JPH06256687A - Antifouling coating composition - Google Patents

Abstract

PURPOSE:To obtain a coating compsn. which is not toxic to fishes and humans and has improved long-lasting antifouling properties, adhesive properties, and applicability by compounding a specific copolymer, a silicone compd., and an antifouling agent. CONSTITUTION:This coating compsn. is prepd. by compounding 10-90 pts.wt. copolymer obtd. from 5-90wt.% silicone macromonomer of formula I or II (wherein R1 is OH, amino, or methyl; (n) is 10-150; and (k) is 1-4) and 10-95wt.% vinyl monomer copolymerizable therewith, 90-10 pts.wt. silicone compd. of formula III (wherein R2 and R3 are each OH or methyl; and (m) is 100-1,500 provided m>n), and an antifouling agent.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an antifouling paint composition used for a novel fishing net or equipment that comes into contact with seawater. More specifically, barnacles, which are marine organisms attached and grown on fishing nets such as aquaculture nets and fixed nets, coastal oil refineries, power plants, and other plants and equipment that utilize seawater,
The present invention relates to an antifouling coating composition that prevents mussels, seaweeds, etc. from adhering to a substrate.

[0002]

2. Description of the Related Art Marine nets such as fishnets such as aquaculture nets and fixed nets, plants and equipment utilizing seawater, such as barnacles, magnolias, squirts, mussels, oysters, and the like,
Algae such as sea lettuce and sea squirrel, various bacteria called slime, fungal, diatomaceous, etc. are attached and parasitized, which reduces the performance of the nets of fishing nets, and also the blocking and corrosion of cooling water channels in plants and equipment. However, if this progresses extremely, it will cause dismantlement and removal, which will cause a great deal of damage such as plant operation stop and equipment renewal, and removal, repair, repainting, etc. were required.

Conventionally, in order to prevent these, antifouling paints containing an organic tin compound have been added (Japanese Patent Publication No. 52-1873).
No. 6) and an antifouling paint using an organic tin polymer as a vehicle (see Japanese Patent Publication No. 57-39250).

However, in recent years, some of these have been found to be highly toxic to humans and animals, and are extremely harmful in terms of environmental pollution and hygiene, which has become a problem.

Therefore, it has been proposed to use an acrylic polymer having a slowly hydrolyzable silyl group in the side chain as a safe and effective antifouling paint which replaces these. These are antifouling paints that are hydrolyzed to be water-soluble and exhibit self-polishing properties (see Japanese Patent Application Laid-Open No. 62-275113), methods for reducing free energy of a coating film, and preventing adhesion of organisms (Japanese Patent Publication No. 61-21828). JP-A-60-5506
No. 7), a low free energy surface is formed when a substrate is treated with a composition in which polysiloxane is mixed with silicone oil and an antifouling agent, and the silicone oil and the antifouling agent gradually elute. An antifouling paint exhibiting an antifouling effect (see JP-A-1-190612), and an underwater antifouling coating agent containing a polymer having an organosilyl group or an organosiloxane group in its side chain (JP-A-2-675). Many proposals have been made. However, these underwater antifouling paints have a good initial antifouling effect, but after the antifouling agent on the surface of the coating film is eluted and lost, the elution rate of the antifouling agent in the deep part of the coating film becomes slow, so long-term It was unavoidable that the antifouling effect would be insufficient.

[0006]

DISCLOSURE OF THE INVENTION The present invention is required for antifouling paints for fishing nets, plants and equipment that come into contact with seawater, etc. (1) Ability to exhibit an excellent antifouling effect for a long period of time (2) For fish No toxicity (3) No toxicity to human body (4) Development of non-organic tin-based antifouling paint that satisfies all requirements such as good adhesion to fishing nets and plants and excellent workability With the goal.

[0007]

The present invention is based on the above (1) to (1).
As a result of repeated research to develop a non-organic tin-based fishing net that satisfies all the requirements of (4) and an antifouling paint for structures that come into contact with seawater, the antifouling paint composition of the present invention has a silicone macromonomer (a). And / or the copolymer containing the silicon macromonomer (b), the silicone compound, and the antifouling agent are gradually eluted, and it is found that the coating film surface always shows activity and has a long-term antifouling effect. The invention was completed.

