JPH06320106A - Ship bottom paint - Google Patents

Abstract

PURPOSE:To provide ship bottom paint capable of increasing release property of sea shells, decreasing generation of plankton and reducing toxicity by substituting silicate and fluoride ore powder having low radiation properties for tin complex salt contained in sea shellproof paint which becomes a cause of marine pollution. CONSTITUTION:Ore powder of silicate, calcium fluoride and aluminum fluoride complex salt having low radiation properties is added as a substitute for tin complex salt of well-known bottom paint. The iron and steel face of a ship wall is previously coated with liquid of copper polyacrylate to form a copper film. The surface of the copper film is undercoated with paint incorporating ore powder of silicate and fluoride having low radiation properties to stick a paint film. Furthermore ship bottom paint for top coating is applied thereto which incorporates silicate and fluoride ore powder having low radiation properties. In such a way, the sea shellproof and algaproof ship bottom paint is obtained.

Description

DETAILED DESCRIPTION OF THE INVENTION In the present invention, a tin compound such as dibutyryl tin or ethiyl / methyl / hydrohalide is mixed in a ship bottom paint and used as an anti-shell shell for a fish net. This tin compound causes pollution of seawater, contaminates fish and shellfish and seaweed, and accumulates in the liver of the human body that eats it.
I reached pm. Therefore, in order to prevent this marine pollution, there is no other way than prohibiting the use of this tin compound that has a shell-repelling effect, and the usage regulations have been met, but there is no good harmless shell-repellent agent to replace this. It was For this reason, the present invention is, as Bokai agent in place of the tin compounds, silicates, _{e.g., SiO 2, Al 2 O 3} , Fe 2 O 3, Ca
O, MgO, K ₂ O, Na ₂ O ₃ , calcium fluoride,
Mineral powder containing a small amount of radiation mainly consisting of natural aluminum fluoride is mixed with the ship bottom paint, and further silicate, zirconium fluoride, titanium fluoride, fluoride, etc. are used. Using the added one, 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, then the well-known No. 1 ship bottom A mixture of silicate / zirconium fluoride / titanium fluoride, fluoride powder, etc. is applied to the undercoat of the paint, and it is applied to the ship bottom paint of No. 2 with silicate / zirconium fluoride / titanium fluoride, It is a mixture of fluoride powder, etc., a top coating of ship bottom paint is applied, and then the surface is finished, and the top coating is silicate / zirconium fluoride /
Paints containing titanium fluoride, fluoride powder, etc. that have been applied and dried have an extremely high anti-shelling effect, and are the same as when tin compounds are used, so they are effective in reducing marine pollution of tin compounds. The content of the paint on the bottom of the ship is possible. General ship bottom paint is (English ship bottom)
coating Germany Schiffsbonnans
(trich), for steel vessels, to prevent corrosion of the bottom of the vessel and to prevent organisms from adhering to prevent propulsion resistance of the vessel from increasing, on wooden vessels paint to prevent organisms from attaching and harm to beetles and beetles. Say. (1) Steel ship bottom paint
After pre-treating the outer surface of the ship's bottom, first apply a rust preventive paint (called No. 1 ship bottom paint or AC) as a base coat, and an antifouling paint (called No. 2 ship bottom paint or AF) on top of it to prevent biological adhesion. To paint. An example of the procedure is shown in Tables I and II.

