JP2007277452A - Antifouling coating against aquatic organisms - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an antifouling coating to be used at a ship bottom that can extend the lasting period of its fouling inhibitory effect against aquatic organisms and is obtained by mixing a fired diatomaceous earth powder whose grain size is controlled with an antifouling coating used at a ship bottom. <P>SOLUTION: The antifouling coating against aquatic organisms is obtained by burning diatomaceous earth in which ≥80% of main components contained is silica in the crust of diatoms and montmorillonite, in a temperature range from 1,000 to 1,200°C, breaking it up into a 5-10 microns spherical fine particle shape and mixing the antifouling coating for the ship bottom with a mixing material comprising a fired diatomaceous earth powder with controlled grain size. <P>COPYRIGHT: (C)2008,JPO&INPIT

Description

  The present invention relates to an improvement of a ship bottom antifouling paint for suppressing adhesion of aquatic organisms, particularly animal microorganisms, to a ship bottom, etc., and uses baked diatomaceous earth powder mixed with a ship bottom antifouling paint. Therefore, the anti-fouling paint for the bottom of the ship has been developed mainly to suppress the adhesion of shellfish and marine microorganisms to the bottom of the ship for a long period of time.

  Aquatic organisms such as barnacle shellfish, mussels, and black sea breams or plant-based aquatic organisms such as blue algae and black algae adhere to and propagate in submerged parts that are exposed to seawater for a long period of time, such as the ship's bottom. There was a problem that the appearance was damaged or the function was impaired. In particular, in the case of ships, shells adhere to the bottom of the ship, resulting in a decrease in speed and a deterioration in fuel consumption. Therefore, the attached shells and the like must be periodically removed, which requires a great deal of labor and cost. It was always.

  Therefore, in order to suppress adhesion and reduce the labor and cost of the removal work, a ship bottom antifouling paint containing copper or lead has been applied to suppress adhesion of aquatic animals such as barnacles. Or, an organic ship bottom antifouling paint is applied to suppress adhesion of plant aquatic organisms such as algae.

  Conventional ship bottom antifouling paints are hydrolyzed by a self-polishing type that prevents the adhesion of marine organisms by dissolving the coating itself, and by a synthetic polymer resin on the coating surface as described in Patent Document 1. It is roughly divided into hydrolyzed types that prevent the adhesion of marine organisms by dissolving uniformly in water. There is a tendency that hydrolyzed ship bottom paints are often used for small ships using FRP materials that have become widespread in recent years.

  However, since the dissolution rate of the ship bottom antifouling paint is greatly affected by the seawater temperature, there is a problem that the effect of suppressing aquatic organism adhesion has been diminished due to the recent increase in seawater temperature worldwide. In addition, the effectiveness of the bay and the brackish water area of the bay where the water from the river flows into was easily diminished, and in fact, barnacles were attached in a short period of about several months.

Japanese Patent Laid-Open No. 11-333374

  In the present invention, in order to solve the above problems, diatomaceous earth composed of silica and montmorillonite in which 80% or more of the main components are baked is crushed into spherical fine particles, and the particle size-adjusted baked diatomaceous earth powder is protected from the bottom of the ship. The purpose of the present invention is to provide a ship bottom antifouling paint that is mixed with a dirt paint and extends the duration of the effect of suppressing the aquatic organisms from adhering to the ship bottom.

  According to the first invention, diatomaceous earth comprising diatom shell silica and montmorillonite, in which 80% or more of the main components are contained, is baked within 1,000 to 1,200 degrees Celsius, and then crushed into spherical fine particles of 5 to 10 microns. Thus, an aquatic organism antifouling antifouling paint characterized in that a mixed material composed of calcined diatomaceous earth powder having a particle size adjusted is mixed with a ship bottom antifouling paint.

  A second invention is the same as that of the first invention, wherein the mixed material is added to the calcined diatomaceous earth powder, 20 to 45 weight percent bentonite, 1 to 2 weight percent mineral spirit, and 2 to 5 weight percent. Anti-fouling antifouling paint for aquatic organisms, which is a mixture of sorbitan monooleate and two sorbitan ester dispersants as a dispersant.

  The third invention is an antifouling antifouling paint for aquatic organisms, wherein the mixed material contains 5 to 45 weight percent of fly ash crushed to 1 to 20 microns in the first or second invention. It is.

  According to a fourth invention, in any one of the first to third inventions, the ship bottom antifouling paint comprises 3 to 5 weight percent zinc, 25 to 30 weight percent cuprous oxide, and 3 to 5 weight percent. Of titanium, 3 to 5 weight percent ferric oxide, 9 to 10 weight percent naphtha, 14 to 15 weight percent ethylbenzene, and 5 to 10 weight percent xylene. This is an antifouling paint that suppresses the adhesion of aquatic organisms.

