JPH11323213A - Seaweedproofing/seashellproofing composition and machine component for submarine use coated therewith - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a composition having excellent seaweedproofing/ seashellproofing effect and seaweed/seashell-removing effect by including inorganic oxide microparticles of specific average size with a specific metal component supported thereon. SOLUTION: This composition is obtained by including inorganic oxide microparticles <=500 nm, pref. 3-500 nm, more pref. 5-250 nm in average size with a metal component having seaweedproofing/seashellproofing function supported thereon; wherein the inorganic oxide is pref. TiO2 , Al2 O3 , ZrO2 , SiO2 or the like; the above metal component to be used is pref. silver, copper, zinc or the like; its amount to be supported is pref. 0.01-50 wt.% based on the metal oxide. More precisely, this composition is obtained, for example, by mixing a metal component salt or an aqueous solution thereof and an anion exchanger in an aqueous sol with the inorganic oxide's colloidal particles as disperse phase to effect supporting the metal component on the colloidal particles.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an anti-algal composition against civilian water, industrial water, seawater, freshwater and the like. The present invention also relates to equipment for underwater use to which the anti-algal shell composition is adhered.

[0002]

2. Description of the Related Art Algae generated at the bottom of ships, waterways of power plants, offshore structures, various facilities and equipment of refineries and steelworks in coastal areas, or cooling towers and water tanks for civil use. BACKGROUND ART In order to prevent or remove adhesion, an anti-algal shell composition has been conventionally used. As the anti-algae composition, an anti-algae agent containing an organotin compound has been used in the past, but due to its toxicity, the use of specific organotin compounds is currently regulated. .

Recently, organic anti-algal compositions such as benzothiazoles and phenyls disclosed in JP-A-4-321608, JP-A-62-239934, and JP-A-62-16934 are disclosed. There is known an inorganic anti-algae shell and shell composition represented by silver, copper and the like as disclosed in Japanese Patent No. 282018.

[0004]

However, the above-mentioned organic anti-algal shellfish composition does not have sufficient sustainability of the effect.
Although there is no problem in terms of toxicity to the human body, it has problems in terms of environmental pollution or environmental safety in ecosystems. On the other hand, the above-mentioned inorganic anti-algae shell composition has a long-lasting effect in a water system from which algae and the like are completely removed from the beginning, but has a weak effect in a system in which algae and the like have already been generated. There is a problem.

[0005] The present invention is to solve the above problems,
It is an object of the present invention to provide an anti-algal shell composition having excellent anti-algal and anti-algal effects and an algae-removing effect, and an underwater equipment to which the present composition is attached.

[0006]

Means for Solving the Problems The anti-algal shell composition of the present invention comprises inorganic oxide fine particles having an average particle diameter of 500 nm or less and carrying a metal component having an anti-algal shell function. Is what you do. The metal component is preferably one or more selected from silver, copper and zinc.

[0007] The underwater equipment according to the present invention is characterized in that the above-mentioned anti-algal and shell-forming composition is adhered thereto.

[0008]

BEST MODE FOR CARRYING OUT THE INVENTION In the present invention, there is no particular limitation on the kind of inorganic oxide constituting the anti-algal shell composition, and either a single oxide or a composite oxide can be used. As a single oxide, Al ₂ O ₃ , SiO ₂ , Ti
O ₂ , ZrO ₂ , ZnO _{2 and the} like are exemplified, and as the composite oxide, SiO ₂ .Al ₂ O ₃ , SiO ₂ .TiO _2
2 , Al ₂ O ₃ .TiO ₂ , SnO ₂ .Sb ₂ O ₃ , T
iO ₂ · ZrO ₂ · SiO ₂ , SiO ₂ · TiO ₂ · A
l ₂ O ₃ , SiO ₂ .Al ₂ O ₃ .MgO, SiO _2.
Al ₂ O ₃ .CaO and the like can be mentioned. Among these, TiO ₂ , Al ₂ O ₃ , ZrO ₂ , S
inorganic oxides including iO ₂ is preferred.

