JP3106329B2 - Ship bottom paint - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a method in which an oxide such as dibutyltin or ethylmethylmethyltin hydrohalide is mixed in a ship bottom paint,
In addition, it was used for shell protection of fishing nets, but this tin compound causes seawater pollution and contaminates fish and shellfish, seaweed,
It accumulates in the liver of the human body that eats it, and 20P. P. It exceeded M. Therefore, there is no other way to prevent this marine pollution except to ban the use of tin compounds that have shell-proofing effect. Was. For this reason, the present invention provides silicates such as SiO2, Al2O3, Fe2O3, CaO, Mg
A mixture of mineral powder containing trace amounts of radiation mainly composed of natural minerals of O, K2O, Na2O, calcium fluoride, and aluminum fluoride, mixed with the bottom paint,
Furthermore, silicate, zirconium fluoride, titanium fluoride,
Using a material to which fluoride or the like has been added, using polyacrylic acid resin copper water as an undercoat, applying it to the polished surface of the wall surface of the iron ship and coating the surface with a cuprous oxide film, and then applying a known The undercoat of No. 1 hull paint was coated with a mixture of silicate, zirconium fluoride, titanium fluoride, fluoride powder, etc., and silicate, zirconium fluoride, fluoride Titanium, a mixture of titanium oxide and fucca powder, a top coat is applied to the bottom of the ship, and the surface is further finished.The top coat is made of silicate, zirconium fluoride, titanium fluoride,
A paint containing fluoride powder, etc., applied and dried exhibits an extremely high anti-shell effect and is not different from the case of using tin compounds, so it can exhibit the effect of reducing marine pollution of tin compounds. The content of General ship bottom paints (Ship bottom coat
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h) For steel boats, paints to prevent the corrosion of the bottom of the ship and to prevent the adhesion of living things to prevent the increase in the propulsion resistance of the ship, and for wooden boats, paints to prevent the adhesion of living things and harm of bark beetles and fungus beetles Say. (1) Steel ship bottom paint After pre-treating the bottom surface of the ship bottom, first, rust-stop paint (No. 1 ship bottom paint or AC
Is applied undercoating, and an antifouling paint (referred to as No. 2 bottom paint or AF) is applied thereon to prevent biofouling. Examples of the procedure are shown in Tables I and II. The two main types of creatures that attach to the bottom of the ship and actually pose a problem are barnacles and serpula, and there are also oysters, mussels, mosses, and sea squirts. These prevention methods are based on the common poisons of mercury (II) iodide, mercury (I) chloride and (II) mercury oxide (I).
I), mercury compounds such as mercury (II) arsenate and mercury soap, and copper (II) oxide, copper (II) nitrate, copper (I) oxide, copper (II) cyanide, copper arsenite, copper soap and the like Copper compounds and organic toxicants such as DDT are effective. Recently, mercury compounds are no longer used, and copper compounds,
In particular, copper (I) oxide is most frequently used. Organic poisons also tend to be increasingly used. Antifouling paints contain these poisons. A sea varnish or the like resistant to seawater has been used as a vehicle for the bottom paints of Nos. 1 and 2, but recently vinyl chloride / vinyl acetate copolymers (for example, vinylite VAGH and VYHH) have been recommended. In recent years, in order to completely prevent corrosion of the bottom of ships, cathodic protection using magnesium, zinc, etc. as anode has been increasingly used in combination with children. (2) Wooden ship bottom paint It is common to apply paint containing copper (I) oxide as the main poison twice. In the United States, materials that come into direct contact with seawater, such as skin and keel, are processed, dried, immersed in a copper naphthenate solution (containing 1.5% or more copper) for 3 to 30 minutes, and dried before use. A generally known natural silicate,
Calcium fluoride and aluminum fluoride are used together with fluorite as a raw material for electrolytic refining of aluminum metal and as a raw material for phosphate fertilizer, and are treated with a phosphoric acid or sulfuric acid solution to separate fluorides. It reacts to remove iron and other impurities to produce high-purity aluminum fluoride, but many of its raw materials include uranium, chromium, vanadium, thorium, lanthanum, strontium and other radiating substances. It is generally eluted by acid decomposition and purified and separated, but in this method, natural silicate, natural calcium fluoride, natural aluminum fluoride, etc. are used as they are, and the radiation properties are utilized. In order to promote the anti-shell effect,
Further, purified fluoride is also used in combination. In the presence of 4 to 2,500 microcuries of this radiating mineral, when mixed with this paint, it blocks the access of plankton, which is the bait of the shellfish, due to its radiating properties, and the water molecules in the contacting seawater. Of the structure of the calcium (measured by magnetic resonance), condensed, encapsulated the solution of calcium, and fluoride reduced the adhesion of the shell, vibration,
