JPH02117606A - Aquatic living body growth-inhibiting agent and aquatic living body attachment preventing composotion - Google Patents

Abstract

PURPOSE:To provide the subject agent comprising noble metal-activated copper prepared by integrally attaching a noble metal on the particle surface of copper powder in such a state as the particle surface of the copper powder is partially exposed or comprising a modified product thereof prepared by further attaching a basic organic dibasic acid copper salt or basic copper carbonate salt to the surface of the noble metal-activated copper. CONSTITUTION:The subject inhibiting agent contains as an active ingredient a noble metal-activated copper prepared by integrally attaching a noble metal (e.g., silver, gold or platinum) to the particle surface of metal copper powder in an amount of <=0.4 pt.wt. (preferably 0.35-0.3X10<-3> pt.wt.) per 100 pts.wt. of the metal copper in such a state as the particle surface is partially exposed or a noble metal-activated copper modified product prepared by integrally attaching a basic organic dibasic acid copper salt (e.g., adipic acid copper salt) or basic copper carbonate salt to the surface of the noble metal-activated copper. The subject composition comprises the noble metal-activated copper or the modified product thereof and a binder (e.g., a coating vehicle or polymer cement covering agent) for keeping the agent in a dispersion state. The agent contains readily ionized copper, is stable for a long period without changing the properties thereof and does not pollute environments.

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Field of Application] The present invention relates to an aquatic organism growth inhibitor and an aquatic organism adhesion prevention composition.

More specifically, the present invention relates to an aquatic organism growth inhibitor and an aquatic organism adhesion prevention composition containing activated copper and its modified product as active ingredients.

[Background of the invention] The purpose of this invention is to prevent various aquatic plants and animals, such as barnacles, oysters, scale insects, and seaweed, from adhering to and growing on the surfaces of steel or concrete objects that are used in contact with seawater. Antifouling agents such as ship bottom paints are used as antifouling agents. Conventionally, the active ingredients of such antifouling agents include;
Organic tin compounds such as tributyltin oxide (TBTO), cuprous oxide, and cuprous oxide containing a small amount of mercury oxide are known. Metals such as tin and mercury, which are the active ingredients mentioned above, have strong toxicity to aquatic animals and plants, and can prevent aquatic animals and plants from adhering to them and inhibit their growth. There is a risk of contaminating the environment. In addition, cuprous oxide (Cu
20) is oxidized by dissolved oxygen in water and becomes copper oxide (Cub) with low solubility, so cuprous oxide, which is effective, only makes up a portion of the total amount used, and is effective in preventing aquatic animals and plants from adhering. The problem is that the period is short.

The present inventor has conducted extensive research on antifouling methods to solve the above problems, and has already applied portland cement or blast furnace cement alone or a mixture of such cement and fine aggregate to the surfaces of steel or concrete objects that come into contact with seawater. After applying and curing a polymer cement coating agent made by blending an aqueous polymer emulsion with a water-based polymer emulsion, a mixture of copper sulfide or metallic copper powder and the polymer cement coating agent is applied to the coated surface. Developing antifouling methods for steel or concrete objects that come into contact with seawater. The above-mentioned antifouling method has been patented by the present applicant and has already been patented (Japanese Patent No. 1386697, Japanese Patent Publication No. 61
-45513, Japanese Patent No. 1401183, and Japanese Patent Publication No. 62-6863).

It is known that copper sulfide or metallic copper is effective in preventing the adhesion of aquatic animals and plants, but when copper adheres to the steel surface, it forms local batteries and severely corrodes the steel, so it is not recommended as a ship bottom paint. was considered virtually impossible to use. The antifouling method described above physically blocks copper sulfide or metallic copper from coming into contact with the steel surface by applying a polymer cement coating agent, and also prevents copper sulfide produced by oxidation of copper sulfide or copper produced from metallic steel. Ions are captured by alkaline calcium to form Cu5O, xCu (OH)
Since it has the effect of forming a stable double salt such as 2.yCa (OH) 2.2H20, the above-mentioned copper sulfide or metallic copper can be advantageously used as an anti-adhesion composition for aquatic animals and plants without corroding the steel surface. can do.