The present invention has the general formula (I)

[Chemical 4] (In the formula, R _{1 represents} OH, an amino group, and a methyl group, and n is an arbitrary number of 10 to 150.) A compound [referred to as a silicon macromonomer (a). ] Or general formula (II)

[Chemical 5] (In the formula, k is an arbitrary number of 1 to 4, and n is 10 to 15
It is an arbitrary number of 0. ) A compound [it is called a silicon macromonomer (b). 5 to 90% by weight, 10 to 90 parts by weight of a copolymer composed of 10 to 95% by weight of a vinyl monomer copolymerizable therewith, and the general formula (III)

[Chemical 6] (In the formula, R ₂ and R ₃ are each independently selected from OH and a methyl group, m; 100 to 1500, and m> n
Is. ) A compound represented by the formula [referred to as a silicone compound. The above object was achieved by developing an antifouling coating composition characterized by containing 90 to 10 parts by weight and an antifouling agent.

Examples of the vinyl-based monomer copolymerizable with the silicon macromonomer (a) and / or the silicon macromonomer (b) used in the present invention include acrylic acid esters such as methyl acrylate, ethyl acrylate and n-butyl acrylate. , Methacrylic acid esters such as methylmethacrylate, ethylmethacrylate, n-butylmethacrylate, and 2-hydroxyethylmethacrylate, styrene, vinyl acetate, and the like, and mixtures thereof.

Macromonomer (a) and / or in copolymer
Alternatively, the blending ratio of the macromonomer (b) is 5 to 90% by weight, preferably 20 to 50% by weight. When this ratio is less than 5% by weight, the antifouling agent is eluted at a high rate and the antifouling effect is insufficient in the long term, which is not preferable. Further, when it is blended in an amount of more than 90% by weight, the polymerizability with a vinyl-based monomer (eg, acrylate and / or methacrylate) that can be copolymerized therewith is lowered, the viscosity is high, or white turbidity occurs, and the copolymer is separated, which is not preferable. . The copolymerization can be easily carried out by a solution polymerization method in the presence of an ordinary radical reaction initiator such as a peroxide or an azo compound.

The blending ratio of the silicone compound is 10 to 90 parts by weight with respect to 10 to 90 parts by weight of the copolymer, preferably 30 to 70 parts by weight of the silicone compound with respect to 30 to 70 parts by weight of the copolymer. is there. When this ratio is less than 10 parts by weight, the initial antifouling effect is good, but the elution rate is fast and the long-term antifouling effect is insufficient, which is not preferable. On the other hand, when the amount is more than 90 parts by weight, the composition becomes cloudy and separates, which is not preferable.

Examples of the antifouling agent used in the present invention include tetramethylthiuram disulphide, tetra-n-propylthuram disulphide, N.N'-ethylenebisthiocarbamoyl sulfide as a turum compound, and pyrophosphoric acid as a copper compound. Copper, copper naphthenate;
As a dithiocarbamate compound, zinc dimethyldithiocarbamate, zinc ethylenebisdithiocarbamate,
Manganese ethylenebisdithiocarbamate, nickel dimethyldithiocarbamate; 3- as urea compounds
(3,4-dichlorophenyl) -1-l-dimethylurea; benzimidazole-based compound 2-thiocyanomethylthiobenzimidazole, 2-methylcaptobenzimidazole zinc; benzothiazole-based compound 2-mercaptobenzothiazole, 2- ( Thiocyanomethylthio) benzothiazole, tetrachlorobenzothiazole; tetrachloroisophthalonitrile as a nitrile compound, 5-chloro-2,4-difluoro-6-methoxyisophthalonitrile; 4,5-dichloro-2 as an isothiazoline compound -N-octyl-4-isothiazolin-3-one, 1,2-benzisothiazolin-
3-one; 2,3,5,6-tetrachloro-4- (methylsulfonyl) pyridine as a pyridine compound, 2,
6-dichloro-3,5-dicyano-4-phenylpyridine; NN'-dimethyl N'-phenyl-N '-(fluorodichloromethylthio) sulfide as N-haloalkylthio compound, N-trichloromethylthiophthalimide; N as maleimide compound There are-(2-chlorophenyl) maleimide, N- (4-fluorophenyl) maleimide and the like, and other organic iodine compounds, pyrithione compounds, agricultural chemicals, pharmaceuticals, seedlings and the like.