The two main types of organisms that actually attach to the bottom of the ship are barnacles and serpula (English serpula).
There are also oysters, mussels, bryozoans, squirts, and so on. These protection methods are usually poisonous substances, and as poisonous substances, mercury compounds such as mercury (II) iodide, mercury (I) and (II) chloride, mercury (II) oxide, mercury (II) arsenate, and mercury soap and Copper compounds such as copper (II) oxide, copper (II) nitrate, copper (I) oxide, copper (II) cyanide, copper arsenite, and copper soap, and organic poisons such as DDT are effective. Recently, mercury compounds are no longer used, copper compounds,
Particularly, copper (I) oxide is most often used. Organic poisons also tend to be used more and more. Antifouling paints contain these poisons. As the color-developing agent used for the No. 1 and No. 2 ship bottom paints, spar varnish resistant to seawater has been used. Recently, vinyl chloride-vinyl acetate copolymers (for example, vinylite VAGH and VYHH) have been recommended. In order to completely prevent corrosion on the ship's bottom, a cathodic protection method using magnesium, zinc or the like as an anode has recently been used in combination. (2) Paint on the bottom of a wooden ship It is common to apply paint containing copper (I) oxide as the main poison twice. In the United States, materials such as skins and keels that come into direct contact with seawater are processed, dried, and then soaked in a copper naphthenate solution (containing 1.5% or more of copper) for 3 to 30 minutes, and dried for use. Commonly known natural silicates, 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. Is separated, and this fluoride is reacted with aluminum to remove iron and other impurities to produce high-purity aluminum fluoride.
Uranium, chrome, vanadium, thorium, lantern,
Contains a rarifying substance such as strontium,
Generally, it is eluted by acid decomposition and purified and separated, but in this method, the natural silicate, natural calcium fluoride, natural aluminum fluoride, etc. are used as they are and the rarification property is utilized. , Is designed to promote the anti-mussel effect,
Further, purified fluoride is also used in combination. In the presence of 4 microcurie to 2,500 microcurie of this ramen, the seawater that interferes with the contact of plankton, which is the bait of the shellfish when mixed in this paint, is also in contact with the seawater. The structuring of the water molecules in it is measured (as measured by magnetic resonance) to condense, the calcium solution is encapsulated, and the fluoride reduces the attachment force of the shell, vibration, and the physical factors of the substance. Thereby exerting the effect of promoting peelability. Therefore, even if it is attached to the bottom paint of the ship, it will starve without allowing the plankton, bacterial bacteria, etc. to approach due to the radiation, thereby suppressing the growth of the shell, thereby exerting a shell-preventing effect, and seaweed. For iron ions that are easily attached, the ship wall surface is plated with a complex salt resin such as copper, tin, chrome, manganese, or vanadium of polyacrylic acid to form a coating film of polyacrylic acid metal and iron ions. Since the solubility is suppressed and the shell-repelling effect of the copper-tin film is exerted, a sufficient paint-like effect can be exerted on ocean voyages. General ship bottom paint is J
There are paints No. 1 and No. 2 which take over the IS standard. Generally, the steel surface on the side wall of the ship is rustproofed and the bottom paint for undercoat is applied. As this ship bottom paint, oily (boil oil type),
Polyester and polyvinyl paints have been standardized. After applying the undercoat ship bottom paint, the top coat ship bottom paint is applied after waiting for drying. After applying several times,
It is common to apply a top coating to the worn surface that contacts the seawater surface. At first, cinnabar powder was used for shellfish and algae protection, but its use was prohibited due to the toxicity of mercury.As a change to this, tin complex salt, which is not less toxic, was mixed with the ship bottom paint. Was being used.
However, this is also used as a bottom paint for fishing boats and large vessels, and the marine pollution is extremely narrow in the Seto Inland Sea where seawater mobility is low, so the concentration of tin complex salts in seawater gradually increases. The sea salt and seaweeds that inhabit the inland sea have gradually become contaminated with tin, and even for humans who eat it, the accumulation of tin in the liver has increased, reaching the limit of the dangerous concentration. However, it has been difficult to develop a substitute component system. Originally, the main purpose of the ship bottom paint is that the hull made of steel is easily corroded by seawater.
It should be protected with a synthetic resin paint. However, when this steel surface is plated with copper or tin, which is resistant to seawater, the corrosion rate of the steel surface decreases to less than 1/10. However, the plating on this large hull is not easy to process, and the wages are expensive. Also, stainless steel and titanium metal do not corrode, but it is generally economical to use ship bottom paint because the material itself is expensive and has a short life and is easy to peel off. It was easy, and it was easy in terms of resources. Therefore, we considered forming a protective film on this steel surface by a metal-to-metal joint with similar expansion and contraction with less peelability, but considered a plating method by electroplating and dipping, In order to make the workability on site more convenient, add a small amount to acrylic acid or organic acid water and dissolve corrosion-resistant metal ions such as copper and tin in a mineral acid solvent to form a complex salt solution. When applying resin with resin or adding resin to a brush, or spraying with a spray, iron on the surface of copper iron is