The average particle diameter of the inorganic oxide fine particles is 50
It must be very fine particles of 0 nm or less. When the average particle diameter of the fine particles is larger than 500 nm, the adhesion to the equipment becomes small, and the sustainability of the anti-algal shell function is reduced, or the texture of the equipment surface is impaired. The average particle diameter of the fine particles is preferably in the range of 3 to 500 nm, and particularly preferably in the range of 5 to 250 nm.

[0010] The metal component having an anti-algal and shell-proofing function includes:
Metal components used in conventional anti-algal shellfish can be used, and silver, copper, and zinc are particularly preferable. Further, the loading amount of the metal component is preferably 0.01 to 50% by weight, more preferably 0.5 to 30% by weight as a metal oxide.

The antialgal composition of the present invention can be produced, for example, by the following method. That is, an aqueous sol containing colloidal particles of the inorganic oxide as a dispersoid (hereinafter, also referred to as an aqueous colloid solution) is added to a metal salt of a metal component having an anti-algal shell-proofing function or an aqueous solution thereof and an anion exchanger. And the metal component having the anti-algal and shell-proofing function is supported on the inorganic oxide colloid particles.

As the aqueous sol, a commercially available aqueous sol can be used. In addition, the above-mentioned colloidal particles of inorganic oxides include not only colloidal particles composed of a single inorganic oxide, but also those composed of composite oxides, hydroxides, or mixtures thereof. The concentration of the aqueous sol is not particularly limited, but is not more than 20% by weight, preferably 0.5% by weight.
It is desirable to use a low concentration colloid solution in the range of 〜5% by weight.

As the metal salt of the metal component having an anti-algal function, a metal salt soluble in water can be used. Inorganic acid salts such as metal nitrates, sulfates, phosphates, hydrochlorides and carbonates can be used. Or an organic acid salt such as acetic acid. Also,
As the metal component, one or more metal components of the above-described metal components can be used.

The above metal salt is preferably used as an aqueous metal salt solution. At this time, the concentration of the aqueous metal salt solution is not particularly limited, but it is desirable to use a dilute aqueous solution of 5% by weight or less, preferably 3% by weight or less. This is because, depending on the metal salt aqueous solution, when the concentration is high, the colloid particles may coagulate.

The anion exchanger mixed with the aqueous sol is
Any material having an anion exchange ability may be used, and examples thereof include a commercially available strong or weakly basic anion exchange resin, a chelate resin, an ion exchange membrane, and an ion exchange filter. These anion exchangers are used alone or in combination.

In order to mix the aqueous sol, the metal salt or the aqueous solution thereof, and the anion exchanger, a method that does not greatly change the pH of the aqueous sol is employed, for example, by the following method.

A dilute aqueous solution of a metal salt prepared in advance is slowly added to the colloid solution so that no precipitate is formed.
At this time, if necessary, the colloid solution may be heated to a temperature lower than the maximum use temperature of the anion exchanger. Next, or an anion exchanger is added simultaneously with the addition of the aqueous metal salt solution, and the pH of the aqueous sol is maintained at the pH before the start of the addition.
After completion of the addition, aging at a temperature of 80 to 90 ° C. for several hours is preferable.

When the pH of the aqueous sol is small when the aqueous metal salt solution is added, the anion exchanger is not added during the addition of the aqueous metal salt solution. The pH of the aqueous sol may be adjusted to the pH before the start of the addition by adding an anion exchanger.

In general, the pH of an aqueous sol has a value far from the isoelectric point because the particles are aggregated and gelled near the isoelectric point of the colloidal particles. However, when a metal salt or an aqueous solution thereof is mixed with the inorganic oxide aqueous sol, the pH of the aqueous sol changes and approaches the isoelectric point.
The aqueous sol becomes gelled.

As described above, since the aqueous sol is mixed with the aqueous metal salt solution and the anion exchanger, the salt ion in the aqueous sol is removed from the aqueous sol having a pH higher than the isoelectric point, and the aqueous sol is removed. Since the pH of the sol does not change, the stable pH range of the aqueous sol is maintained, so that the metal component is supported on the colloid particles. Further, even in an aqueous sol in a pH region lower than the isoelectric point, since the salt ions are removed, there is no excess salt ion in the aqueous sol, so the value of the zeta potential on the surface of the colloid particles does not decrease, The stability of the aqueous sol is maintained.