The organic solvent used in the antifouling coating composition is an aromatic hydrocarbon solvent such as kylylene or toluene, an ester solvent such as ethyl acetate or butyl acetate, an alcohol solvent such as isopropyl alcohol or butyl alcohol, Examples include ketone solvents such as methyl ethyl ketone and methyl isobutyl ketone.

If necessary, the antifouling coating composition of the present invention thus constructed has a pigment such as titanium oxide, an ordinary anti-sagging agent, a color separation preventing agent, an anti-settling agent, an antifoaming agent, etc. It doesn't matter even if you add.

The antifouling coating composition of the present invention is a substrate to be immersed in seawater (a mesh of polypropylene, polyethylene, nylon, etc., or in the case of plants that come into contact with seawater, the coated surface of the rust preventive base coating). It is only necessary to coat the surface of the base material by an appropriate means so as to form a film on the surface of, and then volatilize and remove the solvent at room temperature or under heat drying.

[0016]

As a result of the experiment, it was only confirmed that the antifouling coating composition of the specific combination specified in the present invention has an excellent antifouling effect, and the silicone macromonomer (a) and / or
Alternatively, the respective actions of the copolymer containing the silicon macromonomer (b), the silicone compound and the antifouling agent have not yet been elucidated in detail, but it is speculated that they are due to the following reasons.

In a composition comprising a silicone macromonomer (a) and / or a copolymer containing the silicone macromonomer (b), a silicone compound and an antifouling agent, n of the silicone macromonomers and m of the silicone compound are m>
We believe that n is the most effective.

That is, n of the silicone macromonomers grafted in the copolymer is replaced by m of the silicone compound.
The larger the value, the less the inclusion of the silicone compound in the grafted branch part, and the greater the sustained release effect of elution into seawater. When n of the silicone macromonomers is smaller than m of the silicone compound, the silicone compound is grafted into the grafted branch part. It is thought that the sustained release effect of elution into seawater is reduced due to the inclusion of saccharine.

On the other hand, it is considered that the antifouling agent used as an essential component acts synergistically with the silicone macromonomer-containing copolymer and the silicone compound to exert a remarkable antifouling effect.

As described above, the antifouling coating composition containing the copolymer / silicone compound containing the silicon macromonomers and the antifouling agent in the present invention as an essential component is an antifouling agent while the coating film gradually dissolves in seawater. It is believed that the antifouling effect is maintained for a long time by eluting the.

[0021]

EXAMPLES The present invention will be described below with reference to examples and comparative examples. (Examples 1 to 4) 80 g of n-butyl acrylate, 8 g of ethyl acrylate, 12 g of silicon macromonomer (a) (R ₁ ; hydroxyl group, n) were placed in a 1-liter 4-necked flask equipped with a thermometer, a stirrer, and a reflux condenser. = 13
0), octyl thioglycolate 1 g, azobisisobutyl nitrile 3 g, xylene 20 g, butyl acetate 20 g
Was charged and polymerized at a reaction temperature of 95 to 110 ° C. for 8 hours.
After the reaction is completed, the mixture is diluted with 60 g of xylene. The resulting copolymer solution had a copolymer concentration of 50.2% and a viscosity of 30.
It was a clear solution at 0 cp / 30 ° C. Examples 2, 3 and 4 were reacted in the same manner as in Example 1 except that the raw materials shown in Table 1 were used.