The above-mentioned method uses copper sulfide or metallic copper powder instead of cuprous oxide as the active ingredient of the aquatic animal and plant growth inhibitor, and provides antifouling effects for a longer period of time compared to cuprous oxide. It will be done.

The above-mentioned antifouling method involves applying a polymer cement coating agent to the surface that comes into contact with seawater and curing it, and then applying a mixture of copper sulfide or metallic copper powder and the polymer cement coating agent to the coated surface. The soiling method provides effective soil protection for a considerable period of time.

However, in the above-mentioned method, since the active ingredient of the aquatic animal and plant growth inhibitor is encapsulated in the polymer cement matrix, the ability to inhibit the growth of aquatic animals and plants is not as strong as that of conventional aquatic animal and plant growth inhibitors containing organotin compounds such as TBTO. This method tends to be inferior to other methods of applying antifouling agents.

Therefore, it is desired to develop a +h agent for the growth of aquatic animals and plants that is less toxic to the environment, has a stable and effective long-term anti-adhesion effect on aquatic animals and plants, and is stronger.

In addition, in recent years, garbage, fish iliac bones, etc. have been flushed away with wastewater. The above-mentioned food waste, fish iliac bones, etc., are prone to adhesion and growth of aquatic bacteria, and there are problems such as bad odors due to decomposition and generation of pathogens.

[Object of the invention] The present invention provides a growth inhibitor for aquatic organisms such as aquatic animals and plants and aquatic bacteria, and a stable and resistant aquatic organism adhesion prevention composition that can prevent the above-mentioned organisms from adhering over a long period of time. The purpose is to provide something.

[Summary of the Invention] The present invention provides that 0.4 parts by weight or less of a noble metal is integrally formed on the particle surface of a metallic copper powder with at least a part of the particle surface exposed, based on 100 parts by weight of the metallic copper. An aquatic organism growth inhibitor characterized by having as an active ingredient noble metal activated copper adhered to a metal, and a basic organic dibasic acid copper or basic copper carbonate integrally formed on the surface of the noble metal activated copper. The present invention provides an aquatic organism growth inhibitor characterized by containing as an active ingredient a noble metal-activated denatured copper adhering to aquatic organisms.

The present invention also resides in an aquatic organism growth inhibitor composition comprising the above-mentioned noble metal-activated copper or its modified product and a binder that holds the copper in a dispersed state.

Preferred embodiments of the present invention are as follows.

(1) The above noble metal activated copper is present on the particle surface at 0.35 to 3xto-' based on 100 parts by weight of the metallic copper powder.
Must be noble metal activated copper with a weight part of noble metal attached.

(2) The above-mentioned noble metal is at least one noble metal selected from the group consisting of Au, Pt, and Ag.

(3) The organic dibasic acid is adipic acid.

(4) The binder is a paint vehicle.

(5) The binder is a polymer cement coating agent.

[Detailed Description of the Invention] The aquatic organism growth inhibitor of the present invention is characterized in that at least part of the particle surface of the metallic copper powder contains 0.4 parts by weight or less of a noble metal based on 100 parts by weight of the metallic copper. It is characterized by containing noble metal activated copper as an active ingredient, which is integrally adhered with exposed parts.

The following reasons can be considered as reasons why the noble metal-activated copper of the present invention is extremely effective as an aquatic organism growth inhibitor.

Generally, when metallic copper is placed in water, it is thought that the ionization of metallic copper and the production reaction of copper compounds occur competitively. Since the growth of aquatic organisms is inhibited in areas with high copper ion concentrations, metallic copper must be used as a growth inhibitor for aquatic organisms. preferable.

The noble metal-activated copper of the present invention forms a local battery in water or seawater because the noble metal, which has a smaller ionization tendency than copper, is in contact with the surface of the metal steel.

For this reason, the noble metal-activated copper tends to generate ions, and the concentration of copper ions becomes high in water or seawater near the noble metal-activated copper, thereby hindering the growth of aquatic organisms.