  The fifth aspect of the present invention is the suppression of aquatic organism adhesion, wherein the mixed material is added to any one of the first to fourth aspects of the invention, wherein the mixed material is blended in an amount of 3 to 5 percent by weight with respect to the ship bottom antifouling paint. Antifouling paint.

  In the first invention, diatomaceous earth is baked within 1,000 to 1,200 degrees Celsius, then crushed into spherical fine particles of 5 to 10 microns, and the particle size adjusted baked diatomaceous earth powder is mixed with a ship bottom antifouling paint. Since it was formulated, it became a ship bottom antifouling paint capable of maintaining the adhesion control effect of aquatic organisms for a long time. This is a porous diatomaceous earth powder with excellent heat-absorbing and heat-dissipating properties, and effectively absorbs and releases the heat accumulated in the bottom of the ship, thereby suppressing the rise in seawater temperature that comes into contact with the bottom antifouling paint. This is probably because of the temperature control action.

  The fired diatomaceous earth powder is obtained by firing diatomaceous earth within 1,000 to 1200 degrees Celsius, so that the water content is properly removed and the bond strength with the solvent is secured, Since it is crushed into spherical fine particles of 5 to 10 microns, it is suitable for mixing with ship bottom antifouling paints. In addition, the present invention is effective for use on the ship bottom, but it can also be used as a paint for suppressing the adhesion of aquatic organisms, especially animal microorganisms, to marine buoys, revetments, marine structures, etc. Is possible.

  Although it is an effect of 2nd and 3rd invention, since the mixed material is easy to mix with calcination diatomaceous earth powder, and bentonite and fly ash in which the effect approximated with calcination diatomaceous earth powder is added, these are added. It is economical because the use ratio of the calcined diatomaceous earth powder whose additional material is expensive can be reduced.

  Hereinafter, the best mode for carrying out the present invention will be described together with examples. First, the first embodiment is prepared as an adhesion suppression antifouling paint A in which the mixed material a and a commercially available ship bottom antifouling paint P1 are mixed. The anti-fouling anti-fouling paint A is prepared by mixing 4 kg of a commercially available bottom antifouling paint P1 in a 4 kg bottom antifouling paint can and a mixing ratio of 5% by weight, that is, 200 g of the mixed material a. It is done.

  The mixed material a was prepared by adding 10 g (5 weight percent) mineral spirit as a solvent to 100 g (50 weight percent) of calcined diatomaceous earth powder and 80 g (40 weight percent) bentonite powder, and further adding 5 g (2.5 weight). Percent) sorbitan monooleate and 5 g (2.5 weight percent) sorbitan ester were added as dispersants and mixed to colloidalize to prepare 200 g.

  The calcined diatomaceous earth powder, which is the first component of the mixed material a, is pulverized into spherical fine particles of 2 to 50 μm (micron), preferably 3 to 5 μm (micron), after calcining diatomaceous earth at 1000 to 1200 ° C. It was obtained. This is a porous glass body, and its components are: thermal oxide silicon (silicon) 70.3%, aluminum oxide (alumina) 25.0%, titanium oxide 0.97%, iron oxide (three It contains 1.51 percent ferric oxide), 0.25 percent calcium oxide (quick lime), and 0.15 percent sodium oxide, and has excellent exhalation moisture characteristics, far-infrared radiation characteristics, and the like.

  As for the diatomaceous earth, if the diatomaceous earth comprising 80% or more of the main component is composed of silica of diatom shell and montmorillonite, those having different content ratios may be used, and the particle size is within the range of 5 to 10 microns. If so, it can be appropriately changed.

  In addition, the compounding quantity of the said baked diatomaceous earth powder can be increased / decreased in the range of 45 to 55 weight percent. The amount of bentonite powder may be increased or decreased in the range of 35 to 45 weight percent, but bentonite powder may not be used. Further, the blending amounts of the solvent and the dispersant can be appropriately increased or decreased within the range of 1 to 5 weight percent, for example.

The ship bottom antifouling paint P1 in the first embodiment has a specific gravity of 1.80 and a viscosity of 85 to 100 KU for a commercially available FRP hydrolyzable ship bottom antifouling paint (manufactured by Dainippon Paint Co., Ltd .: trade name “Sea Blue Ace”, Oily, color = blue) 4 kg was used. This component is generally comprised of 3 to 5 weight percent zinc, 25 to 30 weight percent cuprous oxide, 3 to 5 weight percent titanium, 3 to 5 weight percent ferric oxide, and 9 to 10 A bottom antifouling paint composed of weight percent naphtha, 14 to 15 weight percent ethylbenzene, and 5 to 10 weight percent xylene.
The mixing amount of the mixed material a with respect to the ship bottom antifouling paint P1 can be increased or decreased as appropriate.