That is, the aqueous metal salt solution is dissociated into a positively charged metal ion (M ⁺ ) and a negatively charged salt ion, and the salt ion is a hydroxide ion (OH) of the anion exchanger.
^-) and for exchanging metal ions (M ⁺⁾ and hydroxide ions (OH in the solution - there will ^be). Furthermore, hydroxyl (-OH) hydrogen ions (H ⁺ ) and metal ions (M
⁺ ) Undergoes ion exchange with (−OM) and hydrogen ion (H ⁺ )
The hydrogen ions (H ⁺ ) react with the hydroxide ions (OH ⁻ ) to produce water (H ₂ O). According to the above-described production method, the metal component is thus supported on the surface of the inorganic oxide colloid particles without coagulation. Further, the pH of the aqueous sol is not greatly changed.

Finally, in order to remove the remaining anions if desired, the aqueous sol is cooled to the use temperature of an ultrafiltration membrane, washed with distilled water several tens times the solid content, and concentrated. Good.

The amount of the metal component supported on the inorganic oxide colloid particles can be arbitrarily selected by adjusting the mixing ratio of the metal salt or the aqueous solution of the metal salt with respect to the aqueous sol. 0.01 to above
It can be in the range of 50% by weight.

The anti-algal shell composition of the present invention can be used for sea, river,
The present invention can be applied to any equipment (including facilities and equipment) used in water, including swamps, irrigation canals, and water tanks. Examples of such products include (1) a textile product represented by a culture net, a rope, a fish net, a rope, (2) a resin product represented by a float and a culture rod, and (3) a float product and a culture rod. Examples include natural products, and (4) inorganic products typified by shore tetrapods, waterway mortars, and aquarium glass.

In order to impart the anti-algal and anti-algal properties to these equipment, a method of bringing the equipment into contact with the anti-algal and anti-algal composition of the present invention, followed by drying or baking, or applying the anti-algal and anti-algal properties of the present invention to the equipment A known method such as a method of spraying a shell-proof composition may be employed.

The anti-algal shell-and-shell composition of the present invention can also be used as an anti-algal shell-and-shell coating such as a ship bottom paint. The anti-algal shell composition is composed of the anti-algal composition, a film-forming agent, and a solvent to be blended if necessary. Examples of the algal anti-shell coating include oil-based paint, alcoholic paint, and cellulose. Paints, synthetic resin paints, water-based paints, rubber paints and the like can be mentioned.

The anti-algal shell-resistant coating composition may be prepared by adding the anti-algal shell-proofing composition to a suitable film-forming agent or solvent, or by any other process for producing a coating film composition, or by forming a coating film. Can be prepared by adding and mixing in the step. As such a film-forming agent, a natural resin, rubber, synthetic resin, or the like is usually used, and as a solvent, water, vegetable oil, alcohols, petroleums, esters, ketones, and the like are usually used. You.

[0028]

The present invention will be described more specifically with reference to the following examples.

[0029] (Production of Bomobokai composition) Example 1 Copper nitrate Cu (N0 ₃₎ of 13.7 g ₂ · 3H ₂ O in water 2
740 g was added to prepare a 0.5% by weight aqueous solution of copper nitrate. 4.0 kg of a titanium colloid aqueous solution having a TiO ₂ concentration of 1% by weight was collected in a beaker and heated to 50 ° C. with stirring. At this time, the pH of the aqueous titanium colloid solution was 7.9. The aqueous copper nitrate solution was added to the aqueous titanium colloid solution at a rate of 10 g / min using a peristaltic pump. Addition of aqueous solution of copper nitrate to p
When H began to decrease, an anion exchange resin (manufactured by Mitsubishi Chemical) was added little by little so as to maintain the initial pH of 7.9, and this operation was continued until the addition of the entire aqueous copper nitrate solution was completed.