Immediately replaces copper and tin ions with copper, tin, and plating 1-2
It is carried out in a minute, and a thin metal film or suboxide film is formed, and the steel surface is protected by plating and corrosion resistance is increased by 10 times or more. Therefore, when coating the ship bottom paint on the surface, more corrosion resistance is required. Although increased, the organic acid salt needs to be cleaned as an unnecessary impurity. In particular, the presence of an acid finally promotes corrosion, so that it is preferable to clean it. And after drying well,
If the bottom paint is applied, the peelability will disappear. Even if the copper and tin thus corroded in the bottom paint of the ship, they do not generate a large amount like iron ions on the steel surface, and a small amount of melted metal ions of plankton in the shell. It has the effect of suppressing the generation, is less attached to the hull, and is less toxic like tin complex salts because the amount of dissolved ions is small, so it does not cause excessive marine pollution. Further, since the bondability to the copper or tin surface is also high, the result is that the adhesiveness of the paint is high. Therefore, by adding a silicate, calcium fluoride, aluminum fluoride, etc.
By suppressing the generation of bait of plankton generation and by the property that it is easy to take a planar structure peculiar to fluoride, it is not easy to attach shells and a peelable adhesive structure is formed, so it becomes more peelable by microvibration. It takes advantage of The generally known tin salt kills a large amount of plankton by dissolving the tin salt, so that it stops the feeding of food required for shellfish growth and also produces calcium stannate. Therefore, there is a drawback that crystal drooling due to calcium deposition occurs. Although it was used, it has a relatively high solubility in seawater and is used for many purposes such as seaweed culture fish nets and coating of bamboo poles, so a large amount of tin is washed away in seawater and regulated. Although it is working, there is almost no substitute for it, and it is a long time before it becomes extinct. However, since the use of a more toxic mercury complex salt may cause a Minamata pollution incident, there is still a problem in the use of such as silicate, calcium fluoride, fluoride, etc. In comparison, the toxicity is 20 times less than that of the publicly known toxic tin salt and mercury salt, which is extremely useful. In particular, the rarification property is present in the majority of fluorides in natural products, and at a concentration of 4 to 40 microcuries, it is safe because it does not adversely affect the human body, and the condensation of the molecular structure of water does not occur. Condensed water, that is, 6, 5, 4,
In the member ring, it is not easy for bacterial bacteria to reproduce, and in the low molecular structure of 4 member rings or less, it exerts an effect of promoting the reproduction, so it is useful for reducing the prey of shellfish and plankton. is there. The essential points of the present invention will be described below with reference to the drawings. In Figure (1), J
Introducing IS standard undercoat paint from tanks (5) and (4) into tank (1) and agitating in agitator (2), and then introducing fluoride powder from hopper (3) and agitating Is stored in a tank (7), poured into a paint can (9) on a tongue table (8), and the canned product is conveyed by a belt conveyor (10) to a packaging device (11). Make a base coat by hermetically packing. Similarly, the top-coat paint is introduced into the tank (1 ') into the top-coat paint solution (5') (4 '), fluoride powder or the like is introduced from the hopper (3'), and stirred with a stirrer (2 '). The tank (7 ') is introduced and stored. Then, the mixed solution is filled in the paint can (9 ') on the turntable (8'), is loaded and conveyed on the belt conveyor (10), and is hermetically sealed at (11). The copper polyacrylate is mixed from the hoppers (13), (14) and (15) at a ratio of 1 part of water to 1 part of acrylic acid, copper chloride,
0.1 part and 0.03 part of peroxide are dispersed in water and added,
The ratio is 2 parts of water. This is put in a tank (12) and stirred by a stirrer (16), and hot water is put from a hot water tank (17) and reacted while heating at 50 ° C to 120 ° C, and a cooling tank (18) While adjusting the temperature with
The reaction is completed in about 1 hour. In order to promote this reaction, a little aluminum or iron scrap is added to accelerate the reaction, but copper precipitates are formed, so a pump (19) separates it with a filter (20) to make an undercoat copper paint, a tank. The copper precipitate at the bottom of (12) is collected with the precipitate in the filter (20),
Reuse as copper chloride. Fig. 3 shows a side view of the hull. The hull steel (1a) surface is coated with copper-tin plating, the undercoat paint (3a) is applied on the surface, and the topcoat paint (4
Apply a) and the water-washing paint (5a). The composition of this copper undercoating liquid is as follows.