  2nd Example, adhesion suppression antifouling paint B is mixed material a0.2 kg used in 1st Example, commercially available ship bottom antifouling paint P2 (made by Asahi Pen Co., Ltd .: trade name “multipurpose paint”, water-based, (Color = Blue) A mixture of 4 kg was used. Here too, the amount of the mixed material a added to the ship bottom antifouling paint P2 can be appropriately increased or decreased. In both the first and second embodiments, the mixed material a may contain 5 to 45 weight percent fly ash.

  In the third embodiment, the antifouling antifouling paint C is a bottom antifouling paint P1 similar to that of the first example, ie, a hydrolytic hydrolytic bottom antifouling paint for FRP having a specific gravity of 1.80 and a viscosity of 85 to 100 KU ( Dainippon Paint Co., Ltd. (trade name “Sea Blue Ace”, oiliness, color = blue) 4 kg and a mixed material b were used. The mixed material b is obtained by adding 5 to 45 weight percent fly ash in the mixed material a used in the first and second examples.

  The fly ash is in the form of a powder pulverized to a particle size of 1 to 20 μm (micron), preferably 7 μm (micron), which is 70.9 percent of thermal silicon oxide (silicon) and aluminum oxide (alumina) 19. 9 percent, titanium oxide 1.08 percent, iron oxide (ferric trioxide) 3.14 percent, calcium oxide (quick lime) 0.96 percent, magnesium oxide 0.74 percent, potassium oxide 1.05 percent , It contains 0.28% sodium oxide, has a pore structure similar to diatomaceous earth powder, exhibits pozzolanic activity, and is excellent in long-term strength retaining action and air permeability due to a stable bonding action between molecules. In addition, as fly ash powder, you may use what differs in a content component ratio from what was shown above.

  The color of the bottom antifouling paints 1 and 2 is changed by mixing the mixed material a in Examples 1 and 2 and the mixed material b in Example 3 and the bottom antifouling paint 1 or 2, and the composition thereof. It did not adversely affect. Furthermore, even when the mixed material a and the mixed material b were mixed with other commercially available ship bottom antifouling paints, the color of the ship bottom antifouling paints was not changed or the composition thereof was not adversely affected.

  Subsequently, three types of ship bottom antifouling paints were prepared as comparative ship bottom antifouling paints for experiments. First, a ship bottom antifouling paint P3, which is a product different from the ship bottom antifouling paint P1 to P2, is available in Japan. For this, the mixed materials a and b used in the first to third examples were not prepared. Second, a commercially available ship bottom antifouling paint P4 (trade name “AFO”) made in the United States, which is a product different from the ship bottom antifouling paint P1 to P3, was prepared. Also for this, the mixed materials a and b used in the first to third examples were not prepared. Third, a commercially available ship bottom antifouling paint P5 (trade name “VINKO”), which is another product, was prepared. Also for this, the mixed materials a and b used in the first to third examples were not prepared.

The following experiment was conducted as a first example of the performance evaluation experiment of the adhesion suppression paint and the ship bottom antifouling paint.
First, a total of six types of three types of antifouling antifouling paints A, B and C according to the examples and three types of ship bottom antifouling paints P3 to P5 according to each of the above comparative examples were prepared, each having a size of 300 mm × 150 mm. One surface of the FRP plate was applied by using a brush and a roller and dried for 4 hours. In any FRP plate, no coating was applied to the opposite surface. Then, the FRP plate was submerged 10 to 15 cm in water and moored at the dock, and the progress was observed.

  The condition was as follows after 14 days from the start of the experiment. About 50 barnacles with a size of 1 mm were attached to the coating surface of the FRP plate to which the ship bottom antifouling coating P3 was applied. About 1 mm of green algae had adhered to the paint application surface of the FRP plate to which the ship bottom antifouling paint P4 was applied. No adhesion of aquatic organisms was observed on the other FRP plates with the paint applied.

At the end of 35 days from the start of the experiment, the condition was as follows.
Barnacles attached to the FRP plate coated with the ship bottom antifouling paint P3 have grown to a size of 5 mm, and a 1 mm size barnacle has adhered to the entire paint application surface of the FRP plate, and algae has grown to 20 mm. Was. The slime adhered to the paint application surface of the FRP plate to which the ship bottom antifouling paint P5 was applied, and the color of the paint was faded.

