JP2001348533A - Coating composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a coating composition capable of effectively exterminating ectoparasites parasitic on cultured fishes with a slight labor in operations and a slight stress on the fishes. SOLUTION: This coating composition is characterized in that the coating composition comprises (a) zinc and/or a zinc compound in an amount of >=10 wt.% based on the whole solid content of the coating composition and (b) an antifouling agent in an amount of >=5 wt.% based on the whole solid content of the coating composition and the total amount of the zinc and/or zinc compound (a) and the antifouling agent (b) is <=80 wt.%.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

[0001] The present invention relates to a paint composition used for fishing nets and the like in the field of aquaculture, and more particularly, to the suppression of the propagation of parasites parasitic on cultured fish when used in fishing nets and the like. The present invention relates to a coating composition which can be used.

[0002]

2. Description of the Related Art When ectoparasites occur, cultured fish such as yellowtail, amberjack, and gibberish are anorexia and the growth of fish is hindered and weakened.
Since the parasites are repeatedly propagated in the cultivation area, the yield has been reduced, and this has been regarded as a problem. As the ectoparasites, there are generally found worms, insects, etc. which are parasitic on the body surface of fish. Adults of the spider beetle attach themselves to the body surface of the fish with a sucker and parasitize, and the eggs released from the adult attach to the surface of the mesh with an adhesive thread, swim after hatching, swim with the villi, and encounter the body of the fish body Proliferate by repeating the cycle of attaching to the table.

[0003] As a method for controlling ectoparasites such as spider beetles, a method of immersing a target fish in fresh water has conventionally been adopted. JP-A-10-72344 discloses that an acid such as citric acid, malic acid or acetic acid can be used to adjust the pH to 3 or less.
Parasiticides adjusted to ~ 5 are disclosed. However, since all of the above methods are methods for eliminating ectoparasites by directly immersing fish, the labor involved in the operation is enormous, and there is a problem that stress is also applied to fish. there were. Furthermore, a method is also used in which fish are immersed in breeding water in which chemicals such as formalin and hydrogen peroxide are dissolved.However, they accumulate in fish bodies and generate off-flavor fish, or the treated solution is dumped in seawater. There were also environmental problems.

Japanese Patent Application Laid-Open No. Hei 11-92309 discloses 2-
Cyclohexylcarbonyl-1,2,3,6,7,11
A method for controlling parasites by orally administering a fish feed containing b-hexahydro-4H-pyrazino [2,1-a] isoquinolin-4-one to fish is disclosed. However, this method has a problem that the cost is high.

[0005]

DISCLOSURE OF THE INVENTION An object of the present invention is to provide a coating composition capable of effectively eliminating ectoparasites parasitic on farmed fish, which requires less labor and less stress on fish in view of the above situation. To provide things.

[0006]

According to the present invention, zinc and / or a zinc compound (a) of 10% by weight or more and an antifouling agent (5% by weight or more) based on the total solid content of the coating composition are provided. b)
Wherein the total amount of the zinc and / or zinc compound (a) and the antifouling agent (b) is 8
0% by weight or less of the coating composition. Hereinafter, the present invention will be described in detail.

The coating composition of the present invention contains zinc and / or a zinc compound (a). By adding zinc and / or the zinc compound (a), it is possible to suppress the propagation of ectoparasites parasitized in the cultured fish and to prevent the parasitism from further expanding to other cultured fish. The zinc and / or zinc compound is not particularly limited as long as it gradually dissolves as zinc ions in water when formed into a coating film. For example, zinc powder, zinc white, zinc carbonate, zinc naphthenate And the like. The zinc and / or zinc compound (a) may be used alone or in combination of two or more. In the present invention, it is preferable to use zinc powder because the effect of gradually releasing zinc ions in water is excellent.

The zinc and / or zinc compound (a) is
10% by weight or more based on the total solid content of the coating composition. If it is less than 10% by weight, the effect of suppressing the growth of parasites such as spider beetles cannot be obtained. More preferably, it is at least 15% by weight, even more preferably at least 20% by weight.