Example (1) Polyacrylic acid 30 parts Copper chloride or copper acrylate or tin 8.5 parts Water 60 parts Catalyst and others 1.5 parts Example (2) Undercoat bottom paint 80 parts Silicate or calcium fluoride Aluminum fluoride Mineral stone powder 18 parts Other 2 parts Example (3) Topcoat paint 80 parts Silicate, calcium fluoride, aluminum fluoride, ganja powder 18 parts Zirconium oxide or titanium oxide Other mineral stone powder 2 parts Example (4) Topcoat paint 80 parts Acrylic Acid or polyvinyl acetal Resin mixed resin or ethyl acrylic acid 30 parts Vanadium sulphate or manganese sulphate or titanium sulphate, zirconium chlorite stone powder 2 parts Fluoride fluorite such as silicate, calcium fluoride aluminum fluoride 7 parts Other 1 part 60 parts of water Figure 2 shows the degree of adhesion of shells. After copper coating, undercoating, and further overcoating, and immersing in seawater for 6 months, (A) is an iron plate only (B) is a known tin compound mixed at 5% thing
(C) contains the fluoride of the present application. (D) shows an iron plate previously coated with a copper methyl acrylate solution on a copper plate, and then coated with an undercoat top coat. (E) is 1
The thing which gave 30 cycles of vibration for a minute. From the above results, there is almost no difference from the one containing the known tin compound, but the copper-coated one has a result that the attachment of the shell is less. This shows that the plankton is reduced by the elution of copper ions and that the elution of iron ions is small. Further, even after 6 months, the peeling property of the seashell is strong in the fluoride lachtion product. Thus, the feature of the present invention is to reduce the pollution of the tin complex salt of the known ship bottom paint, in order to further enhance it by copper coating by substituting the fluoride with a low radiation property. Fluoride reduces the marine pollution concentration of tin, which is increasing year by year, and thus reduces tin pollution. And, due to the rarative property of fluoride, etc., it condenses water molecules, suppresses the growth of bacteria and microbiota that feed plankton, and physically exfoliates against the attachment of shells. Is promoted by fluoride, and is also used for fishnets and bamboo poles, and has a wide range of uses as a fungicide,
It is an industrially useful invention.