Due to the physical factors of the object, the effect of promoting peelability is exhibited. Therefore, even if it adheres to the hull bottom paint, it hungry without allowing the access of plankton and bacterial bacteria due to radiation, and by suppressing the growth of its shell, it exerts a shell protection effect, and it is easy for seaweed to adhere For iron ions, the ship's wall surface is plated with a complex salt resin such as copper, tin, chrome, manganese, vanadium, etc. of polyacrylic acid to form a coating of metal polyacrylate, suppressing iron ion solubility, The repelling effect of the shell by the copper film is exhibited, so it has a sufficient paint-like effect on marine navigation. According to the JIS standard, general ship bottom paints are No. 1 and No. 2 paints. Generally, the steel surface on the side of the ship wall is rust-proof and the undercoat paint for undercoat is applied. Oil-based (boil oil-based), polyester-based, and polyvinyl-based paints are standardized as the ship bottom paint. After applying the undercoat bottom paint, the top coat bottom paint is applied after drying. In general, a top coat is applied to the wear surface in contact with the seawater surface after several applications. Cinnabar flour was initially used for shell and alga protection, but its use has been banned due to the toxicity of mercury, and as a substitute, tin complex salt, which is even less toxic, is mixed with ship bottom paint. Was. However, also from the fishing boats to large vessels, marine pollution is remarkable when used as bottom paint, especially in the narrow Seto Inland Sea, where the mobility of seawater is small, so the concentration of tin complex in seawater gradually increases. Fish and shellfish and seaweed inhabiting the inland sea gradually become tin-contaminated, and even for those who eat it, the accumulation of tin in the liver has increased to the limit of dangerous concentrations. However, it was not easy to develop a substitute component system. Originally, the main purpose of ship bottom paint is that the steel hull is easily corroded by seawater, and the direct contact with seawater is protected by oily or synthetic resin paint.
However, when the steel surface is plated with seawater-resistant copper or tin, the degree of corrosion of the steel surface is reduced to 1/100 or less.
However, plating on this large hull is not easy to process and the labor costs are high. In addition, corrosion does not occur with things like stainless steel or titanium metal,
These materials themselves are expensive, and it is generally economical to use ship bottom paint that has a short life and is easy to peel off.
It was also easy in terms of resources. Therefore, we considered the formation of a protective film on the steel surface by metal-to-metal bonding similar to expansion and contraction with less peelability, but considered a plating method by electroplating and immersion. Add a small amount to acrylic acid or organic acid water to dissolve copper corrosion-resistant metal ions in a solvent of mineral acid to make a complex salt solution and make it resin When paint is applied by brushing or spraying with resin added, the iron on the copper iron surface is replaced with copper ions, and copper and plating are immediately applied.
It takes about 2 minutes to make a thin metal film or sub-oxide film, protect the steel surface by plating, and increase the corrosion resistance more than 10 times. Therefore, when applying the ship bottom paint to the surface, the corrosion resistance is further increased However, the organic acid salt needs to be cleaned as an unnecessary impurity. In particular, the presence of an acid promotes corrosion at last, so that it is preferable to wash it. Then, if the ship bottom paint is applied after drying sufficiently, the releasability is lost. Even if the copper thus corroded in the hull bottom paint, it did not generate a large amount like iron ions on the steel surface, and a small amount of these metal ions suppressed the generation of plankton in the shell. There is little adhesion to the hull, and there is little toxicity due to the low toxicity of copper complex salt and small amount of dissolved ions, and it does not cause excessive marine pollution. And since the adhesiveness to a copper surface is also high, the result that adhesiveness of a paint is also high is obtained. Therefore, by adding radiating substances such as silicate, calcium fluoride, aluminum fluoride, etc., it is possible to suppress the occurrence of plankton-producing bait and to easily adopt a fluoride-specific planar structure, so that shells, etc. Since the adhesive structure is not easily attached and a peelable adhesive structure is formed, the advantage that the peeling property is improved by the microvibration is used. The well-known tin salt kills a lot of plankton by dissolving the tin salt, so that it stops the supply of food necessary for the growth of the shellfish and produces calcium stannate, so it takes advantage of the disadvantage that the crystals fall out due to calcium deposition. However, it has a relatively high solubility in seawater, and is used for coating seaweed, cultured fish nets and bamboo pillars, etc., and a large amount of tin is washed away in seawater. However, there are few substitutes for it, so it is far from being extinct.
However, the use of more toxic mercury complex salts may lead to the Minamata pollution case, so there is still a problem with their use, and silicates, calcium fluoride, fluoride, etc. Compared to these known toxic tin salts and mercury salts, the toxicity is 1/20 or less, which is extremely useful.