[0009] The coating composition of the present invention contains an antifouling agent (b). The antifouling agent is not particularly limited. For example, in addition to inorganic antifouling agents such as cuprous oxide, as an organic antifouling agent, manganese ethylenebisdithiocarbamate (maneb, manufactured by Tokyo Organic Chemical Industry Co., Ltd.) , Zinc dimethyldithiocarbamate (Chemical Products Industry Association, Ziram), zinc ethylenebisdithiocarbamate (Zineb, manufactured by Tokyo Organic Chemical Industry Co., Ltd.), 2-methylthio-4-t-
Butylamino-6-cyclopropylamino-S-triazine (Irgarol 1051 manufactured by Ciba-Geigy),
2,4,5,6-tetrachloroisophthalonitrile (manufactured by Sannopco, marine side), N, N-dimethyldichlorophenylurea (manufactured by Hodogaya Chemical Industry), rodan copper,
4,5-dichloro-2-n-octyl-3 (2H) -isothiazoline (manufactured by Rohm and Haas Japan, SE
ANINE 211), N- (fluorodichloromethylthio) phthalimide (manufactured by Bayer Japan, Preventol A-3), N, N'-dimethyl-N'-phenyl- (N-fluorodichloromethylthio) sulfamide (manufactured by Bayer Japan) , Preventol A4S), N
-Dichlorofluoromethylthio-N ', N'-dimethyl-N-p-tolylsulfamide (manufactured by Bayer Japan, Preventol A5S), 2-pyridinethiol-
1-oxide zinc salt (zinc pyrithione), 2-pyridinethiol-1-oxide copper salt (kappa-pyrithione), 2,3,5,6-tetrachloro-4- (methylsulfonyl) pyridine (Densil S100), 3-
Iodo-2-propynyl butyl carbamate (TRO
YSAN POLYPHASE P100), diiodomethyl paratolyl sulfone (AMICAL 48), bisdimethyldithiocarbamoyl zinc ethylenebisdithiocarbamate (TOC-3204), pyridine-triphenylborane (PK) and the like.

Further, as the antifouling agent, triphenylborane-amine complex compounds such as stearylamine-triphenylborane and laurylamine-triphenylborane;
Triphenylborane-alkoxy group-containing amine complex compounds such as-(2-ethylhexyloxy) propylamine-triphenylborane; thiuram-based compounds such as tetraethylthiuram disulfide and tetrabutylthiuram disulfide can also be used.

[0011] The content of the above antifouling agent is 5% by weight or more based on the solid content of the whole coating composition. When the amount is less than 5% by weight, the coating composition does not have an antifouling effect, and the surface of the coating film is remarkably covered with aquatic organisms, thereby preventing the release of zinc ions. The effect of suppressing reproduction cannot be obtained.

The total amount of the zinc and / or zinc compound (a) and the antifouling agent (b) is not more than 80% by weight based on the total solid content of the coating composition. If the content exceeds 80% by weight, the physical properties of the coating film become poor, so that the coating film cannot be retained on a fishing net or the like for a long time.

As a vehicle used in the coating composition of the present invention, a synthetic resin and / or a natural resin is used.
Examples of the synthetic resin vehicle include vinyl chloride /
Vinyl acetate copolymer, vinyl chloride / alkyl vinyl ether copolymer, vinyl resin such as vinyl chloride resin, alkyd resin, acrylic resin, urethane resin, polyester resin, synthetic rubber, chlorinated polyethylene, etc. be able to. As the natural resin vehicle,
For example, rosin resins such as wood rosin, gum rosin, modified rosin, and rosin ester can be used. From the viewpoint of long-term antifouling properties, acrylic resins are preferred.

In the present invention, a hydrolysis type resin is also preferable. The hydrolyzable resin is gradually hydrolyzed in water and the surface of the coating film is constantly renewed. Therefore, for a long time, the antifouling effect against organisms attached to water and the effect of suppressing the growth of parasites are excellent. Paint composition can be obtained. As the above-mentioned hydrolysis type resin, a metal ester-containing acrylic resin is preferable. The metal ester-containing acrylic resin is an acrylic resin having at least one group having a chemical structure represented by the following general formula (1) at an end of at least one side chain.