[Brief description of drawings]

 Fig. 1 is a process diagram for the production of top and bottom coatings. Fig. 2 is its characteristic of preventing shell attachment. Fig. 3 is a side view of the hull.

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[Procedure amendment]

[Submission date] December 24, 1993

[Procedure Amendment 1]

[Document name to be amended] Statement

[Name of item to be amended] Claims

[Correction method] Change

[Correction content]

[Claims]

[Procedure Amendment 2]

[Document name to be amended] Statement

[Name of item to be amended] Detailed explanation of the invention

[Correction method] Change

[Correction content]

DETAILED DESCRIPTION OF THE INVENTION In the present invention, a tin compound such as dibutyryl tin or ethiyl / methyl / hydrohalide is mixed in a ship bottom paint and used as an anti-shell shell for a fish net. This tin compound causes pollution of seawater, contaminates fish and shellfish and seaweed, and accumulates in the liver of the human body that eats it.
I reached pm. Therefore, in order to prevent this marine pollution, there is no other way than prohibiting the use of this tin compound that has a shell-repelling effect, and the usage regulations have been met, but there is no good harmless shell-repellent agent to replace this. It was For this reason, the present invention is, as Bokai agent in place of the tin compounds, silicates, _{e.g., SiO 2, Al 2 O 3} , Fe 2 O 3, Ca
O, MgO, K ₂ O, Na ₂ O ₃ , calcium fluoride,
Mineral powder containing a small amount of radiation mainly consisting of natural aluminum fluoride is mixed with the ship bottom paint, and further silicate, zirconium fluoride, titanium fluoride, fluoride, etc. are used. Using the added one, 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, then the well-known No. 1 ship bottom A mixture of silicate / zirconium fluoride / titanium fluoride, fluoride powder, etc. is applied to the undercoat of the paint, and it is applied to the ship bottom paint of No. 2 with silicate / zirconium fluoride / titanium fluoride, It is a mixture of fluoride powder, etc., a top coating of ship bottom paint is applied, and then the surface is finished, and the top coating is silicate / zirconium fluoride /
Paints containing titanium fluoride, fluoride powder, etc. that have been applied and dried have an extremely high anti-shelling effect, and are the same as when tin compounds are used, so they are effective in reducing marine pollution of tin compounds. The content of the paint on the bottom of the ship is possible. General ship bottom paint is (English ship bottom)
coating Germany Schiffsbonnans
(trich), for steel vessels, to prevent corrosion of the bottom of the vessel and to prevent organisms from adhering to prevent propulsion resistance of the vessel from increasing, on wooden vessels paint to prevent organisms from attaching and harm to beetles and beetles. Say. (1) Steel ship bottom paint
After pre-treating the outer surface of the ship's bottom, first apply a rust preventive paint (called No. 1 ship bottom paint or AC) as a base coat, and an antifouling paint (called No. 2 ship bottom paint or AF) on top of it to prevent biological adhesion. To paint. An example of the procedure is shown in Tables I and II. There are two main types of organisms that actually attach to the bottom of the ship and are problematic: barnacles and serpula (English serpula), as well as oysters, mussels, bryozoans and ascidians. These prevention methods are generally based on poisonous substances, such as mercury (II) iodide, mercury (I) and (II) chloride, mercury (II) oxide, mercury (II) arsenate, mercury compounds such as mercury soap and oxidation. Copper compounds such as copper (II), copper (II) nitrate, copper (I) oxide, copper (II) cyanide, copper arsenite and copper soap, and organic poisons such as DDT are effective. Recently, mercury compounds are no longer used, copper compounds,
Particularly, copper (I) oxide is most often used. Organic poisons also tend to be used more and more. Antifouling paints contain these poisons. As the color-developing agent used for the No. 1 and No. 2 ship bottom paints, spar varnish resistant to seawater has been used. Recently, vinyl chloride-vinyl acetate copolymers (for example, vinylite VAGH and VYHH) have been recommended. In order to completely prevent corrosion on the ship's bottom, a cathodic protection method using magnesium, zinc or the like as an anode has recently been used in combination. (2) Paint on the bottom of a wooden ship It is common to apply paint containing copper (I) oxide as the main poison twice. In the United States, materials such as skins and keels that come into direct contact with seawater are processed, dried, and then soaked in a copper naphthenate solution (containing 1.5% or more of copper) for 3 to 30 minutes, and dried for use. Commonly known natural silicates, 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. Is separated, and this fluoride is reacted with aluminum to remove iron and other impurities to produce high-purity aluminum fluoride.
Uranium, chrome, vanadium, thorium, lantern,
Contains a rarifying substance such as strontium,
Generally, it is eluted by acid decomposition and purified and separated, but in this method, the natural silicate, natural calcium fluoride, natural aluminum fluoride, etc. are used as they are and the rarification property is utilized. , Is designed to promote the anti-mussel effect,