The above-mentioned noble metal activated copper can be produced by treating metallic copper powder with an aqueous solution of a noble metal salt.

The above-mentioned noble metal is preferably at least one kind of noble metal selected from the group consisting of silver, gold, and platinum, and examples of water-soluble salts of the above-mentioned noble metal include silver nitrate, chloroauric acid, and chloroplatinic acid. be able to.

The amount of the above water-soluble noble metal salt used is metal'j! 4100 parts by weight, it is necessary that the amount of precious metal is 0.4 parts by weight or less, and 0.35 to 0.3 x 1o-31,54
It is preferable that it is in the range of The amount of water used when making the water-soluble noble metal salt into an aqueous solution is sufficient as long as it can dissolve the noble metal salt and keep the metallic copper powder in a wet state, and there is no need to use an excessive amount of water.

The amount of water is usually 20 parts by weight per 100 parts by weight of metallic copper.
-80 parts by weight, preferably 25-75 parts by weight.

The noble metal activated copper is obtained as a black-gray powder by adding metallic copper powder to the aqueous solution of the noble metal salt described above, stirring the mixture several times at regular intervals, and then leaving it to stand. The above operation can be carried out, for example, by adding metal copper powder to a noble metal salt aqueous solution, stirring it thoroughly, and then stirring it for 1 to 2 minutes.
It is preferable to repeat the operation of stirring for about 2 to 10 minutes every hour 5 to 7 times, and then leave it for 10 to 20 hours.

Another aquatic organism growth inhibitor of the present invention is applied to the particle surface of metallic copper powder in an amount of 0.4% per 100 parts by weight of metallic copper.
Parts by weight or less of a noble metal is made of noble metal-activated copper attached with at least a part of the surface of the particle exposed,
In addition, it is characterized in that the active ingredient is a noble metal-activated copper modified product to which basic organic dibasic acid copper or basic copper carbonate is integrally adhered.

The above-mentioned modified product is a patina-like substance in which basic organic dibasic copper dibasic acid or basic copper carbonate is integrally attached to its surface, but like the above-mentioned noble metal activated copper, due to the action of the noble metal, copper ions It has the property of being prone to occur. Furthermore, the above-mentioned modified substance has extremely low toxicity to aquatic animals and plants compared to copper oxide or cuprous oxide, and is superior in environmental safety. The present applicant has already filed a patent application for
(Refer to Publication No.-124154). The noble metal-activated copper modified product of the present invention is produced by applying the production method described in the above-mentioned publication, and adding noble metal-activated copper to a wet state in the presence of an organic dibasic acid that is solid at room temperature and a volatile organic acid. It can be advantageously produced by contacting with a carbon dioxide-containing gas.

Examples of the organic dibasic acids include maleic acid, fumaric acid, malonic acid, succinic acid, glutaric acid, adipic acid, phthalic acid, and anhydrides thereof, with adipic acid being particularly preferred. The amount of the organic dibasic acid used is 10 to 2 parts by weight per 100 parts by weight of noble metal activated copper.
Preferably, the amount is in the range of 0.00 parts.

The volatile organic acid acts as a reaction initiator and also serves to keep the raw materials, noble metal activated copper and solid organic dibasic acid, in a wet state.

As the above-mentioned volatile organic acid, lower aliphatic monocarboxylic acids, especially acetic acid, can be preferably used, and noble metal activated copper 1
It is preferable to use an aqueous solution of 4 to 20 parts by weight per 00 parts by weight, and 20 to 300 parts by weight per 100 parts by weight of noble metal activated copper. The volatile organic acid is volatilized due to heat generated during the reaction.

The noble metal-activated copper modified product is produced by adding the above-mentioned volatile organic acid aqueous solution to a mixture of noble metal-activated copper and the above-mentioned solid organic dibasic acid, and stirring the mixture at regular intervals to bring the mixture into contact with carbon dioxide in the atmosphere. By repeating this procedure several times and then allowing it to stand, a greenish-blue powder is obtained. The above operation is
For example, immediately after adding the above-mentioned volatile organic acid aqueous solution to a mixture of noble metal activated copper and the above-mentioned solid organic dibasic acid, the above-mentioned volatile organic acid aqueous solution is sufficiently stirred, and then stirring is performed for about 5-20 minutes every 1-2 hours. It is preferable to repeat this 5 to 7 times and then leave it for 20 to 50 hours.

