JPS6224022B2 - - Google Patents

Description

[Detailed description of the invention]

INDUSTRIAL APPLICATION FIELD The present invention relates to a novel underwater antifouling paint. For more details, see the general formula () The present invention relates to an underwater antifouling paint characterized by containing a tetraphenyl boron derivative represented by the following formula (wherein R represents a lower alkyl group) as an active ingredient. Conventional technology and problems Aquatic organisms such as sea lettuce, seaweed, sea cucumber, and other marine creatures can be found on the bottoms and water lines of ships, the inner surfaces of water intakes and cooling pipes in power plants, fish tanks, fishing nets, and other marine or freshwater structures. algae, barnacles, serpura, kanzane, sea squirts, mussels,
When animals such as oysters, aquatic organisms such as various bacteria called slime, mold, and diatoms grow on these structures, it causes great damage in terms of conservation and maintenance of these structures. For example, in the case of ships, the frictional resistance between the hull and the seawater increases, resulting in significant economic losses such as a reduction in ship speed and an increase in fuel costs.Also, when the ship is docked for maintenance, the above-mentioned deposits increase. Removal requires a lot of effort. 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, measures have been taken to prevent the attachment and growth of aquatic organisms on these ships and underwater structures. The active ingredients of this underwater antifouling paint for biofouling are:
Cuprous oxide, copper rhodan, organotin compounds, organotin polymers, thiocarbamates, etc. are used. It is desirable for these components to maintain a certain antifouling effect for a long period of time and not to release highly toxic substances into water from the standpoint of environmental pollution. The present inventors have previously discovered that a tetraphenylboron-ammonium compound (Japanese Patent Publication No. 1571/1983) is useful as a new low-toxicity antifouling compound in place of conventional poisonous substances. This tetraphenylboron-ammonium compound has extremely low toxicity and there is no need to worry about skin irritation during paint manufacturing or coating, improving workability.
It has advantages such as less environmental pollution. Furthermore, since it has low solubility in seawater, it does not elute in large amounts into seawater at once. Therefore, compared to conventional organometallic compounds, it is possible to prevent the adhesion of seawater organisms over a long period of time. However, in recent years, there has been a demand for compounds with better long-lasting effects from an economic standpoint. Means for Solving the Problems The present inventors focused on the low toxicity of the compounds described in the above publication, synthesized a large number of tetraphenylboron derivatives, and investigated their usefulness as active ingredients for underwater antifouling paints. Tested. As a result, the general formula of the present invention () The tetraphenylboron derivative represented by has extremely low selectivity in antifouling activity, almost completely inhibits the adhesion of all marine organisms, and has a longer lasting antifouling effect than the similar compounds described in the above publication. The present invention was completed based on the discovery that it has an excellent long-lasting property. Detailed Disclosure of the Invention Examples of the compound of general formula () which is an active ingredient of the underwater antifouling paint of the present invention include the following, but the present invention is not limited thereto. The above-mentioned active ingredient compound can be produced in the same manner as described in Japanese Patent Application No. 59-9516 (Japanese Unexamined Patent Publication No. 60-155185). The antifouling paint of the present invention can also contain a known copper-based, organotin-based, and/or dithiocarbamic acid-based antifouling agent in addition to the compound of the above general formula. Examples of copper-based antifouling agents include:
Examples include cuprous oxide, rhodanic copper, copper hydroxide, and metallic copper. Tin-based antifouling agents include bis(tributyltin) oxide, tributyltin chloride,
Tributyltin fluoride, tributyltin acetate, tributyltin nicotinate, tributyltin versatate, bis-(tributyltin)-α・α′-dibromsuccinate, triphenyltin hydroxide, triphenyltin chloride, triphenyltin fluoride, triphenyl Examples include tin acetate, triphenyltin nicotinate, triphenyltin dimethyldithiocarbamate, triphenyltin versatate, bis-(triphenyltin)-α·α′-dibromsuccinate, bis(triphenyltin) oxide, and the like. Examples of dithiocarbamic acid derivatives include tetramethylthiuram monosulfide (abbreviated as TS), tetramethylthiuram disulfide,
