JPH04325571A - Material for preventing deposition of aquatic organism - Google Patents

Abstract

PURPOSE:To prepare the title material which prevents the deposition of aquatic organisms such as barancles on a ship bottom, a port facility, etc., by incorporating a specific substance into a coating component. CONSTITUTION:Tourmaline is incorporated into a coating component pref. in combination with at least one metal (e.g. powdered copper) and/or PVA to give the title materials.

Description

[Detailed description of the invention]

0001

[Purpose of the invention]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a material for preventing aquatic organisms such as barnacles and mussels from adhering to ship bottoms, port facilities, fish preserves, etc.

0002

[Background of the Invention] Barnacles, mussels, etc. live on things that are exposed to seawater, such as ships, various port facilities, fishing nets, fish pens, and other fish-catching facilities. It causes sexual deterioration. For this reason, paints have been developed that can be applied to the bottom of ships to prevent these aquatic organisms from adhering to them. However, the effectiveness of these paints in controlling aquatic organisms has not always been satisfactory, and in addition, many of these paints contain tin compounds, which can cause damage to surrounding sea areas and other areas due to their elution and diffusion. Contamination of marine life has also been pointed out. In addition, under these circumstances, the present applicant has already developed several types of paints, but the applicant has filed an application focusing on the ability to prevent aquatic organisms from adhering to them by electrically stimulating them. (Patent Application No. 63-204420).

0003

[Technical matters for which the development was attempted] The present invention was developed in view of this background, and is intended to prevent aquatic organisms from adhering to the bottom of a ship, etc. due to a partial change in the environment due to electrical stimulation or electrolysis. This is an attempt to develop a material that prevents aquatic organisms from adhering to it.

0004

[Structure of the invention]

[Means for achieving the object] That is, the first invention of the present application, which is a material for preventing the adhesion of aquatic organisms, is characterized by containing tourmaline in the paint component.

[0005] Further, the second invention of the present application, a material for preventing the adhesion of aquatic organisms, contains tourmaline in the paint component, and also contains one or more metals and/or polyvinyl alcohol. It is characterized by the following.

[0006] Further, the third invention of the present application, which is a material for preventing adhesion of aquatic organisms, has, in addition to the above-mentioned requirements, that the tourmaline is supported alone or together with one or more metals on a water-absorbing resin. It is characterized by the following.

[0007] Furthermore, the fourth invention of the present application is a material for preventing adhesion of aquatic organisms, in which, in addition to the above-mentioned requirements, the tourmaline is supported alone or together with one or more metals in a porous fine powder. It is characterized by this. These inventions attempt to achieve the above object.

The present invention will be explained in detail below. First, tourmaline, which is a characteristic component of the present invention, will be explained. The general formula of the chemical composition of this product is Wx3B3Al3(Al
Si2O9)3(O,OH,F)4 represented (W=
Na, Ca, . As the name suggests, these minerals exhibit remarkable electrical properties, and they easily generate electricity especially when heated, rubbed, etc., and some produce positive electricity at one end and negative electricity at the other end. The hemi-polar image is revealed by the shape of the ends, the difference in color and the pyroelectricity, and it also shows very strong dichroism. The cleavage is incomplete, the hardness is 7-7.5, the specific gravity is 2.9-3.2, and it has a glassy luster.

[0009] This substance is widely found in crystalline schist, gneiss, contact metamorphic rocks, etc., and often forms megacrystals in pegmatites of granite. Specifically, Lithia Tourmaline Na (L
i, Al)3Al6(BO3)3Si6O18(OH)
4. Magnesium tourmaline Na Mg3Al6(BO3)3Si
6O18(OH)4, Iron Tourmaline Na Fe3+2Al
6(BO3)3Si6O18(OH)9, etc., and their beautiful colors are used not only as jewelry but also as polarizing plates. Representative production areas in Japan include the Obira Mine in Oita Prefecture and the Naegi region in Gifu Prefecture.