[0015]

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In the formula, M represents zinc or copper. R ¹ is
Represents an organic acid residue. More specifically, R ¹ includes organic acid residues such as levulinic acid, naphthenic acid, oleic acid, and abietic acid.

The acrylic resin constituting the metal ester-containing acrylic resin is not particularly limited, and includes any resin having a main chain formed by an acrylic bond. These include, for example, resins made of (co) polymers of alkyl (meth) acrylates and copolymers of alkyl (meth) acrylates with other polymerizable monomers copolymerizable therewith. be able to. In the above copolymerization,
An ordinary radical polymerization initiator or an appropriate solvent can be used if necessary. The metal ester-containing acrylic resin can be synthesized according to the method described in JP-A-62-57464.

As the above-mentioned hydrolyzable resin, a resin obtained by copolymerizing triorganosilyl (meth) acrylate represented by the following general formula (2) and other polymerizable monomers is also preferable.

[0019]

Embedded image

In the formula, R ² represents a hydrogen atom or a methyl group, and R ³ is the same or different and represents an alkyl group having 3 or more carbon atoms. As the alkyl group of R ³ , an i-propyl group is excellent because it has excellent storage stability and a coated film obtained after storage can obtain a coating composition having excellent long-term antifouling properties. preferable. Further, from the viewpoint of flexibility and flexibility of the coated film, the weight ratio of tri-i-propylsilyl methacrylate to tri-i-propylsilyl acrylate is preferably 50/50 to 0/100. Other polymerizable monomers copolymerized with the above-mentioned triorganosilyl (meth) acrylate are not particularly limited.

The triorganosilyl (meth) acrylate represented by the general formula (2) and other polymerizable monomers are mixed with a polymerization initiator such as an azo compound and a peroxide to prepare a mixed solution. For example, a triorganosilyl (meth) acrylate copolymer can be obtained by, for example, dropping it into a solvent such as xylene and reacting it under heating conditions.

In the present invention, the molecular weight of the resin used as a vehicle is not particularly limited.
Usually, the number average molecular weight is about 4,000 to 40,000, preferably in the range of 6,000 to 35,000. 4
If it is less than 000, the film-forming properties of the paint may be reduced. If it exceeds 40,000, the hardness of the paint becomes high, which is not suitable for practical use. This is because it is not preferable in terms of properties and the like.

As the resin used as the vehicle, the above-mentioned natural resins, synthetic resins and hydrolyzable resins may be used alone or in combination of two or more. In the present invention, the amount of the resin used as a vehicle as a solid content is usually preferably 10% by weight or more based on the total solid content of the coating composition. If it is less than 10% by weight, the physical properties of the obtained coating film are inferior. Preferably, it is at least 15% by weight.

[0024] The coating composition of the present invention may also contain an elution aid such as silicone oil, petrolatum, paraffins, polybutene, and polysulfide. By blending the above-mentioned dissolution aid, the effect of the present invention, that is, the antifouling effect against organisms attached to water, and the effect of suppressing the growth of parasites can be more sustained, and the coating film properties are also excellent. It can be a coating composition. As the dissolution aid, it is preferable to use polyether-modified silicone oil or vaseline alone, or to use a combination of at least one of polyether-modified silicone oil and vaseline with polybutene or polysulfide. The compounding amount of the dissolution aid is in the solid content of the coating composition,
Usually, it is 0.5 to 40% by weight.

The above-mentioned coating composition can be blended with coloring pigments, extender pigments and the like generally used in coating compositions. The color pigment is not particularly limited, and examples thereof include titanium oxide, carbon black, red iron oxide, phthalocyanine blue, phthalocyanine green, and quinacridone. The extender is not particularly limited, and examples thereof include zinc white, talc, clay, precipitated barium sulfate, and calcium carbonate.

