 parts by weight of the resin component which is the component (A). If the content of the surfactant is less than 3 parts by weight, the antifouling property is insufficient, while if it exceeds 10 parts by weight, the hydrophilicity of the coating film becomes too large and the strength of the coating film in water becomes insufficient. At the same time, when an antifouling agent is mixed, the elution of the antifouling agent is promoted and the long term antifouling property cannot be maintained.

Examples of the waxes as the component (C) in the coating composition of the present invention include liquid paraffin, solid paraffin, petrolatum and the like. The amount of this wax compounded is
0.1 to 100 parts by weight of resin component (A)
10 parts by weight. When the amount of the waxes is less than 0.1 part by weight, the synergistic effect on the antifouling property due to the water repellency of the wax is not exerted, while when it exceeds 10 parts by weight, the state of the coating is adversely affected and a non-uniform state is exerted. And a good coating film cannot be obtained.

The coating composition of the present invention contains the above-mentioned components (A), (B) and (C) as essential components. Further, in order to improve the antifouling property, other than the organotin compound as the component (D),
An antifouling agent recognized as safe can be contained.

Examples of the antifouling agent which is the component (D) include 2-pyridinethiol-1-oxide zinc salt and 2-
Pyridine thiol-1-oxide copper salts, pyridine-based antifouling agents such as tetraphenylboron pyridine salt; tetramethylthiuram monosulfide, tetramethylthiuram disulfide, tetraethylthiuram disulfide,
Sulfide antifouling agents such as tetrabutyl thiuram disulfide; tetramethylisophthalonitrile, 2,
Nitrile antifouling agents such as 4,5,6-tetrachloro-1,3-isophthalonitrile; urea antifouling agents such as N, N-dimethyldichlorophenylurea; N- (fluorodichloromethylthio) phthalimide, 2, Acid amide antifouling agents such as 4,6-trichlorophenylmaleimide and N, N'-dimethyl-N'-phenyl- (N-fluorodichloromethylthio) sulfamide; thiazoles such as 2- (thiocyanomethylthio) benzothiazole Antifouling agent;
Isothiazolone antifouling agents such as 4,5-dichloro-2-N-octyl-3 (2H) isothiazolone; triazine antifouling agents such as 2-methylthio-4-t-butylamino-6-cyclopropylamino-S-triazine Fouling agents: Other organic antifouling agents and antifouling agents such as cuprous oxide. These antifouling agents can be used alone or in admixture of two or more, but it is advantageous to use in admixture of two or more from the viewpoint of antifouling property.

The amount of the above-mentioned antifouling agent is preferably 150 parts by weight or less with respect to 100 parts by weight of the resin component as the component (A), and in order to exert the effect as an antifouling agent, it is 30 to 30 parts by weight. The range of 150 parts by weight is more preferable. If the amount of the antifouling agent is more than 150 parts by weight, the film strength tends to be insufficient, the solubility and dispersibility in the solvent to be used are insufficient, and it is expensive from the economical aspect.

The coating composition of the present invention comprises the above (A), (B), (C).
In addition to the component (D), if necessary, a solvent, a plasticizer,
An anti-sagging agent, a coloring pigment, an extender pigment and the like can be contained as appropriate.

[0020]

EFFECTS OF THE INVENTION According to the present invention, by using a surfactant and wax in combination with a resin component obtained by mixing a small amount of a specific water-soluble resin with a water-insoluble acrylic resin, the marine organisms can be prevented from adhering to the fishing net. It can be held for a long time,
Since the excellent antifouling property can be exhibited without containing an organotin compound as the antifouling agent, a highly safe antifouling paint for fishing nets can be obtained.

[0021]

The present invention will be described in more detail with reference to the following examples. Examples 1 to 8 and Comparative Examples 1 to 7 Raw materials were blended with the compositions shown in Table 1 below, and stirred for about 30 minutes until the solution became uniform to prepare antifouling paints. The blending amount in Table 1 is indicated by "part by weight". Further, Comparative Example 8 was a commercially available antifouling paint for fishing nets (tin polymer type) containing an acrylic resin having a tin ester group.

[Note] in Table 1 is as follows. (* 1) LR164: Mitsubishi Rayon Co., Ltd., water-insoluble acrylic resin, glass transition temperature -5 ° C, number average molecular weight 5
10,000-60,000. (* 2) Dianal BR-105: Mitsubishi Rayon Co., Ltd., water-insoluble acrylic resin, glass transition temperature 50
° C, number average molecular weight of about 57,000. (* 3) Lutonal M-40: A water-soluble resin that is polyvinyl methyl ether manufactured by BASF. (* 4) Lutonal A-25: a water-soluble resin made by BASF, which is polyvinyl ethyl ether. (* 5) SH-8400: Toray Silicone Co., Ltd., polyether modified polysiloxane surfactant, HLB
9.1. (* 6) Sunceller TETG: Tetraethyl thiuram disulphide manufactured by Sanshin Kagaku. (* 7) Sancelent TMB: Sanshin Chemical Co., Ltd., 2- (thiocyanomethylthio) benzothiazole. (* 8) Preventor A-4S: Bayer, N,
N'-dimethyl-N'-phenyl- (N-fluorodichloromethylthio) sulfamide. (* 9) Preventor A-3: Bayer N-
(Fluorodichloromethylthio) phthalimide. (* 10) IT354: 2, 4, manufactured by Ihara Chemical Co., Ltd.
6-Trichlorophenylmaleimide. (* 11) Irgalol 1051: 2-methylthio-4-t-butylamino-6-cyclopropylamino-S-triazine, manufactured by Ciba-Geigy. (* 12) Caisson 930: manufactured by Rohm and Haas Company, 4,5-dichloro-2-N-octyl-3 (2H).
Isothiazolone.

Test Method The antifouling paints obtained in the above Examples and Comparative Examples were 20 × 40 cm.
After being applied to a fishing net (Shimizu Seimitsu Co., Ltd., polyethylene, 400 denier, 60 pieces, mesh: 60 mm) and dried, it is immersed in Nagaura Bay, Yokosuka City, Kanagawa Prefecture to periodically attach the marine organisms. And the antifouling property was evaluated. The results are shown in Table 2 below. Table 2 shows the types of adherent organisms and the adhered area (%). Table 2 shows the results of the antifouling property of the unpainted fishing net as Comparative Example 9.

The attached organisms in Table 2 are indicated by the following abbreviations. HY: sea squirt, FK: fucorice beetle, FJ: barnacle.

[0025]

[Table 1]

[0026]

[Table 2]

Claims (3)

[Claims] 1. (A) 90 to 99.9% by weight of a water-insoluble acrylic resin having a glass transition temperature of less than 20 ° C. and at least one selected from rosin and polyvinyl ether resins.
Resin component 1 consisting of 0.1% to 10% by weight of water-soluble resin
An antifouling paint for a fishing net, which comprises 3 to 10 parts by weight of a surfactant (B) and 0.1 to 10 parts by weight of a wax (C) with respect to 00 parts by weight. 2. The antifouling coating composition according to claim 1, which comprises 30 to 150 parts by weight of (D) an antifouling agent other than the organotin compound with respect to 100 parts by weight of the resin content (A). 3. The antifouling coating composition according to claim 1 or 2, wherein the surfactant (B) is an oxyalkylene group-containing organopolysiloxane having an HLB of 3 to 12.