[0010] The present invention aims to prevent aquatic organisms from adhering to the paint by electrical stimulation by including tourmaline having such electrical properties in the paint component. In this way, when tourmaline is contained alone in a paint component, it has the following effects. In other words, a tourmaline generates positive electricity at one end and negative electricity at the other end, and can be thought of as a type of battery in itself. Therefore, if this substance is included in the paint component and the parts that become each pole come out of the paint film and are exposed to seawater, a phenomenon similar to that of energizing seawater will occur and the nearby seawater will be electrolyzed. Ru. In particular, near both ends of tourmaline, seawater components differ from the normal equilibrium state, and it is thought that aquatic organisms avoid this state.

Furthermore, in the present invention, in order to make the electrical repellent effect of tourmaline more effective, polyvinyl alcohol or metal can be added to the paint components. That is, when polyvinyl alcohol is mixed with tourmaline into a paint, the possibility that polyvinyl alcohol, which is a water-absorbing resin, will take in seawater increases, and the possibility that tourmaline will be exposed to seawater increases accordingly. This makes it easier for seawater to undergo electrolysis, and once polyvinyl alcohol takes in seawater, it is difficult to replace the seawater in that area, so that area remains in a state where its composition has changed due to electrolysis. It is possible to easily maintain the repellent effect.

[0012] Furthermore, when a metal is mixed with tourmaline into a paint, in addition to the electrolytic action described above, a repellent effect on aquatic organisms is expected due to the electric current generated between the tourmaline and the ionized metal in seawater. can. Note that the metal is not limited to one type, and two or more types of metals having different ionization tendencies may be mixed. Incidentally, in this case, not only current flows between tourmaline and various metals, but also current flows between different types of metals, forming a battery having an electromotive force corresponding to the difference in standard electrode potential. Furthermore, when an electric current flows between a metal and a tourmaline, if the metal has a relatively large tendency to ionize and the ions are repellent to aquatic organisms, the tourmaline side accepts electrons. Therefore, metal ionization occurs continuously without reaching an equilibrium state. As a result, the repellent effect of the metal ions themselves can be exerted continuously.

Next, the state of dispersion of tourmaline in the paint components will be explained. Tourmaline may be crushed into powder or granules and mixed and dispersed in the paint as it is, but tourmaline may be used alone or together with one or more metals in water-absorbing resin or porous resin. It may also be made into a fine powder and then dispersed into the paint components. This point will be specifically explained below. First, regarding the effect when a water-absorbing resin supports tourmaline, etc., when the water-absorbing resin absorbs seawater, the possibility that the tourmaline is exposed to seawater becomes very high, and the electrolytic action of the seawater takes place accordingly. It becomes easier to fall. In addition, when the water-absorbing resin takes in seawater, it becomes difficult for the seawater in that area to be replaced, and the area is likely to remain in a state where its composition has changed due to electrolysis, making it possible to maintain the repellent effect. In addition, compared to the case where tourmaline and polyvinyl alcohol are included together in the paint component,
When tourmaline is supported on a water-absorbing resin, there is a much higher probability that the tourmaline will come into contact with seawater, so the above-mentioned effect will be much more pronounced.

[0014] In addition, when tourmaline or the like is supported on porous fine powder, the pores of the porous fine powder that do not support tourmaline or metal tend to take in seawater due to capillary action. There is a high probability that tourmaline, etc. will come into contact with seawater.

Next, a method for producing an anti-adhesion material containing tourmaline supported on a water-absorbing resin will be explained. This method involves placing tourmaline granules in a water-absorbing resin, then taking them out and heating and drying them to create granules with the surface of the tourmaline covered with the water-absorbing resin. There are two methods: mixing and dispersing tourmaline into the paint components, and dispersing tourmaline particles in a water-absorbing resin solution, and then mixing and dispersing them as they are into the paint components. I don't mind.