The total amount of the anion exchange resin used was 230 g, and the final pH of the aqueous colloid solution was 8.1. This aqueous colloid solution was washed with water 200 times the weight of TiO ₂ in an ultrafiltration membrane device, and then concentrated to obtain a stable aqueous copper-supported titanium colloid solution (A) having a solid concentration of 3% by weight. Cu in the solid content of the aqueous colloid solution (A)
The amount of O carried was 10.0% by weight.

The average particle diameter (Dp) of the fine particles dispersed in the aqueous colloid solution was measured by an ultracentrifugal automatic particle size distribution analyzer (CAPA-700) to find that the average particle diameter was 7.0.
nm.

[0032] In Example 1, copper nitrate _{Cu (N0 3) 2 · 3H} 2 O
Was replaced with 3.3 g of silver nitrate AgNO ₃ , and the same operation as in Example 1 was carried out to obtain a silver-supported titanium colloid aqueous solution (B). This aqueous colloid solution (B) maintained a stable colloidal state even after one month of standing. Ag ₂ O carried in the solid content of the aqueous colloid solution (B) was 5.1% by weight.
And the total amount of the anion exchange resin used was 101.0 g. The average particle diameter (Dp) of the fine particles as the dispersoid of the aqueous colloid solution (B) was 7.0 nm.

(Improvement of anti-algal and shell-proofing properties) Example 3 200 g of the aqueous colloid solution (A) obtained in Example 1 was added to 100 g.
A 1.0% by weight aqueous colloid solution was prepared by adding ml of pure water. This aqueous solution was sprayed on a float of urethane foam, and then dried at 100 ° C. to obtain a seaweed- and shellfish-proof float (C1).

Example 4 The same treatment as in Example 3 was carried out except that the aqueous colloidal solution (B) obtained in Example 2 was used instead of the aqueous colloidal solution (A). Processing float (C2)
I got

Example 5 100 g of the aqueous colloidal solution (A) obtained in Example 1
By adding 00 ml of pure water, a 1.0% by weight aqueous colloid solution was prepared. This aqueous solution was sprayed onto a glass plate, and then baked at 300 ° C. to obtain a seaweed-proof and shell-proof treated glass plate (D
1) was obtained.

Example 6 The same treatment as in Example 5 was carried out except that the aqueous colloidal solution (B) obtained in Example 2 was used instead of the aqueous colloidal solution (A) in Example 5, to obtain an antialgal shell Treated glass plate (D
2) was obtained.

(Test for anti-algal shell-proofing property) Example 7 As a sample, an algal-proof shell-proofing float (C1), (C2) and an untreated float (blank) were used, and immersed in the sea in Aioi Bay, Hyogo Prefecture for 1 hour. Conducted annually. In the function test, the degree of biofouling (%) was measured by visual evaluation for three items: slime (slime), adherent plants, and adherent animals. Table 1 shows the measurement results.

[0038]

[Table 1]

Example 8 As samples, glass plates (D1) and (D2) treated with algae- and shell-proofing
And untreated glass plate (blank), body length about 5
The fish were immersed in a 50 L home aquarium containing 10 cm-thick goldfish for 2 weeks. In the function test, the degree of biological fouling (%) was measured by visual evaluation for two items, slime and adherent plants. Table 2 shows the measurement results.

[0040]

[Table 2]

[0041]

The anti-algae composition of the present invention has an excellent anti-algae effect in water. In addition, the anti-algal shell composition of the present invention can easily impart an anti-algal shell function to equipment including the above-described various facilities, devices, equipment, and the like. Furthermore, it is excellent in safety and there is no risk of polluting the natural environment.

Continued on the front page (51) Int.Cl. ⁶ Identification code FI C08K 9/02 C08K 9/02 C09D 5/16 C09D 5/16

Claims (3)

[Claims] 1. An anti-algal shell composition comprising inorganic oxide fine particles having an average particle diameter of 500 nm or less, on which a metal component having an anti-algal shell function is supported. 2. The metal component having an anti-algal shell-and-shell function is silver,
The anti-algal shell composition according to claim 1, wherein the composition is at least one selected from copper and zinc. 3. An underwater equipment to which the anti-algal shell composition of claim 1 or 2 is attached.