  No deposits were observed on the coating surface of the FRP plate coated with the adhesion-suppressing antifouling paint A and the adhesion-suppressing antifouling paint C. On the FRP plate to which the antifouling antifouling paint B was applied, some scale and slime adhered to the entire coating surface.

At the end of 43 days from the start of the experiment, the condition was as follows.
Barnacles (5mm in size) adhere to the entire surface of the FRP plate coated with ship bottom antifouling paint P3, and algae also adhere to the entire surface, so that the color of the original ship bottom antifouling paint P3 can be observed at all. It was gone. Barnacles and algae adhered to the entire coating surface of the FRP plate to which the ship bottom antifouling paint P4 was applied, and the color of the original ship bottom antifouling paint could hardly be observed. The barnacles did not adhere to the paint application surface of the FRP plate to which the ship bottom antifouling paint P5 was applied, but slime adhered, and the color of the ship bottom antifouling paint was faded.

  No adhesion of barnacles, algae, or slime was observed on the coating surface of the FRP plate to which the adhesion-suppressing antifouling paint A and the adhesion-suppressing antifouling paint C were applied. Some scale and slime adhered to the coating surface of the FRP plate to which the antifouling antifouling coating material B was applied.

The condition was as follows after 50 days from the start of the experiment.
Barnacles were attached to the coating surfaces of the FRP plates to which the ship bottom antifouling coatings P3 to P5 were applied. The FRP plate coated with the antifouling antifouling paints A, B, and C showed no adhesion of barnacles and algae although some scales and slime were attached. Further, no fading of the paint itself was observed on the paint application surface of each FRP plate to which the antifouling antifouling paints A, B and C were applied.

According to this experiment, a conventional commercially available ship bottom antifouling paint is also configured as in the present invention, and a ship bottom antifouling paint mixed with the mixed material according to the present invention is applied, and this is applied to maintain the antifouling effect. It was confirmed that can be extended.
In addition, since no paint was applied to the surface opposite to the paint application surface of each of the FRP plates, barnacles started to attach from the time when 14 days had passed since the start of the experiment, and on the entire surface when 30 days passed. It was attached.

The following experiment was conducted as a second example of the performance evaluation experiment of the antifouling antifouling paint and the bottom antifouling paint.
Shells and algae attached to the bottom of the 2-ton FRP fishing boat were removed, and the bottom was washed with water and dried. For the convenience of follow-up, the bottom of the ship is divided into six blocks 1 to 6 shown in FIG. 1, and the anti-fouling antifouling paint A is applied to the blocks 1 to 3 and the blocks 4 to 6 are attached. Applied antifouling antifouling paint B by brush and roller, applying 180 to 185 g per square meter, wet film thickness of 80 μm (dry film thickness of 40 μm), and drying for 4 hours. After that, the hull was landed and moored at the dock for a long time, and the progress was observed. The antifouling paints A and B used here are a mixture of a fired diatomaceous earth powder and bentonite powder mixed with a solvent and a dispersant. The antifouling antifouling paint A is an oil-based, antifouling antifouling agent. The paint B is water-based.

The condition after 6 months from the start of the experiment was as follows.
In blocks 1 to 3, scales adhered, but no shellfish or algae adhered. Blocks 4 to 6 were attached with slimy scale, but no shellfish or algae were observed.

The state after 12 months from the start of the experiment was as follows.
Blocks 1 to 3 were adhered to scales by long-term mooring, but no shellfish or algae were observed. In blocks 4 to 6, as in the case of 6 months from the start of the experiment, scales adhered, but shellfish and algae did not adhere.

The state after 18 months from the start of the experiment was as follows.
As for Blocks 1 to 3, scales on the bow side of Block 1 were darkened due to the waves, but shellfish and algae were not observed on other parts. In addition, 32 to 35 barnacles having a size of 1 to 1.5 mm adhered to the stern portion of the block 6.

The state after 24 months from the start of the experiment was as follows.
Two barnacles of 1 mm or less adhered to the stern helicopter of Block 3. Grown barnacles with a size of 5 mm overlapped and adhered to portions other than the portion near the bow of block 4 and the entire surfaces of blocks 5 and 6.

  As described above, the blocks 1 to 3 to which the antifouling antifouling paint A is applied are almost free of shellfish (barnacles) even though they are moored for a long period of at least 18 months. I couldn't see it. By the way, after 28 months from the start of the experiment, 2 mm-large barnacles started to attach from the stern side of block 3. Even in blocks 4 to 6 to which the antifouling antifouling paint B was applied, the adhesion of shellfish was not observed for at least about 15 months, but the adhesion of barnacles began with the peeling of the paint after 18 months.