The composition for preventing the adhesion of aquatic organisms of the present invention is characterized by comprising the above-mentioned noble metal-activated copper or its modified product, and a binder that holds the copper in a dispersed state.

The above-mentioned noble metal-activated copper or modified form thereof has a greater tendency to ionize than patina-like substances made from metallic copper or metallic steel, so it can be used as a composition encapsulated in a binder matrix. It is also possible to effectively prevent the adhesion of aquatic organisms. A paint vehicle or a polymer cement can preferably be used as the binder.

In particular, the above-mentioned noble metal activated copper or its modified product is obtained by applying the antifouling method of the above-mentioned Patent No. 1386697 or Patent No. 1401183 and a mixture of an aquatic organism growth inhibitor and a polymer cement coating agent. A technology that improves the effect of preventing aquatic organisms from attaching by embedding a conductive wire in the antifouling coating layer and passing a weak current through it.
It can be advantageously used as a composition formed by dispersing and blending it into a polymer cement coating agent.

Regarding the latter technique mentioned above, a patent application has been filed by the present applicant for a method of using a patina-like substance obtained from metallic copper as described in JP-A-62-124154 as an aquatic organism growth inhibitor. (Refer to the specification of Application No. 138289/1989).

In the above-mentioned technique of passing a weak current through the conductive wire embedded in the antifouling coating layer, the noble metal-activated modified copper is
Furthermore, on the surface, Fe, Ni, Co, Mn%AIL%
It is preferable that at least one base metal selected from the group consisting of Zn and Ca is integrally attached. The noble metal-activated copper modified product to which the above-mentioned base metal is attached is prepared by adding the above-mentioned base metal to an organic dibasic acid that is solid at room temperature and a volatile organic acid in the above-mentioned manufacturing method of the noble metal-activated copper modified product. It can be obtained by coexisting acetate or hydroxide.

[Effects of the Invention] The aquatic organism growth inhibitor obtained by the present invention contains as an active ingredient precious metal-activated copper in which the precious metal is attached to the surface of copper particles. Since copper is easily ionized by forming a local battery and does not easily react with oxygen and carbon dioxide, it can effectively inhibit the growth of aquatic organisms.

In addition, the modified product obtained by treating the above noble metal activated copper with an organic dibasic acid has the property of easily generating copper ions like the above noble metal activated copper, and is also stable over a long period of time and is resistant to deterioration. . In addition, the above-mentioned modified product has lower toxicity to aquatic organisms than copper oxide and copper oxide, so
There is no risk of polluting the environment.

Therefore, the above-mentioned noble metal-activated copper or its modified product can be advantageously used as a component of an aquatic organism antifouling composition.

Furthermore, in the technology of passing a weak current through a conductive wire embedded in an antifouling coating layer, the above-mentioned noble metal-activated modified copper having a specific base metal attached to the surface of the antifouling coating layer; By using a composition comprising a binder and a binder in which it is maintained in a dispersed state, garbage, fish iliac bones, etc. can be sterilized advantageously.

Next, examples of the present invention will be shown.

[Example 1] 100 mg of 9 Jl of nitric acid was placed in a plastic container, 25 cc of tap water was added thereto, and the mixture was thoroughly stirred and dissolved.

Next, electrolytic copper powder (manufactured by Mitsui Mining & Co., Ltd., MD) was placed in the container.
-1) 100 g of the copper powder was poured into the solution and thoroughly mixed using a stainless steel spoon so that the copper powder was evenly moistened. The reddish color of the copper powder gradually changed to blackish gray in about 30 minutes. Furthermore, about 20% of the above mixture is added every hour.
After repeating the stirring operation for 6 minutes, it was left to stand for 10 hours, and silver-activated copper (copper 100
(in which 63 mg of silver was attached with part of the copper exposed) was obtained.