[0016] When preparing an anti-adhesion material containing one or more metals in addition to tourmaline, the tourmaline particles and metal powder are mixed and this is dispersed in a water-absorbing resin. Alternatively, the tourmaline and metal powder may be dispersed in separate water-absorbing resins. When the material prepared by the former method is mixed and dispersed in paint components, tourmaline E and metal powder M are present in dispersed droplets B of the same water-absorbing resin, as shown in Figure 1(a). I will do it. Incidentally, when tourmaline and metal powder are supported in such a state, when the water-absorbing resin absorbs seawater, electrons are transferred between the tourmaline and the metal in one dispersed droplet. Therefore, it becomes easier for current to flow, and the electrolytic action, energization stimulation action, and continuous metal ionization action are promoted accordingly.

On the other hand, when the materials prepared by the latter method are separately mixed and dispersed in the paint components, tourmaline E and metal powder M are dispersed in different water-absorbing resins, as shown in FIG. 1(b). It will be present in drops B1 and B2. Incidentally, when tourmaline and metal powder are supported in such a state, when the water-absorbing resin absorbs seawater, different dispersed droplets B
Since no current will flow unless electrons are transferred between 1 and B2, the electrolytic action, energization stimulation action, and continuous metal ionization action will be less likely to occur. It is possible to prepare various kinds of materials in advance, select a suitable combination of tourmaline and metals from these according to the application, and mix them into the paint components, so there is a degree of freedom in the types of metals to be combined. Various anti-adhesion materials can be created as needed depending on the sustainability of the repellent effect and other characteristics.

The water-absorbing resins include polyvinyl alcohol, polyacrylic acid sorg, methylcellulose, carboxymethylcellulose, polyethylene oxide, polyvinylpyrrolidone, acrylamide, gelatin, glue, casein, polypeptide, starch, cellulose, dextrin, Examples include, but are not limited to, water-soluble resins such as albumin, soybean protein, gum arabic, gum tragacanth, funori, agar, and sodium alginate. In addition, saponified vinyl acetate-methyl acrylate copolymer, vinyl alcohol-acrylate copolymer, acrylic acid-acrylic acid ester copolymer, saponified polyacrylonitrile, starch
Highly absorbent resins such as acrylonitrile graft copolymers or starch-acrylic acid copolymers may also be applied.

Next, a method for supporting tourmaline alone or together with one or more metals on a porous fine powder and its effect will be explained. First of all, what is porous fine powder?
Generally, the particle size is about 0.1 μm to 100 μm, and the surface morphology of the particles is formed with various shapes of irregularities, holes, and grooves. Examples include nylon powder,
Examples include organic substances, inorganic substances, and metals such as polyethylene powder, acrylic powder, styrene powder, ABS powder, polypropylene powder, gelatin, various waxes, sulfur, copper powder, and silver powder.

[0020] As a method for supporting tourmaline or the like on the surface of such porous fine powder, a method of mechanical surface modification is applied. That is, while dispersing porous fine powder and tourmaline powder in the gas phase in the same processing chamber, mechanical and thermal energy, mainly impact force, is applied to these particles to form porous particles as shown in Figure 2. Tourmaline powder is buried or fixed on the surface of fine powder. Incidentally, methods such as sandblasting can be applied to this type of processing method, as well as Japanese Patent Application Laid-Open No. 62-83029.
No., JP-A-62-262737 and JP-A-62-29
The method described in No. 8443 etc. can be used. Examples of such processing machines include the Nara Hybridization System manufactured by Nara Kikai Seisakusho Co., Ltd. and the Angmill manufactured by Hosokawa Micron Co., Ltd.

[0021] This mechanical surface modification method is also applied when the porous fine powder supports one or more metal powders together with tourmaline, but in this case, tourmaline powder and metal powder are supported on the porous fine powder. In this method, only the tourmaline powder or metal powder is first subjected to mechanical surface modification treatment to be supported, and then the porous fine powder is coated with the other powder. Possible methods include a method in which powder is further supported, and a method in which tourmaline and metal powder are separately supported on separate porous fine powders. Although it is not necessarily clear how tourmaline powder and metal powder are supported on porous fine powder due to differences in these methods, the point is that tourmaline powder E is supported on one porous fine powder S as shown in Fig. 3. It is preferable that both the powder and the metal powder M be supported.