[0022]

[Table 1] * Silicon macromonomer (b) (k = 3, n = 5
0)

Comparative Examples 1 and 2 In a 1-liter 4-necked flask equipped with a thermometer, a stirrer, and a reflux condenser, n-butyl acrylate (92 g) and ethyl acrylate (8) were added.
g, octyl thioglycolate 1 g, azobisisobutyl nitrile 3 g, xylene 20 g, and butyl acetate 20 g were charged, and polymerization was carried out at a reaction temperature of 95 to 110 ° C. for 8 hours. After the reaction is completed, the mixture is diluted with 60 g of xylene. A transparent solution having a copolymer concentration of 50.6% and a viscosity of 405 cp / 30 ° C. was obtained. In Comparative Example 2, the raw materials were as shown in Table 2, and the following reaction was performed in the same manner as in Comparative Example 1.

[0024]

[Table 2]

[Formulation of Antifouling Paint] Based on the composition shown in Table 3, the antifouling paint was prepared using the copolymers of Examples 1 to 4 and the copolymers of Comparative Examples 1 and 2, and the composition is shown below. The performance was compared and examined according to the procedure. As a test method, a Ford cup No. 4 was used to adjust the paint for 12 to 15 seconds. Test mesh: Polyethylene unknotted mesh 60 strands 6 knots (400 mm
× 400 mm) was impregnated (20 seconds), taken out, and dried in the sun. Coating rate = [(dry weight of mesh after coating-weight of mesh before coating) / (weight of mesh before coating)] × 100

[0026]

[Table 3]

Table 4 shows the results of marine experiments of antifouling paints.

[Table 4] * Control net: untreated (no coating) test net (weight: 56 g) Date: May 1, 1992-July 27, 1992 (3
Ketsu) Test location: Fukura, Nantan-cho, Mihara-gun, Hyogo Prefecture (suspension depth 1.5)
m)

[Evaluation Criteria] Enter the percentage of adhered organisms on the control net in% (total 100%) ◎: No adhesion ○: Adhesion within 1/3 of control net △: Adhesion within 2/3 of control net X: Adhesion is 2/3 or more of control net

Algae: Sea lettuce, Blue sea bream Amphipods: Bivalve bivalve: Blue sea bream

[0030]

The effect of the antifouling coating composition of the present invention has not been elucidated, but the production of a copolymer containing the raw material silicon macromonomer (a) and / or silicon macromonomer (b) is not possible. It is easy and the coating composition can be easily produced by simply blending a commercially available silicone compound and an antifouling agent. The application of this coating composition is simple, and the formed coating film gradually dissolves in seawater and, at the same time, the antifouling agent is eluted and the antifouling effect can be maintained for a long period of time. The copolymers and silicone compounds used in the present invention are toxic to fish.
There is no problem in terms of safety, and it has sufficient adhesion even to fishing nets and the like that require bending. For this reason, the coating obtained by the antifouling coating composition of the present invention shows a remarkable antifouling effect even in marine structures such as ship bottoms and cooling water pipes that require prevention of marine biological fouling and prevents biological fouling. It is an excellent antifouling coating composition that can be obtained.

Continuation of front page (51) Int.Cl. ⁵ Identification number Office reference number FI technical display location // C08F 299/08 MRY 7442-4J

Claims (1)

[Claims] 1. A compound represented by the general formula (I): (In the formula, R _{1 represents} OH, an amino group, and a methyl group, and n is an arbitrary number of 10 to 150.) A compound [referred to as a silicon macromonomer (a). ] Or general formula (II) (In the formula, k is an arbitrary number of 1 to 4, and n is 10 to 15
It is an arbitrary number of 0. ) A compound [it is called a silicon macromonomer (b). 5 to 90% by weight, 10 to 90 parts by weight of a copolymer composed of 10 to 95% by weight of a vinyl-based monomer copolymerizable therewith, and a compound represented by the general formula (III): (In the formula, R ₂ and R ₃ are each independently selected from OH and a methyl group, m; 100 to 1500, and m> n
Is. ) A compound represented by the formula [referred to as a silicone compound. ] An antifouling coating composition comprising 90 to 10 parts by weight and an antifouling agent.