200 mg of silver-activated copper produced above, in which 100 g of copper was activated with 63 mg of silver, was kneaded with 200 mg of alkyd paint vehicle (Alkyd 365-70 manufactured by Hitachi Chemical) to obtain an aquatic organism growth-preventing composition. .

A copper ion elution test was conducted using the above composition according to the test method described below. The results are shown in Table 1.

[Example 2] A black-gray powder of silver-activated copper (315 mg of silver attached to 100 g with a part of the copper exposed) was obtained in the same manner as in Example 1 except that 500 mg of silver nitrate was used. Ta. The color of the silver-activated copper was slightly darker or stronger than that of the silver-activated copper obtained in Example 1.

[Example 3] A chloroauric acid aqueous solution was prepared by adding pure water to chloroauric acid (HA u CI14.4 H20; manufactured by Yojima Chemical Co., Ltd., reagent special grade) Ig to make 300 cc. This will be referred to as aqueous solution A.

In the same manner as in Example 1, except that 30 cc of the above aqueous solution A (containing 100 mg of chloroauric acid) was used instead of silver nitrate in Example 1, powdered fully activated copper (47 mg of gold was added to 100 g of copper as part of the copper) was used. was attached in an exposed state).

200 mg of total activated copper prepared above, in which 100 g of copper was activated with 47 mg of gold, was kneaded with 200 mg of the same alkyd paint vehicle used in Example 1 to obtain an aquatic growth inhibiting composition.

A copper ion elution test was conducted using the above composition according to the test method described below. The results are shown in Table 1.

[Example 4] A portion of the aqueous solution A used in Example 3 was diluted 10 times with pure water to prepare an aqueous solution B.

Instead of 30 cc of aqueous solution A in Example 3, the above ice-water solution 8
A fully activated copper powder was prepared in the same manner as in Example 3, except that 6 cc (containing 2 mg of chloroauric acid) was used (0.94 mg of gold was attached to 100 g of copper with part of the copper exposed). ) was obtained.

[Example 5] Instead of 30 cc of aqueous solution A in Example 3, the above ice aqueous solution 8
A fully activated copper powder was prepared in the same manner as in Example 3, except that 3 cc (containing 1 mg of chloroauric acid) was used (0.47 mg of gold was attached to 100 g of copper with part of the copper exposed). ) was obtained.

The colors of all activated copper obtained in Examples 3 to 5 are as follows:
It had a reddish black-gray color that was thinner than that of silver-activated copper, and the higher the amount of chloroauric acid used, the stronger the blackness was.

[Example 6] Pure water was added to chloroplatinic acid (H2ptcI1g-6H20; manufactured by Wako Pure Chemical Industries, Ltd., special grade reagent) Ig to make 300 cc to prepare a chloroplatinic acid aqueous solution.

This will be referred to as aqueous solution C.

Powdered platinum-activated copper (100 g of copper to 37 g of platinum was used in the same manner as in Example 1, except that 30 cc of the above aqueous solution C (containing 100 mg of chloroplatinic acid) was used instead of silver nitrate in Example 1.
(mg was attached with part of the copper exposed) was obtained.

200 mg of platinum-activated copper prepared above, in which 00 g of copper i was activated with 37 mg of platinum, were kneaded with 200 mg of the same alkyd paint vehicle used in Example 1.
An aquatic organism growth-preventing composition was obtained.

A copper ion elution test was conducted using the above composition according to the test method described below. The results are shown in Table 1.

[Example 7] A portion of the aqueous solution C used in Example 6 was diluted 10 times with pure water to prepare an aqueous solution.

Instead of 30 cc of the aqueous solution C in Example 6, the above ice-water solution D
Powdered platinum-activated copper (copper i 00
0.74 rng of platinum was attached to the copper plate with part of the copper exposed).

[Example 8] Instead of 30 cc of the aqueous solution C in Example 6, the above ice aqueous solution D
Powdered platinum activated 'iA (copper 10
(0.37 mg of platinum was attached to 0.0 g of copper with part of the copper exposed) was obtained.