The coating composition may further contain known additives such as a plasticizer. Examples of the additive include a plasticizer such as dioctyl phthalate; a run-off agent such as organic bentonite and colloidal silica;

The coating composition of the present invention can be produced by blending and mixing the above components. The mixing method, mixing order, and the like of each component and additive can be performed by various methods. The coating composition prepared as described above can be applied to fishing nets and the like by various coating methods such as dip coating and spray coating. When applied to fishing nets and the like, dip coating is preferred. Thereafter, the solvent can be volatilized and removed at room temperature or under heating to form a dried coating film.

The coating composition of the present invention is applied to fishing nets such as aquaculture nets and stationary nets, and accessories for fishing nets, etc., so that it is possible to control the external appearance of cultured fish such as yellowtail, amberjack, gibberfish, tiger pufferfish, carp and crucian carp. It is possible to suppress the propagation of parasites and prevent the parasitism from further spreading to other cultured fish. Furthermore, this effect lasts for a long period of time, and the labor and stress on the fish are small, and ectoparasites can be effectively controlled.

[0029]

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. Parts represent parts by weight.

Production Example 1 Preparation of Varnish A In a four-necked flask equipped with a stirrer, a reflux condenser and a dropping funnel, 64 parts of xylol and 16 parts of n-butanol were added and kept at 100 ° C. In this solution, 20.0 parts of isobornyl acrylate, 50.9 parts of ethyl acrylate, 14.1 parts of acrylic acid, and NK ester M-90G were added to the solution.
A mixed solution of 0 parts and 3 parts of t-butylperoxy-2-ethylhexanoate was added dropwise at a constant speed over 4 hours, and the mixture was kept warm for 2 hours. The solid content of the obtained varnish is 50.
0% and a viscosity of 7.5 poise. 100 parts of the varnish obtained above, 16.0 parts of zinc oxalate, 27.7 parts of oleic acid, and 120 parts of xylol were added to a four-necked flask equipped with a stirrer, a reflux condenser, and a decanter.
C. to remove oxalic acid together with the solvent.
0.8 part of varnish A having a viscosity of 8.3 poise was obtained.

Production Example 2 Preparation of Varnish B To a four-necked flask equipped with a stirrer, a cooler, a temperature controller, a nitrogen inlet tube and a dropping funnel, was added 42 parts of xylene, and
It was kept at 0 ° C. In this container, 50 parts of triisopropylsilyl acrylate, 5 parts of triisopropylsilyl methacrylate, 20 parts of methoxyethyl acrylate, 25 parts of methyl methacrylate, and 1 part of dimethyl 2,2'-azobisisobutyrate The mixture was dropped at a constant speed over 3 hours, and after the dropping was completed, the temperature was kept for 30 minutes. Thereafter, a mixed solution of 7.24 parts of xylene and 0.15 parts of dimethyl 2,2'-azobisisobutyrate was dropped at a constant speed over 30 minutes, and after the completion of the dropping, the temperature was maintained for 2 hours. Then, it heated at 110 degreeC and kept warm for 30 minutes. Then, xylene 17.4
3 parts were added to obtain Varnish B. The solids content in varnish B is 6
0% by weight and Gardner viscosity (25 ° C.) was Z1.

Examples 1 to 5, Comparative Examples 1 to 3 Pigments excluding zinc dust shown in Table 1 (antifouling agents, coloring pigments, etc.)
And a resin component were blended and dispersed by an SG mill to prepare a dispersion base. Thereafter, additives such as zinc dust and silicone oil were added, and the mixture was stirred with a disper to prepare each coating composition. The units of the components in Table 1 are parts by weight. Table 1
The acrylic resin is NT100 (manufactured by Nitto Kasei; solid content 50% by weight), antifouling agent 1 is triphenylborane-pyridine (PK; manufactured by Hokuko Chemical Co .; solids content 100% by weight), and antifouling agent 2 is 2 -Pyridinethiol-1-oxide copper salt, antifouling agent 3 is tetraethylthiuram disulfide, and antifouling agent 4 is triphenylborane-stearylamine (YN18-2
0: manufactured by Yoshitomi Fine Chemical Co., Ltd .; xylol solution having a solid content of 20% by weight), silicone oil: silicone oil PA-01 (manufactured by Toray Dow Silicone Co., Ltd.), vaseline: white petrolatum (Wako Pure Chemical Industries, Ltd.), and polybutene: polybutene HV100 (Manufactured by Nippon Petrochemical Co., Ltd.).