Zinc bis(dimethyldithiocarbamate) (abbreviation ZDMC), ethylene-bis(dithiocarbamate) zinc (abbreviation ZTNEB), ethylene-bis(dithiocarbamate) manganese, bis-(dimethyldithiocarbamate) copper (abbreviation TTCu), etc. . It is appropriate that the compound of the general formula () occupies 0.5 to 50% by weight, preferably 1 to 30% by weight of the entire 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 vinyl chloride resin, chlorinated rubber resin, chlorinated polyethylene resin, chlorinated polypropylene resin,
Examples include acrylic resin, styrene-butadiene resin, polyester resin, epoxy resin, polyamide resin, petroleum resin, oil resin, rosin ester, rosin soap, and rosin. In addition, as a vehicle with antifouling properties, a polymerizable compound obtained by the reaction of a polymerizable unsaturated carboxylic acid such as (meth)acrylic acid with an organic tin compound such as bis(tributyltin) oxide and triphenyltin hydroxide is used. Acrylic copolymer resins containing organotin compound salts of unsaturated carboxylic acids as constituent units can also be used. In addition, commonly used plasticizers, coloring pigments, extender pigments, solvents, etc. can be contained in arbitrary proportions. 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. Examples The present invention will be explained in detail below using Examples and Comparative Examples. In these terms, "parts" means "parts by weight." Example 1 20 parts of Compound No. 1, 7 parts of VAGH (vinyl chloride resin manufactured by Union Carbide Co., USA; the same applies hereinafter), 6 parts of W.W rosin, 1 part of colloidal silica, 4 parts of red iron oxide, titanium oxide Part 5, evil lead flower
A paint is prepared by uniformly mixing 20 parts of dioctyl phthalate, 2 parts of dioctyl phthalate, 30 parts of xylene, and 5 parts of methyl isobutyl ketone. Example 2 A paint is prepared according to Example 1, except that Compound No. 2 is used as the active ingredient. Example 3 A paint is prepared according to Example 1, except that Compound No. 3 is used as the active ingredient. Example 4 10 parts of compound No. 1, 20 parts of cuprous oxide,
TBT-acrylic copolymer solution (a mixture of 65 parts of tributyltin methacrylate and 35 parts of methyl methacrylate was dissolved in 60 parts of xylene, and 0.35 parts of
40 parts of colloidal silica, 5 parts of titanium oxide, 40 parts of colloidal silica, and 5 parts of titanium oxide after polymerization reaction for 8 hours to give a viscosity of 4.5 poise at 25°C.
10 parts of zinc white and 14 parts of xylene are uniformly mixed to prepare a paint. Example 5 10 parts of compound No. 2, 38 parts of cuprous oxide,
Prepare a paint by uniformly mixing 6 parts of VAGH, 6 parts of W/W rosin, 1 part of colloidal silica, 4 parts of red iron, 5 parts of zinc white, 2 parts of dioctyl phthalate, 23 parts of xylene, and 5 parts of methyl in butyl ketone. . Example 6 10 parts of compound No. 1, 5 parts of triphenyltin chloride, 7 parts of VAGH, 6 parts of W/W rosin,
1 part colloidal silica, 4 parts red iron oxide, 5 parts titanium oxide, 25 parts zinc white, 2 parts dioctyl phthalate
30 parts of xylene and 5 parts of methyl isobutyl ketone are uniformly mixed to prepare a paint. Example 7 A paint was prepared according to Example 6 except that Compound No. 3 was used as the active ingredient. Example 8 5 parts of Compound No. 2, 10 parts of cuprous oxide, 5 parts of triphenyltin chloride, 7 parts of VAGH, W.
A paint is prepared by uniformly mixing 6 parts of W rosin, 1 part of colloidal silica, 4 parts of red iron oxide, 5 parts of titanium oxide, 20 parts of zinc white, 2 parts of dioctyl phthalate, 30 parts of xylene, and 5 parts of methyl isobutyl ketone. Comparative example 1 40 parts of cuprous oxide, 7 parts of VAGH, 6 parts of W/W rosin
A paint is prepared by uniformly mixing 1 part of colloidal silica, 4 parts of red iron oxide, 5 parts of titanium oxide, 2 parts of dioctyl phthalate, 30 parts of xylene, and 5 parts of methyl isobutyl ketone. Comparative Example 2 20 parts of triphenyltin chloride, 7 parts of VAGH,
Prepare a paint by uniformly mixing 6 parts of W/W rosin, 1 part of colloidal silica, 4 parts of red iron oxide, 5 parts of titanium oxide, 20 parts of zinc white, 2 parts of dioctyl phthalate, 30 parts of xylene, and 5 parts of methyl isobutyl ketone. do. Comparative example 3 38 parts of copper zincide, 10 parts of triphenyltin chloride
A paint is prepared by uniformly mixing 6 parts of VAGH, 6 parts of W/W rosin, 1 part of colloidal silica, 4 parts of red iron oxide, 5 parts of titanium oxide, 2 parts of dioctyl phthalate, 23 parts of xylene, and 5 parts of methyl isobutyl ketone. do. Comparative example 4