The color of the platinum-activated copper obtained in Examples 6 to 8 is a black-gray color with a stronger blackness than that of silver-activated copper, and the blackness increases as the amount of chloroplatinic acid used increases. It was strong.

[Comparative Example 1] 200 mg of metallic copper powder was mixed with the same paint vehicle used in Example 1, and a copper ion elution test was conducted using the composition according to the test method described below. The results are shown in Table 1.

The composition obtained in the above-mentioned Examples or Comparative Examples was made into a glass fiber lattice woven fabric manufactured by Asahi Glass Co., Ltd., with 23 stitches in a 2.5 mm width and 1 thread width of 0.5 mm. 5mm) Apply in a 3cm x 3cm square, dry for 2 days, then add 50c of artificial seawater.
C, and replace the artificial seawater with fresh water every 6 hours.

The above operation is continued for 30 days, and the copper ion concentration in the artificial seawater is measured on the 7th, 200th, and 300th days.

Margin below Table 1 Copper ion concentration (ppIII) 7th day 200th day 300th day Example 1 Example 3 Example 6 Comparative example 1 1 1 1 [Examples 9 to 15] Example 1 and Examples 3 to Seven aquatic growth inhibiting compositions were prepared by mixing 3 g of the precious metal activated copper prepared in Example 8 with the same amount of polymer cement in place of the alkyd paint vehicle. The composition of the polymer cement is shown below.

Polymer cement 9 White Portland cement 3g SBR latex 1.6g No. 7 silica sand
3.5g water
0.2~0. 5cc In the above formulation, S
The BR latex used was Tomac Super made by Japan Synthetic Rubber. Water was also added to adjust the viscosity.

A copper ion elution test was conducted using the above composition according to the test method described below. The results are shown in Table 2.

[Comparative Example 2] 3 g of metallic copper powder was mixed with the same polymer cement as used in Example 9, and a copper ion elution test was conducted using the mixture according to the test method described below. The results are shown in Table 2.

The composition obtained in the above-mentioned example or comparative example was applied to a 6 cm
Apply to one side of a slate board of 5cm x 5cm x O, 1
After leaving it for day and night, immerse it in 100 cc of artificial seawater.
Replace the artificial seawater with fresh water every day and night. The above operation is continued for 30 days, and the copper ion concentration in the artificial seawater is measured on the 6th, 200th, and 300th days.

Table 2 Copper ion concentration (ppm) 6th day 200th day 300th day Examples Example 1 Example 1 Example 1 Example 1 Example 1 Example 1 Comparative example 2 [Usage example 1] Example 1 and Metallic copper 1007fr, rit in the same way
140 g of unactivated copper (63 mg of silver is attached to 100 g of copper with a part of the copper exposed) obtained by activating the copper with 0.1 part by weight of silver nitrate, or the same as in Example 3. Totally activated copper obtained by activating 100 parts by weight of metal steel with 0.1 parts by weight of chloroauric acid (47 mg of gold per 100 g of copper)
140 g of the copper (with some of the copper attached in an exposed state) were kneaded with polymer cement to produce an aquatic organism growth-preventing composition. The composition of the polymer cement is shown below.

Polymer cement combination White Portland cement 140g SBR latex 74g No. 7 silica sand
170g water
20cc In the above formulation, the SBR latex used was Tomac Super manufactured by Japan Synthetic Rubber@.

The above composition was divided into 30.5cm×45.5cmXo, 5
After applying the solution to one side of a cm slate board and leaving it in the air for 2 days, the solution was suspended in seawater at a port on the Matsuyama coast in Ehime Prefecture to observe the state of adhesion and growth of aquatic organisms. The results are shown in Table 3.

[Usage Example 2] Instead of silver-activated copper, metallic copper 1 was used in the same manner as in Example 3.
00 parts by weight with 0.1 parts by weight of chloroauric acid (47 mg of gold is attached to 100 g of copper with a part of the copper exposed) 140 g was used. In the same manner as in Use Example 1, the state of adhesion and growth of aquatic organisms was observed. The results are shown in Table 3.