In particular, the radiating property is present in the majority of fluorides in natural products, and at a concentration of 4 to 40 microcuries, there is no adverse effect on the human body. Bacterial bacteria are not easily propagated in condensed water, that is, in 6, 5, 4, or membered rings, and have an effect of promoting propagation in a low molecular structure having four or less rings. Because it demonstrates
It helps to reduce shellfish and plankton prey. The embodiment of the present invention will be described below with reference to the drawings. In FIG. 1, a stirrer (2) is introduced into a tank (1) from an undercoat paint tank (5), (4) according to JIS.
The mixed liquid is stored in a tank (7), and the mixture is stored in a tank (7) and poured into a paint can (9) on a tank table (8). The canned product is conveyed by a belt conveyor (10) and sealed and packaged in a packaging device (11) to prepare an undercoat paint. Similarly, the top coat is introduced into the tank (1 ') into the top coat liquid (5') (4 '), the fluoride powder is introduced from the hopper (3'), and the tank is stirred by the stirrer (2 '). Introduce and store in (7 '). Then, the mixture is filled in a paint can (9 ') on a turntable (8'), loaded and conveyed on a belt conveyor (10), and sealed and packaged in (11). Copper polyacrylate is a hopper (13) (14) (15) in a ratio of 1 part of water to 1 part of acrylic acid.
And 0.1 part of copper chloride and 0.03 part of peroxide are dispersed in water and added to make a ratio of 2 parts of water. This is put in a tank (12), stirred by a stirrer (16), heated from a hot water tank (17), heated to 50 ° C. to 120 ° C., and reacted, and cooled in a cooling tank (18). The reaction is completed in about one hour while adjusting. In order to promote this reaction, a little aluminum or iron scrap is added to accelerate the reaction. However, a copper precipitate is formed, so that it is filtered with a filter (20) by a pump (19) to prepare an undercoated copper paint. The copper precipitate at the bottom of the tank (12) is recovered together with the precipitate in the filter (20) and reused as copper chloride. FIG. 3 is a side view of the hull, in which copper plating is applied to the hull steel (1a) surface, an undercoat paint (3a) is applied to the surface thereof, and a topcoat paint (4a) and a draft paint (5a) are further applied. Apply. The composition of this copper undercoat liquid is as follows. [Example 1] Polyacrylic acid 30 parts Copper chloride or copper acrylate 8.5 parts Water 60 parts Catalyst etc. 1.5 parts [Example 2] Undercoating bottom paint 80 parts Silicate or calcium fluoride Aluminum fluoride ore powder 18 parts Other 2 parts [Example 3] Top coat 80 parts Silicate, calcium fluoride, aluminum fluoride, ore powder 18 parts Zirconium oxide or titanium oxide and other ore powder 2 parts [Example 4] Top coat 80 parts Acrylic acid or poly Vinyl acetal resin mixed resin or ethyl acrylate 30 parts Vanadium sulfate or manganese sulfate or titanium sulfate, zirconium chloride ore powder 2 parts Fluoride ore powder such as silicate, calcium fluoride, aluminum fluoride 7 parts Others 1 part Water 60 The part [Fig. 2] shows the degree of adhesion of the shell, after coating the iron plate with copper in seawater, Then, the product which was further overcoated and finished was immersed in seawater for 6 months, (A) is a case of iron plate only, (B) is a mixture of 5% of a known tin compound, and (C) is It contains the fluoride of the present application.
(D) shows an iron plate that has been previously copper-coated with a copper methyl acrylate solution and is then coated with an undercoat. (E) Vibration of 30 cycles for 1 minute. According to the above results, there is hardly any difference from the case where a known tin compound is added, but the case where a copper coating is applied further results in less adhesion of shells. This indicates that iron ions are less eluted due to the decrease in plankton due to the elution of copper ions. In addition, even after 6 months, the radiated product of fluoride has strong peelability of the shell. As described above, the feature of the present invention is to reduce the pollution of tin complex salts in known hull bottom paints by replacing them with low-radiation fluorides to enhance them with a copper coating, which has been increasing year by year. It reduces tin marine pollution levels with fluoride and thus reduces tin pollution. Water molecules are condensed by the radiating property of fluoride, etc., and the growth of bacteria and microbial bacteria that feed on plankton is suppressed. It is also used for fishing nets and bamboo poles, and has a wide range of uses for defense, and is an industrially useful invention.

[Brief description of the drawings] Fig. 1 Schematic diagram of production of top and bottom coatings [Fig. 2] Characteristics of preventing shell adhesion FIG. 3 is a side view of the hull.

Claims (1)

(57) [Claims] Low radiating silicate, fluoride, zirconium, titanium oxide on the surface of a ship by coating the surface of a ship wall with copper polyacrylate and forming a plating film with copper polyacrylate Bottom paint with a base coat and a top coat mixed with material powder, and a top coat containing silicate, fluoride, zirconium and titanium oxide powder to protect the waterline.