  The conventional anti-fouling paint on the bottom of the ship, when applied to the bottom of the ship as it is, will have barnacles attached in about 5 months at the earliest and about 10 months at the latest. On the other hand, it was necessary to repaint the ship bottom antifouling paint. On the other hand, when the antifouling antifouling paint of the present invention is used, even if it is applied once, the aquatic organism adhesion is suppressed for at least one year. It was found that the effect was maintained. Accordingly, it is possible to reduce the frequency of removing the aquatic organisms adhering to the ship bottom and applying the ship bottom antifouling paint again, thereby reducing the work cost and the work effort.

The following experiment was conducted as a third example of the performance evaluation experiment of the antifouling antifouling paint.
Shells and algae attached to the bottom of a 3 ton FRP fishing boat were removed, the bottom of the vessel was washed with water, dried, and attached with anti-fouling antifouling paint C on the entire surface, and dried for 6 hours. After that, the hull was landed on the sea and operated three to five days a week to observe the progress. In addition, the adhesion suppression antifouling paint C used here is a paint according to the third embodiment, and as described above, the ash diatomaceous earth powder is mixed with fly ash powder in the mixed material b.

  Six months after the start of the experiment, the hull was lifted with a crane and the condition of the bottom of the ship was verified, but no shells were found attached. At the end of 12 months from the start of the experiment, the hull was lifted again with a crane to verify the state of the bottom of the ship, but no aquatic organisms such as shellfish were attached. However, barnacles with a size of 5 to 8 mm were firmly attached to the fixed part of the screw rotating blades to which the adhesion suppressing antifouling paint C was not applied.

  Even after 16 months from the start of the experiment, shellfish did not adhere to the bottom of the ship. However, barnacles were adhered to the portions of the metal portion of the engine fixing portion where the adhesion-preventing antifouling paint C was not applied without any gaps.

  As is clear from the above performance evaluation experiments, if the antifouling antifouling paint according to Examples 1 to 3 is applied to the bottom of a ship, the duration of the effect of suppressing the adhesion of animal aquatic organisms can be greatly extended. Can do. This is a porous diatomaceous earth powder with excellent heat-absorbing and heat-dissipating properties, and effectively absorbs and releases the heat accumulated in the bottom of the ship, thereby suppressing the rise in seawater temperature that comes into contact with the bottom antifouling paint. This is probably because of the temperature control action.

  Therefore, the conventional ship bottom antifouling paint in which the duration of the effect of suppressing the adhesion of aquatic organisms in the sea is shortened due to the rise in seawater temperature can be extended by introducing the production method of the present invention. In addition to suppressing the adhesion of shellfish etc. to the ship's bottom, if the paint of the present invention is applied to the surface of seawater submerged areas such as marine traffic marking buoys, marine structures, revetments, etc. Adhesion can be suppressed.

Explanatory drawing showing the position of the ship's bottom

Explanation of symbols

1. . . . . . Block 1
2. . . . . . Block 2
3. . . . . . Block 3
4). . . . . . Block 4
5). . . . . . Block 5
6). . . . . . Block 6

Claims (5)

The particle size was adjusted by calcination of diatomaceous earth consisting of silica and montmorillonite of 80% or more of the main component contained within 1,000 to 1,200 degrees Celsius and then crushed into spherical fine particles of 5 to 10 microns. An antifouling paint for preventing the adhesion of aquatic organisms, characterized by mixing a mixed material made of calcined diatomaceous earth powder with a ship bottom antifouling paint.
The mixed material is a diatomaceous earth powder containing 20 to 45 weight percent bentonite, 1 to 2 weight percent mineral spirits, and 2 to 5 weight percent dispersing agent of sorbitan monooleate and sorbitan ester. 2. The antifouling antifouling paint for aquatic organisms according to claim 1, which is a mixture of two types of agents.
3. The antifouling antifouling paint for aquatic organisms according to claim 1 or 2, wherein the mixed material contains 5 to 45 weight percent of fly ash crushed to 1 to 20 microns.
The ship bottom antifouling paint comprises 3 to 5 weight percent zinc, 25 to 30 weight percent cuprous oxide, 3 to 5 weight percent titanium, 3 to 5 weight percent ferric oxide, and 9 The antifouling antifouling paint for aquatic organisms according to any one of claims 1 to 3, comprising 10 weight percent naphtha, 14 to 15 weight percent ethylbenzene, and 5 to 10 weight percent xylene. .
  5. The antifouling antifouling paint for aquatic organisms according to claim 1, wherein the mixed material is blended in an amount of 3 to 5% by weight based on the ship bottom antifouling paint.

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