[Comparative Use Example 1] 140 g of metallic copper powder was mixed with polymer cement having the same composition as in Use Example 1, and the composition was mixed into a 30.5 cm x 45.5 c.
After applying it to one side of a slate board of m x 0.5 cm and leaving it in the air for 2 days, the state of adhesion and growth of aquatic organisms was observed in the same manner as in Use Example 1. The results are shown in Table 3.

Table 3 Status of Aquatic Organisms 1 Rikitsuki 2 Rikitsuki 3 Rikitsuki Usage Example I AA AA AA Usage Example 2 AA AA BB Comparison Usage Example I AA AA CC Condition of Aquatic Organisms AA: BB with no animals or plants attached: No shellfish attached, but a slight amount of seaweed attached CC: Shellfish and seaweed attached [Example 16] Using the same electrolytic copper powder as that used in Example 1, In the same manner as in 1, 100 g of the electrolytic copper powder, SFi nitric acid
loomg, and 25 cc of water were mixed. The operation of stirring the above mixture for 10 minutes every hour was repeated six times to produce silver-activated copper (3163 mg of copper adhered to 100 g of copper with a portion of the copper exposed).

Next, 50 g of adipic acid and 25 cc of acetic acid aqueous solution (5 cc of glacial acetic acid, 20 cc of water) were added to the silver-activated copper and mixed thoroughly, and then the operation of stirring for 10 minutes every hour was repeated 6 times and allowed to stand. did. The mixture became an air-dried powder in 48 hours. The powder was ground in a ball mill for 24 hours and passed through a 150 mesh sieve.
A silver-activated copper modified product was obtained. The yield was 84%.

The silver-activated copper modified product had basic copper carbonate and basic copper adipate attached to its surface along with silver, and had a green-blue color.

[Example 17] A whole copper chloride modified product was obtained in the same manner as in Example 16, except that the aqueous solution Blcc used in Example 3 was used instead of the silver nitrate in Example 16. The yield was 85%.

The above-mentioned whole copper modified product had basic carbonate steel and basic copper adipate attached to its surface along with gold, and had a greenish-blue color.

[Example 18] A platinum-activated copper modified product was obtained in the same manner as in Example 16, except that the aqueous solution Dlcc used in Example 6 was used instead of the silver nitrate in Example 16. The yield was 85%.

The above-mentioned platinum-activated copper modified product has platinum on its surface.
Basic copper carbonate and basic copper adipate were attached, giving it a greenish-blue color.

[Example 19] Using the same electrolytic copper powder as that used in Example 1, 100 g of the electrolytic copper powder and S15 nitric acid were prepared in the same manner as in Example 1.
00 mg, and 25 cc of water were mixed. The above mixture was stirred for 1 hour and silver-activated copper (100 g of copper had 315 g of silver).
(mg was attached with a part of the copper exposed) was manufactured.

Next, 50 g of adipic acid, 25 cc of acetic acid aqueous solution (5 cc of glacial acetic acid, 20 cc of water), and 20 g of nickel acetate were added to the above silver-activated copper, and stirring was continued for 24 hours. was gotten. The powder was pulverized in a ball mill for 24 hours and passed through a 150-mesh sieve to obtain a modified silver-activated copper product with nickel integrally attached to its surface. The yield was 83%.

22g of the silver-activated modified copper with nickel integrally attached to the above surface was coated with fluororesin paint (Lumiflon 2 manufactured by Asahi Kasei).
00, main agent Bog, and 12 g of curing agent) to produce an aquatic organism growth-preventing composition.

[Usage example 3] Carbon fiber twisted yarn (GF-8Y manufactured by Nippon Carbon Co., Ltd., 3 strands) made by carbonizing rayon yarn is wound around the outer circumference of a Monel metal alloy wire with a length of 28 m and an outer diameter of 0.7 mm to make it conductive. Manufactured wire rods. The length of the carbon fiber strands required for the above treatment was 94 m. The resistance between the Monel metal alloy wire at the center and the carbon fiber at the outer periphery was 5Ω.

