JPS6042471A - Underwater antifouling paint - Google Patents

Abstract

PURPOSE:To provide an underwater antifouling paint which does not cause environmental pollution and prevents the deposition of harmful aquatic organisms on vessels and underwater structures, by incorporating a specified thiourea compd. CONSTITUTION:An underwater antifouling paint contains a compd. of the formula (wherein R1, R2 are each H, a straight-chain satd. or unsaturated hydrocarbon group, a phenyl group-substd. straight-chain satd. or unsaturated hydrocarbon group) as an active ingredient. Examples of the compds. are N,N'-dimethylthiourea and N,N'-benzylthiourea. Examples of R1 and R2 groups are pref. H, 4C or lower alkyl, alkenyl and benzyl. When a 5C or higher straight- chain hydrocarbon group is used, effects are lowered. Examples of vehicles used for the antifouling paint are vinyl chloride resin, chlorinated polyethylene resin and acrylic resin. Optionally, additives such as plasticizer, color pigment, extender pigment, solvent, etc. can be added.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention provides for the prevention of harmful aquatic organisms to ships and underwater structures.
This invention relates to underwater antifouling paint that prevents staining.

Ship bottoms and main lines, power plant water intakes and inside surfaces of cooling pipes,
Fishing nets, fishing nets, and other types of marine or freshwater structures that contain aquatic organisms such as sea lettuce, blue seaweed, seaweed, algae such as Hibimidoguchi, fujibbo, serpura, kasane kanzashi,
When animals such as sea squirts, mussels, and oysters, and aquatic organisms such as various bacteria called slime, mold, and diatoms proliferate, it causes great damage to the conservation and maintenance of these structures. For example, in the case of a ship, the frictional resistance between the ship's hull and the seawater increases, resulting in significant economic losses such as reduced acceleration and increased fuel costs. A great deal of effort is required to remove the deposits.

In cages and fishing nets, there are problems such as poor growth of farmed fish and lack of oxygen; fixed nets cause the nets to float up, reducing the amount of fish caught; and on the inside of cooling pipes, the heat exchanger gets clogged, resulting in operational stoppages and a drop in cooling efficiency.

Conventionally, these ships and underwater structures have been equipped with measures to protect against and prevent the growth of aquatic organisms. Cuprous oxide, copper rhodan, organic tin compounds, organic tin polymers, thiocarbamates, and the like are used as the 9JJ components of underwater antifouling paints for biofouling. It is desired that these components maintain a constant level of antifouling properties for a long period of time and that highly toxic substances are not released into the water from the standpoint of environmental pollution.

According to the present invention, an underwater antifouling paint containing an active ingredient that satisfies these requirements is provided.

The underwater antifouling paint of the present invention contains, as an active ingredient, the general formula: It is characterized by containing a compound represented by (representing a chain saturated or unsaturated hydrocarbon group).

Examples of compounds represented by the above general formula include thiourea, N,
Includes N'-dimethylthiourea, N,N'-diethylthiourea, N,N'-dipropylthiourea, N,N''-dibutylthiourea, N,N'-dibenzylthiourea, etc. Groups represented by R1 and R2 A hydrogen atom, an alkyl or alkenyl group having 4 or less carbon atoms, or a benzyl group is preferable, and in the case of a quenched hydrocarbon group, the effect tends to decrease when the number of carbon atoms is 5 or more. For thio derivatives, either symmetric or asymmetric types can be used.

The antifouling paint containing the compound of the above general formula as an active ingredient does not have any drawbacks that impair the storage stability of the paint, such as thickening or deterioration, and is highly safe, improving workability and reducing environmental pollution. There are also few. That is, toxicity and skin irritation are hardly a problem during paint manufacturing and painting.

Furthermore, the antifouling paint of the present invention has the advantage that it has low bioselectivity, has a high antifouling effect against most harmful young aquatic organisms, has excellent slime resistance, and has long-lasting efficacy. It can also be safely used on light alloy type ships.

The anti-teta coating material of the present invention can also contain a known copper-based, organotin-based, and/or dithiocarbamate-based antifouling agent in addition to the compound of the above general formula. For example, copper-based lη inhibitors include cuprous oxide, copper rhodan,
Examples of tin-based antifouling agents include copper hydroxide and metallic copper.
Bis-(1-butyltin) oxide, tributyltin chloride, tributyltin fluoride, tributyltin acetate, tributyltin nicotinate, tributyltin herzatate, bis-(tributyltin)-
α, α°−dibromusak? triphenyltin hydroxide, triphenyltin chloride, triphenyltin fluoride, triphenylsus acetate, triphenyltin nicotine-1, triphenyltin dimethyldithiocarbamate, triphenyltin hersate, bis -(triphenyltin)-α, α゛
-dibrome succinate, his-(triphenyltin)
There are oxides, etc. As a dithiocarbamic acid derivative, tetramethylthiuram monosulfide (abbreviated as TS
), tetramethylthiuram disulfide, bis-(
Zinc dimethyldithiocarbamate (abbreviated as ZIJMC)
, ethylene-bis(dithiocarbamate) zinc (abbreviation Z
INEB), ethylene-bis(dithiocarbamic acid)
Manganese, bis-(dimethyldithiocarbamic acid) tears (
The abbreviation is TTCu).