Incidentally, if tourmaline supported on porous fine powder is mixed into the paint component, multiple tourmaline powders or multiple metal powders will be supported on one porous fine powder. Since the comrades or the tourmaline and the metal are present in close proximity, the electrolytic action, energization stimulation action, and continuous ionization action of the metal are promoted accordingly. Furthermore, when tourmaline or metal is a fine powder, it tends to aggregate, so if it is mixed into a paint component as it is, its dispersion in the paint will be poor. During storage, such anti-adhesive materials may cause the battery function to be depleted in the agglomerated fine powder, or if applied to the bottom of a ship, the battery function may not be uniform, and the effect of repelling aquatic organisms may vary depending on the location. There are negative effects. In such a case, if a fine powder such as tourmaline is supported on a porous fine powder, agglomeration of the fine powders will be eliminated, and the state of dispersion of tourmaline and metal will be improved, thereby eliminating the above-mentioned disadvantages. In addition, it is also possible to have tourmaline supported on a porous fine powder and then further supported on an absorbent resin, or conversely, it is also possible to have tourmaline supported on an absorbent resin and then supported on a porous fine powder. be.

Next, the paint components applied to the present invention can have the same composition as those of ordinary ship bottom antifouling paints. That is, it is a mixture of resin components, extender pigments, coloring pigments, plasticizers, additives, etc. in appropriate proportions as necessary. Here, resin components include, for example, chlorinated rubber, vinyl chloride, vinyl chloride/vinyl propionate, chlorinated polyolefin, acrylic resin, styrene/butadiene, rosin, rosin ester, rosin soap, etc., and extender pigments include calcium carbonate. , talc, silica powder, barium sulfate, clay, etc. Furthermore, the colored pigments include titanium white, Bengara, the plasticizers include dioctyl phthalate, tricresyl phosphate, parahin chloride, and the additives include suspending agents, anti-sagging agents, and leveling agents.

[0024]

Effect of the Invention In the present invention, when the anti-adhesion material applied to the bottom of a ship comes into contact with seawater, this seawater acts as a medium to prevent tourmaline particles contained in the anti-adhesion material, or between tourmaline stones and metals. A current flows through the metal, and the resulting electrolytic action, current stimulation action, and repellent action of the metal itself due to continuous ionization of the metal prevent aquatic organisms from adhering to it. In addition, the anti-adhesion material of the present invention can be applied not only to the sea but also to buildings, piping, etc. used in lakes, rivers, power plants, and dams. It acts as a medium and has the same effect as when used in seawater.

[0025]

【Example】

<Example I> Anti-adhesion material I was prepared by mixing 50 parts of tourmaline crushed using a coffee mill and a ball mill with 50 parts of acrylic resin.

<Example II> 10 parts of tourmaline ground using a coffee mill and a ball mill and 10 parts of polyvinyl alcohol powder were mixed with 60 parts of acrylic resin to form adhesion prevention material II. Created.

<Example III> 10 parts of tourmaline ground using a coffee mill and a ball mill, and 10 parts of copper powder
Adhesion prevention material III was prepared by mixing 60 parts of acrylic resin with 60 parts of acrylic resin.

<Example IV> Two parts of tourmaline crushed to some extent are mixed into 50 parts of a 10% polyvinyl alcohol aqueous solution, dried while stirring, and further crushed using a coffee mill and a ball mill. . 40 parts of this pulverized material was mixed and dispersed in 60 parts of acrylic resin to prepare adhesion prevention material IV.

<Example V> 1 part of tourmaline crushed to some extent and 1 part of copper powder were mixed into 50 parts of a 10% aqueous solution of polyvinyl alcohol, and the mixture was dried while stirring, and the mixture was further milled in a coffee mill. and a ball mill. Adhesion prevention material V was prepared by mixing and dispersing 40 parts of this pulverized material in 60 parts of acrylic resin.

[0030] The acrylic resin is Acridic A198xB manufactured by Dainippon Ink Chemical Co., Ltd., and the polyvinyl alcohol powder is OKS911 manufactured by Nippon Gosei Kagaku Co., Ltd.
9. Copper powder is copper powder (MF-D) manufactured by Mitsui Mining & Smelting Co., Ltd.
3 average particle size: 13 μm) and Gohsenol GM-14 manufactured by Nippon Gosei Kagaku Co., Ltd. was used as the polyvinyl alcohol aqueous solution.