[Formula] [Compound disclosed in Japanese Patent Publication No. 54-1571] 20 parts, VAGH 7 parts, W.
A paint is prepared by uniformly mixing 6 parts of W rosin, 1 part of colloidal silica, 4 parts of red iron oxide, 5 parts of titanium oxide, 20 parts of zinc white, 2 parts of dioctyl phthalate, 30 parts of xylene, and 5 parts of methyl isobutyl ketone. Comparative Example 5 A commercially available chlorinated rubber antifouling paint was obtained and used. Effects of the Invention Next, the usefulness of the underwater antifouling paint of the present invention will be explained with reference to test examples. Test examples (aquatic organism adhesion control test and slime adhesion control test) The paints prepared in Examples 1 to 8 were each coated with anti-corrosion coating (commercially available ship bottom No. 1 paint based on coal tar/vinyl chloride resin).
A test steel plate with a size of 100 x 300 mm was coated with one coat to give a dry film thickness of 60 to 80 microns, and after drying for 24 hours, it was placed on a test raft off the coast of Uno Port, Tamano City, Okayama Prefecture, at a depth of 0.5. m, immersed in 1.5 m of sea 2
We conducted various tests. The test board immersed at a depth of 1.5 m was evaluated by visual observation of the amount of animals such as barnacles and serpura and plants such as sea lettuce and green laver attached as percentage of the attached area. Also depth 0.5
The test plate immersed in water was used to evaluate the slime resistance, and the change in the amount of slime adhesion was evaluated by visual observation using the adhesion area as %. The exam period is 56 years 4
It was a two-year period from March to April 1958. Also, for comparison, paints prepared using known antifouling compounds as active ingredients (Comparative Examples 1 to 4)
A commercially available chlorinated rubber stain paint (Comparative Example 5) containing zincated copper and an organic tin compound was similarly tested. The results are shown in Table 1 (1.5m depth test) and Table 2 (0.5m depth test), and the antifouling paint of the present invention was better than known comparative antifouling paints in terms of biofouling resistance and slime resistance. It has also been proven that it is significantly superior. Furthermore, slime is a general term for diatoms, a viscous film of various underwater bacteria and bacterial metabolites, and when this slime adheres, spores of sea lettuce, blue seaweed, or barnacle larvae enter, promoting the reproduction of contaminant organisms. Antifouling paints must have excellent slime resistance.

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Claims (1)

[Claims] 1. General formula An underwater antifouling paint characterized by containing a tetraphenyl boron derivative represented by the formula (wherein R represents a lower alkyl group) as an active ingredient.