The aquatic organism growth-preventing composition produced in Example 19 was applied to the conductive wire. The above coating was performed four times.

Next, in a wooden frame of 40 cm x 31 cm x 10 cm,
A structure was manufactured in which a conductive wire coated with the above-mentioned composition for inhibiting the growth of aquatic organisms was wound into a coil shape, and both ends were fixed so that an alternating current could be passed therethrough. The above structure has an internal volume of 50j! It was fixed with bricks in the water tank to prevent it from surfacing.

Pour water into the aquarium above, introduce air from two places in the aquarium,
While an alternating current of 10 volts was being applied to the above-mentioned structure, 500 g of sardine fish iliac bone coarsely crushed using a disposer was put into the water tank.

Immediately after the fish iliac bone died, the water in the aquarium turned slightly red and cloudy due to the blood, but the red color immediately disappeared and became cloudy 1 hour after the fish was added, and turned slightly black after 3 hours. . Turn off the electricity and drain the water where blue-green algae are growing (hereinafter referred to as blue-green algae water)
When the water in the aquarium was added and air was continued to be supplied, the water in the aquarium turned slightly green in 48 hours and there was no smell of putrefaction.

[Comparative use example 2] Crushed copper powder (manufactured by Kashi Metal Foil, CC-3) 100, natural aluminum silicate (Kueya Kaolin ■, ASp-i'yo) 1
00g, butylacetate cellulose butyrate (manufactured by Eastman Kodak, CAB531) 100g, and adipic acid 100g
After stirring and mixing thoroughly, add 130 cc of water containing 12 cc of glacial acetic acid, and if some lumps form, take them out and continue stirring while crushing them. After 48 hours, the mixture turns greenish-blue and air-dried. of powder was obtained. The powder was pulverized in a ball mill for 24 hours, and the material that passed through a 150-mesh sieve was obtained as a verdigris-like material. The patina-like material is not activated by noble metals.

Instead of the silver-activated modified copper on which nickel was integrally adhered to the surface of the aquatic organism growth-preventing composition prepared in Example 9, the above-mentioned patina-like material not activated with noble metals was used. An aquatic organism growth-preventing composition was produced. A treatment test on sardine fish iliac bones was conducted in the same manner as in Use Example 2, except that the composition was used.

It took 10 hours for the water in the aquarium to lose its slightly red color due to blood, become cloudy, and then turn slightly black. Also, even when orchid wet water was added, the color did not turn slightly green.

Patent applicant Hi-Max Ka Co., Ltd. Patent attorney Yasuo Yanagawa

Claims (1)

[Scope of Claims] 1. 0.4 parts by weight or less of noble metal per 100 parts by weight of the metallic copper is integrally formed on the particle surface of the metallic copper powder with at least a part of the particle surface exposed. An aquatic organism growth inhibitor characterized by containing as an active ingredient precious metal-activated copper formed by adhesion. 2. Noble metal activated copper, in which 0.4 parts by weight or less of a noble metal is attached to the particle surface of a metallic copper powder with at least a part of the particle surface exposed, based on 100 parts by weight of the metallic copper. What is claimed is: 1. An aquatic organism growth inhibitor characterized by containing as an active ingredient a noble metal-activated copper modified product having a basic organic dibasic acid copper or a basic copper carbonate integrally attached to its surface. 3. Noble metal activity, in which 0.4 parts by weight or less of noble metal is integrally attached to the particle surface of metallic copper powder, with at least a part of the particle surface exposed, based on 100 parts by weight of the metallic copper. An aquatic organism adhesion prevention composition comprising copper chloride and a binder that holds it in a dispersed state. 4. Noble metal activated copper in which 0.4 parts by weight or less of a noble metal is attached to the particle surface of metallic copper powder with at least a part of the particle surface exposed, based on 100 parts by weight of the metallic copper. consisting of a precious metal-activated copper modified product, on which basic organic dibasic acid copper or basic copper carbonate is integrally adhered, and a binder that holds it in a dispersed state. Aquatic organism adhesion prevention composition.