Further, purified fluoride is also used in combination. In the presence of 4 microcurie to 2,500 microcurie of this ramen, the seawater that interferes with the contact of plankton, which is the bait of the shellfish when mixed in this paint, is also in contact with the seawater. It measures the structuring of the water molecules in it, condenses it (measured by magnetic resonance), entraps the calcium solution, and fluoride diminishes the attachment force of the shell, causing vibrations and physical factors of the substance. Thereby exerting the effect of promoting peelability. Therefore, even if it is attached to the bottom paint of the ship, it will starve without allowing the plankton, bacterial bacteria, etc. to approach due to the radiation, thereby suppressing the growth of the shell, thereby exerting a shell-preventing effect, and seaweeds. For iron ions that are easily attached, the ship wall surface is plated with a complex salt resin such as copper, tin, chrome, manganese, or vanadium of polyacrylic acid to form a coating film of polyacrylic acid metal and iron ions. Since the solubility is suppressed and the shell-repelling effect of the copper-tin film is exerted, a sufficient paint-like effect can be exerted on ocean voyages. General ship bottom paint is J
There are paints No. 1 and No. 2 which take over the IS standard. Generally, the steel surface on the side wall of the ship is rustproofed and the bottom paint for undercoating is applied. As this ship bottom paint, oily (boil oil type),
Polyester and polyvinyl thread paints have been standardized. After applying the undercoat ship bottom paint, the top coat ship bottom paint is applied after waiting for drying. After applying several times,
It is common to apply a top coating to the worn surface that contacts the seawater surface. At first, cinnabar powder was used for shellfish and algae protection, but its use was prohibited due to the toxicity of mercury.As a change to this, tin complex salt, which is not less toxic, was mixed with the ship bottom paint. Was being used.
However, this is also used as a bottom paint for fishing boats and large ships, and the sea water is less mobile in the Seto Inland Sea where ocean pollution is particularly narrow. The sea salt and seaweeds that inhabit the inland sea have gradually become contaminated with tin, and even for humans who eat it, the accumulation of tin in the liver has increased, reaching the limit of the dangerous concentration. However, it has been difficult to develop a substitute component system. Originally, the main purpose of the ship bottom paint is that the hull made of steel is easily corroded by seawater.
It should be protected with a synthetic resin paint. However, when this steel surface is plated with copper or tin, which is resistant to seawater, the corrosion rate of the steel surface decreases to less than 1/10. However, the plating on this large hull is not easy to process, and the wages are expensive. Also, stainless steel and titanium metal do not corrode, but it is generally economical to use ship bottom paint because the material itself is expensive and has a short life and is easy to peel off. It was easy, and it was easy in terms of resources. Therefore, we considered forming a protective film on this steel surface by a metal-to-metal joint with similar expansion and contraction with less peelability, but considered a plating method by electroplating and dipping, In order to make the workability on site more convenient, add a small amount to acrylic acid or organic acid water and dissolve corrosion-resistant metal ions such as copper and tin in a mineral acid solvent to form a complex salt solution. When applying resin with resin or adding resin to a brush, or spraying with a spray, iron on the surface of copper iron is
Immediately replaces copper and tin ions with copper, tin, and plating 1-2
It is carried out in a minute, and a thin metal film or suboxide film is formed, and the steel surface is protected by plating and corrosion resistance is increased by 10 times or more. Therefore, when coating the ship bottom paint on the surface, more corrosion resistance is required. Although increased, the organic acid salt needs to be cleaned as an unnecessary impurity. In particular, the presence of an acid finally promotes corrosion, so that it is preferable to clean it. And after drying well,
If the bottom paint is applied, the peelability will disappear. Even if the copper and tin thus corroded in the bottom paint of the ship, they do not generate a large amount like iron ions on the steel surface, and a small amount of melted metal ions of plankton in the shell. It has the effect of suppressing the generation, is less attached to the hull, and is less toxic like tin complex salts because the amount of dissolved ions is small, so it does not cause excessive marine pollution. Further, since the bondability to the copper or tin surface is also high, the result is that the adhesiveness of the paint is high. Therefore, by adding a silicate, calcium fluoride, aluminum fluoride, etc.
By suppressing the generation of bait of plankton generation and by the property that it is easy to take a planar structure peculiar to fluoride, it is not easy to attach shells and a peelable adhesive structure is formed, so it becomes more peelable by microvibration. It takes advantage of The generally known tin salt kills a large amount of plankton by dissolving the tin salt, so that it stops the feeding of food required for shellfish growth and also produces calcium stannate. Therefore, there is a drawback that crystal drooling due to calcium deposition occurs. Although it was used, it has a relatively high solubility in seawater and is used for many purposes such as seaweed culture fish nets and coating of bamboo poles, so a large amount of tin is washed away in seawater and regulated. Although it is working, there is almost no substitute for it, and it is a long time before it becomes extinct. However, since the use of a more toxic mercury complex salt may cause a Minamata pollution incident, there is still a problem in the use of such as silicate, calcium fluoride, fluoride, etc. In comparison, the toxicity is 20 times less than that of the publicly known toxic tin salt and mercury salt, which is extremely useful. In particular, the rarification property is present in the majority of fluorides in natural products, and at a concentration of 4 to 40 microcuries, it is safe because it does not adversely affect the human body, and the condensation of the molecular structure of water does not occur. Condensed water, that is, 6, 5, 4,
