JPH04325569A - Antifouling coating composition - Google Patents

Abstract

PURPOSE:To prepare the title compsn. excellent in the effect of preventing the deposition of harmful aquatic organisms on a ship, etc., by incorporating a specific maleimide compd. as an antifouling agent into the compsn. CONSTITUTION:A maleimide compd. of the formula wherein R is halogen, is incorporated as an antifouling agent into the title compsn.

Description

[Detailed description of the invention]

0001

[Industrial Application Field] The present invention is applicable to ships, underwater structures (e.g., port facilities, buoys, pipelines, bridges, undersea bases, undersea oil field drilling equipment, power plant conduit pipes, fixed nets, aquaculture nets, etc.) This invention relates to an antifouling paint composition for the purpose of preventing the adhesion of harmful aquatic organisms to surfaces.

[0002] Plants such as green algae and brown algae, animals such as barnacles, selbula, kanzane, sea squirts, mussels, and oysters;
When aquatic organisms such as various bacteria, mold, and diatoms called slime adhere to the bottom of a ship or underwater structures, it causes a great deal of damage in terms of preservation and maintenance of these structures. If it adheres to a ship, the frictional resistance between the ship and the seawater will increase, resulting in a significant economic loss for ship operations such as a reduction in ship speed and an increase in fuel costs. It requires a great deal of effort to remove, and there is also a large economic loss in this respect. The same can be said for underwater structures.

0003

BACKGROUND OF THE INVENTION Conventionally, as antifouling agents for underwater antifouling paints, cuprous oxide, copper rhodanide, organotin compounds, organotin polymers, thiocarbamates, etc. have been used. These compounds have the effect of preventing the adhesion of the above-mentioned aquatic plants, animals, slime, etc., and are widely used in practical applications, but the metals they contain are not desirable from a public health or ecological point of view. There is an urgent need to develop safer antifouling agents.

0004

[Problems to be Solved by the Invention] One of the characteristics required of an antifouling paint is that the effect must last for a long period of time, for example, one year or more. This is because ships and the like sail for long periods of time, and once they leave port, it is impossible to reapply the antifouling paint on the bottom of the ship until the next port of call. Furthermore, applying antifouling paint to underwater structures requires skill, and it is disadvantageous to repaint frequently, so a long-life paint is desired.

[0005]

DISCLOSURE OF THE INVENTION Therefore, the present inventors have endeavored to search for an antifouling agent that is highly safe, has excellent antifouling effects, and can maintain its effectiveness for a long time when added to an underwater antifouling paint, and has developed the present invention. It was completed.

[0006] The present invention uses the formula -(I) as an antifouling active ingredient.
)

[0007]

[Case 2]

This is an antifouling paint composition containing a maleimide compound represented by the formula (wherein X is a halogen atom) as an antifouling component.

In the formula, examples of the halogen atom of X include fluorine, chlorine, bromine and iodine. The following may be exemplified as the maleimide compound. Compound no. 1 N-(4-chloro-1-naphthyl)maleimide m. p1
38.5-141°C Compound No. 2 N-(4-bromo-1-naphthyl)maleimide compound N
o. 3 N-(4-iodo-1-naphthyl)maleimide The maleimide compound is preferably one in which X is chlorine.

The maleimide compound represented by the general formula (I) can be prepared, for example, by any of the following production methods [A] and [B].

[0011]

[Chemical formula 3]

The solvent used in the first step of the reaction may be any solvent as long as it does not inhibit the reaction, such as aromatic hydrocarbons such as benzene, toluene, and xylene; chloroform, carbon tetrachloride, and chloride. Halogenated hydrocarbons such as methylene; ethers such as diethyl ether, dioxane, and tetrahydrofuran; ketones such as acetone, methyl ethyl ketone, and methyl isobutyl ketone; nitriles such as acetonitrile and propionitrile; dimethylformamide, N-methyl-pyrrolidone, Examples include aprotic polar solvents such as dimethyl sulfoxide and sulfolane, and any solvent used in the second step may be used as long as it does not inhibit the reaction. For example, aromatic carbonization such as benzene, toluene, xylene, etc. One example is hydrogen.

[0013]

[C4]

[0014] Furthermore, when the compound of formula (I) is blended into a paint, it does not have any adverse effects on the storage stability of the paint, such as thickening or deterioration of the paint, and is highly safe, improving workability and reducing environmental pollution. There are also few. Furthermore, the compound of formula (I) has almost no toxicity or skin irritation during the production and application of paints.

The antifouling paint composition of the present invention has the advantage of having low bioselectivity, high antifouling effects on almost all aquatic fouling organisms, and lasting for a long period of time, as well as being non-corrosive to materials. This makes it especially safe for use on ships and underwater structures made of steel, light metals, and concrete.

As the paint vehicle used in the antifouling paint composition of the present invention, commonly used resin vehicles can be used. For example, vinyl chloride resin, vinyl chloride-vinyl acetate copolymer, vinyl chloride/vinyl isobutyl ether copolymer, chlorinated rubber resin, chlorinated polyethylene resin, chlorinated polypropylene resin, acrylic resin,
Styrene-butadiene resin, polyester resin, epoxy resin, phenol resin, synthetic rubber, silicone rubber, silicone resin, petroleum resin, oil-based resin,
Examples include rosin ester resin, rosin soap, rosin, and the like. Also, as a vehicle with antifouling properties, (meth)
An acrylic copolymer resin composition containing as a constituent unit an organotin compound salt of an unsaturated mono- or dicarboxylic acid obtained by a condensation reaction of acrylic acid and an organotin compound such as bis(tributyltin) oxide or triphenyltin hydroxide. You can also use

The antifouling agent of formula (I) used in the present invention is blended in an amount of 0.1 to 60% by weight, preferably 1 to 40% by weight, based on the entire coating composition. Furthermore, the antifouling coating composition of the present invention may further contain other known inorganic or organic antifouling agents, if necessary.