[0033]

[Table 1]

[0034]Antifouling test  Using a paint having the composition shown in Table 1, a polyethylene
For fishing nets (60 knots without knots, 6 knots, 20cm x 30cm)
A test raft off the coast of Tamano City, Okayama Prefecture
From the sea to a depth of about 1m in the sea, its antifouling performance for 6 months
Observed periodically. The results are shown in Table 2. table
The numbers in the middle represent the biofouling area (%).

[0035]

[Table 2]

[0036]Test for effectiveness of beetle prevention  A 3m-square aquaculture net coated with a paint having the composition shown in Table 1
10 hamachi weighing about 500g (2 of which are
Worms) and bred for one month,
The number of infested parasites and the number of
I did it. Comparative example where practicality was not recognized in the antifouling test
This test was not carried out for the paints of Comparative Example 2 and Comparative Example 3.
Was. The results are shown in Table 3. In Table 3,
It is the number of adults of beardworms that can be visually confirmed
You. In addition, a hamachi parasitized by a wasp rubs its body against the net.
The number of hamachi in Table 3 is
Infested hamachi and fish injured
It is the total number of hamachi.

[0037]

[Table 3]

The coating compositions of Examples 1 to 5 were able to suppress the growth of Hadamushi parasitoids infested with Hamachi and prevent the parasitism from spreading further to other Hamachi. Further, in the test for the effect of controlling beetles, the number of adults of beetles parasitized in Hamachi did not reach 0 after 2 weeks, but gradually decreased. This is considered to be due to the fact that the wasp, which had been infested in two Hamachi from the beginning, had a lifespan of the adult Hadamushi, or dropped off when the hammer rubbed the body surface against the net. Therefore, the coating composition of the present invention acts on spawning and / or hatching processes of beetles that occur near the fish body or on a fishing net, rather than directly acting on the adult wasp parasitic on Hamachi. it is conceivable that. Since the coating composition of Comparative Example 1 had a low content of zinc dust, it was not possible to sufficiently suppress the growth of the wasp parasitic on Hamachi. Since the coating composition of Comparative Example 2 had a low content of the antifouling agent, the antifouling property was not maintained for a long time, and was inferior in practical use. The coating composition of Comparative Example 3 was poor in practicality because the content of zinc dust and the antifouling agent was too large, so that the coating film properties were poor, the antifouling property was not maintained for a long time, and the practicality was poor.

[0039]

Since the coating composition of the present invention has the above-mentioned constitution, the labor and stress on the fish are small, and ectoparasites parasitic on the cultured fish can be effectively controlled.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme court ゛ (Reference) C09D 5/16 C09D 5/16 7/12 7/12 Z (72) Inventor Hiroko Sagawa Koma, Nagata-ku, Kobe-shi 1-26, Kabayashi Minamimachi Nippon Paint Marine Co., Ltd. F-term (reference) 4H011 AD01 BA01 BA06 BB09 BB13 BB16 BB18 BC16 BC19 DA23 DD01 DD07 DH02 4J038 CB021 CB171 CD021 DD001 DD121 DG001 HA066 HA216 HA296 JA47 KA02 KA20 NA05 PC10

Claims (2)

[Claims] 1. Zinc and / or zinc compound (a) in an amount of 10% by weight or more based on the total solid content of the coating composition, and
A coating composition containing 5% by weight or more of an antifouling agent (b), wherein the total amount of the zinc and / or zinc compound (a) and the antifouling agent (b) is 80% by weight or less. A coating composition comprising: 2. The coating composition according to claim 1, wherein the zinc and / or the zinc compound (a) is zinc powder.