In the member ring, it is not easy for bacterial bacteria to reproduce, and in the low molecular structure of 4 member rings or less, it exerts an effect of promoting the reproduction, so it is useful for reducing the prey of shellfish and plankton. is there. The essential points of the present invention will be described below with reference to the drawings. In Figure (1), J
Introducing IS standard undercoat paint from tanks (5) and (4) into tank (1) and agitating in agitator (2), and then introducing fluoride powder from hopper (3) and agitating Is stored in a tank (7), poured into a paint can (9) on a tongue table (8), and the canned product is conveyed by a belt conveyor (10) to a packaging device (11). Make a base coat by hermetically packing. Similarly, the top-coat paint is introduced into the tank (1 ') into the top-coat paint solution (5') (4 '), fluoride powder or the like is introduced from the hopper (3'), and stirred with a stirrer (2 '). The tank (7 ') is introduced and stored. Then, the mixed solution is filled in the paint can (9 ') on the turntable (8'), is loaded and conveyed on the belt conveyor (10), and is hermetically sealed at (11). The copper polyacrylate is mixed from the hoppers (13), (14) and (15) at a ratio of 1 part of water to 1 part of acrylic acid, copper chloride,
0.1 part and 0.03 part of peroxide are dispersed in water and added,
The ratio is 2 parts of water. This is put in a tank (12) and stirred by a stirrer (16), and hot water is put from a hot water tank (17) and reacted while heating at 50 ° C to 120 ° C, and a cooling tank (18) While adjusting the temperature with
The reaction is completed in about 1 hour. In order to promote this reaction, a little aluminum or iron scrap is added to accelerate the reaction, but copper precipitates are formed, so a pump (19) separates it with a filter (20) to make an undercoat copper paint, a tank. The copper precipitate at the bottom of (12) is collected with the precipitate in the filter (20),
Reuse as copper chloride. Fig. 3 shows a side view of the hull. The hull steel (1a) surface is coated with copper-tin plating, the undercoat paint (3a) is applied on the surface, and the topcoat paint (4
Apply a) and the water-washing paint (5a). The composition of this copper undercoating liquid is as follows. Example (1) Polyacrylic acid 30 parts Copper chloride or copper acrylate or tin 8.5 parts Water 60 parts Catalyst and others 1.5 parts Example (2) Undercoat bottom paint 80 parts Silicate or calcium fluoride Aluminum fluoride Mineral stone powder 18 parts Other 2 parts Example (3) Topcoat paint 80 parts Silicate, calcium fluoride, aluminum fluoride, ganja powder 18 parts Zirconium oxide or titanium oxide Other mineral stone powder 2 parts Example (4) Topcoat paint 80 parts Acrylic Acid or polyvinyl acetal Resin mixed resin or ethyl acrylic acid 30 parts Vanadium sulphate or manganese sulphate or titanium sulphate, zirconium chlorite stone powder 2 parts Fluoride fluorite such as silicate, calcium fluoride aluminum fluoride 7 parts Other 1 part 60 parts of water Figure 2 shows the degree of adhesion of shells. After copper coating, undercoating, and further overcoating, and immersing in seawater for 6 months, (A) is an iron plate only (B) is a known tin compound mixed at 5% thing
(C) contains the fluoride of the present application. (D) shows an iron plate previously coated with a copper methyl acrylate solution on a copper plate, and then coated with an undercoat top coat. (E) is 1
The thing which gave 30 cycles of vibration for a minute. From the above results, there is almost no difference from the one containing the known tin compound, but the copper-coated one has a result that the attachment of the shell is less. This shows that the plankton is reduced by the elution of copper ions and that the elution of iron ions is small. In addition, even after 6 months, the release of the shell is strong with the fluoride radiation. Thus, the feature of the present invention is to reduce the pollution of the tin complex salt of the known ship bottom paint, in order to further enhance it by copper coating by substituting the fluoride with a low radiation property. Fluoride reduces the marine pollution concentration of tin, which is increasing year by year, and thus reduces tin pollution. And, due to the rarative property of fluoride, etc., it condenses water molecules, suppresses the growth of bacteria and microbiota that feed plankton, and physically exfoliates against the attachment of shells. Is promoted by fluoride, and is also used for fishnets and bamboo poles, and has a wide range of uses as a fungicide,
It is an industrially useful invention.

Claims (1)

[Claims] As will be described later, with copper tin polyacrylate, as described below, the surface of the ship wall is coated to form a plating film of copper tin polyacrylate, a low-radiation silicate, a fluoride, zirconium, A bottom paint that is obtained by applying an undercoat paint and a topcoat paint mixed with titanium oxide powder, and then applying a topcoat paint containing silicate, fluoride, zirconium, and titanium oxide powder that protects the water line.