Examples of such compounds include cuprous oxide, copper rhodanide, copper hydroxide, copper naphthenate, metallic copper, various tin compounds, and dithiocarbamic acid derivatives, such as tetramethylthiuram monosulfide, tetramethylthiuram di Sulfide, bis-(dimethyldithiocarbamate) zinc, ethylene-bis(dithiocarbamate) zinc, ethylene-bis(dithiocarbamate) manganese, and bis-(dimethyldithiocarbamate) copper.

In addition, the antifouling coating composition of the present invention may contain commonly used plasticizers, coloring pigments, extender pigments, organic solvents, and the like.

The antifouling paint composition of the present invention can be prepared by methods known per se in the paint manufacturing field. For example, ball mill, pebble mill, roll mill,
Use a sand glider mill, etc.

The antifouling paint composition of the present invention described above provides antifouling properties and slime resistance for a very long period of time, and exhibits an excellent effect in preventing the attachment of harmful underwater organisms to ships and underwater structures. .

The present invention will be explained in more detail below using experimental examples, synthesis examples, and examples. In the examples, "parts" are by weight.

Experimental Examples The symbols and trade names of resins used in the examples below have the following meanings.

[0024] Raroflex MP-35 West Germany BAS
Vinyl chloride-vinyl isobutyl ether copolymer manufactured by Company F

NT-100 Hydrophilic acrylic resin manufactured by Nitto Kasei Co., Ltd.

A TBT-acrylic copolymer solution was prepared as follows. That is, 40 parts of a mixture of 65 parts of tributyltin methacrylate and 35 parts of methyl methacrylate was placed in a reaction tank equipped with a means for heating and cooling xylene 6.
0 parts and to this add 0.35 parts of benzoyl peroxide. To control the temperature increase due to exotherm, the temperature of the solution was increased to a final temperature of 11 over a period of 10 hours using a cooling means.
The temperature is gradually increased to 0° C. under reflux. The final solution viscosity was 4.5 poise at 25°C.

Cu-acrylic copolymer solution was prepared as follows. That is, xylene 10 was placed in a four-necked flask equipped with a reflux condenser, a stirrer, a nitrogen introduction tube, and a dropping funnel.
0 parts, add 20 parts of n-butanol, and heat to 100°C to 110°C.
Warmed to ℃. A mixed solution of 7.7 parts of methacrylic acid, 64.4 parts of methyl methacrylate, 28 parts of 2-ethylhexyl acrylate, and 3 parts of azobisisobutyronitrile was added dropwise into this solution over 4 hours.

[0028] After completion of dropping, keep warm at 110°C for 30 minutes,
A mixed solution of 20 parts of xylene, 10 parts of n-butanol, and 0.5 parts of azobisisobutyronitrile was added dropwise over 1 hour, and the temperature was kept for 2 hours after the addition. The solid content in the obtained resin solution was 39.8 wt%, and the solid content acid value was 50 mgKOH.
/g of varnish A was obtained.

100 parts of varnish A, 7.4 parts of copper propionate, 10 parts of naphthenic acid, and 20 parts of deionized water were added to a four-necked flask equipped with a reflux condenser, a stirrer, a nitrogen introduction pipe, and a decanter, and the mixture was heated at 100°C. The propionic acid produced as the reaction progressed along with water was removed.

The end point of the reaction is determined by quantifying the amount of propionic acid in the effluent solvent, and the water in the system is completely removed to complete the reaction.
Added xylene. The resulting varnish had a solid content of 52.3
A varnish with wt% and viscosity P (value of P on a bubble viscometer) was obtained.

Synthesis Example Synthesis of N-(4-chloro-1-naphthyl)maleimide (Compound No. 1) 153 ml of 4-chloro-1-naphthylamine in 100 ml of 100% acetic acid
g and 93 g of maleic anhydride were mixed and refluxed for 4 hours. Thereafter, most of the acetic acid was distilled off using a rotary evaporator, 1000 ml of water was added, and the mixture was extracted with ethyl acetate. The extracted ethyl acetate layer was washed with aqueous sodium bicarbonate until neutralized, then washed twice with water, dried over anhydrous sodium sulfate, and then the solvent was distilled off. Silica gel column chromatography (developing solvent: 1 part methylene chloride to 1 part hexane)
), then recrystallized from ethyl acetate and hexane to a melting point of 1.
148 g of the target compound (compound No. 1), which is a yellow crystal with a temperature of 38.5 to 141° C., was obtained.

[0032]

[Example] The ingredients shown in Table 1 were charged into a ball mill, and 1
Dispersion was carried out for 6 hours to prepare an underwater antifouling paint. For comparison, a paint containing a known antifouling agent was prepared. The formulation is shown in Table-2.

An antifouling test was conducted using these antifouling paints. The antifouling test was conducted on a 100 x 300 mm test coated with the antifouling paints shown in Tables 1 and 2 (commercially available ship bottom No. 1 paint based on coal tar/vinyl chloride resin). The coating was applied twice to a dry film thickness of 60-80 microns on a steel plate, and after drying for 24 hours, it was immersed in a test raft to a depth of 1 m in the sea to remove animals such as barnacles, celbula, and other animals such as sea lettuce and green laver. The amount of attached plants was examined and evaluated by visual observation in terms of attached area %. The test period is two years. Table 3 shows the changes in the amount of biofouling.

[0034]

[Table 1]

[0035]

[Table 2]

[0036]

[Table 3]

Claims (1)

[Claims] 1. An antifouling paint composition comprising a maleimide compound represented by the general formula: [Image Omitted] (wherein X is a halogen atom) as an antifouling component.