Suitably, the compound of the above general formula accounts for 0.5 to 50% by weight, preferably 1 to 30%, of the total coating composition.

The resin vehicle used in the antifouling paint of the present invention may be a resin commonly used in antifouling paints, such as hinyl chloride resin, chlorinated rubber resin, chlorinated polyethylene resin, chlorinated polypropylene resin, acrylic resin, Styrene-butadiene resin, polyester resin, epoxy resin 1.
Examples include myriamide resin, petroleum-based resin, oil-based resin, rosin cosstill, rosin-based soap, rosin, and the like. In addition, as a vehicle with antifouling properties, a polymerizable compound obtained by the reaction of a polymerizable unsaturated carboxylic acid such as (tsuku)acrylic acid with an organic tin compound such as bis(tributyltin) oxide and triphenyltin hydroxide is used. Acrylic copolymer 4fi containing unsaturated carboxylic acid organic tin compound JF as a constituent unit + fat can also be used.In addition, commonly used build-up agents, coloring type T-1 extender pigments, solvents, etc. It can be contained in any proportion.

The antifouling paint of the present invention can be prepared by a method known per se in the field of paint manufacturing technology. For compounding, a known machine such as a ball mill, pebble mill, roll mill, speed run mill, etc. is used.

The present invention will be explained in detail below using Examples and Comparative Examples. In these, "part" means "part by weight", Δ
Taste.

In addition, the resin symbols and trade names used therein have the following meanings.

If'-45: Product of BASF, West Germany, vinyl chloride-vinyl isobutyl ether copolymer Prioride 5-5B: Product of Gutdeyer Co., Ltd., USA, styrene-butadiene copolymer VAGH: Product of UCC, USA, vinyl chloride 40 parts of a mixture of 65 parts of nitributyltin methacrylate and 35 parts of methyl methacrylate in acrylic copolymer solution are dissolved in 60 parts of xylene in a reaction vessel equipped with heating and cooling means, 0.35 for this
of hendiyl peroxide was added. The temperature of the /8 liquid was gradually increased under reflux to a final temperature of 110° C. over a period of 10 hours using the necessary cooling means to control the oxidation. The final solution viscosity was 4.5 voids at 25°C.

Examples and Comparative Examples The compound of the above general formula and the components of the pond were charged into a ball mill and dispersed for 24 hours to prepare an underwater antifouling paint. Table 1 shows the formulation of the antifouling paint according to the invention.

Due to the specific axis, a known comparative antifouling paint was prepared in the same manner. The formulation is not shown in Table 2.

An antifouling test was conducted using these antifouling paints. In the antifouling test, after preparing the antifouling paints shown in Tables 1 and 2, 100
Dry film 17 is 60 to 80 on a test steel plate with a size of ++.
Apply one coat to a micron size, and after drying for 24 hours,
Test raft underwater 1, off the coast of Gomanoura, Tamano City, Okayama Prefecture
It was immersed at a depth of n, and the amount of adhesion of animals such as Fujitbo and Serpura, and plants such as Ulva and Blue Nori was examined and evaluated by visual observation as a percentage of adhesion area.

At the same time, changes in the amount of slime adhesion were visually examined and evaluated as adhesion area %.

The test period is from January 1980 to January 1980.

Table 3 shows the changes in the amount of biological adhesion, and Table 4 shows the changes in the amount of slime 11 attached.

Note that slime is a viscous film of metabolites of various underwater grouper cheeks and bacterium, and is a general term for diatoms.
When this adheres, spores of green lettuce, green laver, or fujibbo larvae enter, encouraging the reproduction of polluting organisms.
Anti-litter paints must also have slime resistance.

As is clear from the Examples shown in Table 4 and above, the underwater antifouling paint of the present invention shows significantly better results than the comparative examples.

In particular, it exhibits a surprisingly excellent effect in preventing slime adhesion, and the fact that it has such an outstanding effect in slime resistance is very significant.

Claims (1)

[Claims] General formula, (wherein R1 and I?2 represent a hydrogen atom, a saturated or unsaturated hydrocarbon group, or a phenyl-substituted chain saturated or unsaturated hydrocarbon group) An underwater antifouling paint characterized by containing the represented compound as an active ingredient.