[0031]

[Effects of the Invention] The present invention has the configuration described above, and the following effects have been confirmed. First, we will explain the plate test, beaker test, algae adhesion test, and ocean test, which are test methods for confirming effectiveness.

[0032] The plate test was carried out using a polyester F. R. P. On the substrate 1, the aquatic organism adhesion prevention material T of the present invention is applied in a circular shape with a diameter of 5 cm, and a purple mussel A with a shell length of 3 cm is horizontally fixed approximately in the center of the circle, and byssus a from this mussel is attached. This is to see how things are going. Additionally, along with barnacles, mussels are representative aquatic organisms used in adhesion tests.
This organism was used in the experiment because it easily attaches to marine structures. The specific method for fixing the mussel A is to place it on the central part coated with the anti-adhesion material T for 1 to 2 m.
The mussels are fixed using instant adhesive or the like with a piece of rubber having a thickness of m thick interposed between them, and placed in a seawater tank for about a week to observe how the byssus threads settle.

In addition, the beaker test was conducted using a beaker V coated with an anti-adhesion material T on the inner peripheral surface and inner bottom surface, as shown in FIG.
Seawater is poured into the beaker, a mussel A is placed at the bottom of the beaker, and the state of attachment of its bysus threads is observed. This test is carried out in conjunction with the plate test as a kind of double check.In particular, by not fixing the mussels, the degree of freedom of the mussels is increased, and it is possible to observe the settlement status of the mussels in a more realistic environment. it makes sense.

Furthermore, the algae adhesion test was conducted as shown in FIG.
A plate P made of FRP measuring 100 x 1.5 mm was coated with an anti-adhesion material T, and was submerged together with algae U in a flask F filled with seawater for over a month to determine the status of the adhesion of algae to the plate P. This is a test to observe. The significance of testing the status of algae adhesion is that shellfish that adhere to the bottom of a ship reproduce when spores adhere to the bottom of the ship, but if algae adheres to the bottom of the ship, spores are likely to adhere to it. On the other hand, if it is difficult for algae to adhere, spores will not adhere and it will be difficult for shellfish and the like to reproduce, so the effect of repelling aquatic organisms can be determined by looking at the state of algae adhesion.

Furthermore, in the ocean test, a test plate coated with an anti-adhesion material is submerged in the sea for one month or more, and the state of adhesion of aquatic organisms is observed. The number of samples for the plate test was 6, the number of samples for the beaker test was 4, and the number of samples for the algae adhesion test was 2. The results are shown in Table 1.

[0036]

[Table 1]

According to this, although adhesion of the byssus to the paint was observed in some examples of the plate test and beaker test, no algae adhesion was observed in any of the examples in the algae adhesion test, and No aquatic organisms were observed in the test. If we look at the above results comprehensively,
It is recognized that all of the anti-adhesion materials of Examples I to IV have a repellent effect on aquatic organisms.

[Brief explanation of drawings]

FIG. 1 is a skeletal diagram showing two examples of anti-adhesion materials in which tourmaline particles and metal powder are dispersed in an absorbent resin.

FIG. 2 is an explanatory diagram showing step-by-step the manufacturing process of an anti-adhesion material in which tourmaline particles are supported on the surface of porous fine powder.

FIG. 3 is an explanatory diagram showing step by step the manufacturing process of an anti-adhesion material in which tourmaline particles and metal powder are supported on the surface of porous fine powder.

FIG. 4 is a perspective view showing a plate test, which is a test method for the material for preventing adhesion of aquatic organisms according to the present invention.

FIG. 5 is a perspective view showing a beaker test, which is a testing method for the material for preventing adhesion of aquatic organisms according to the present invention.

FIG. 6 is a perspective view showing an algae adhesion test, which is a testing method for the material for preventing adhesion of aquatic organisms according to the present invention.

[Explanation of symbols]

1 F. R. P. substrate A Murasaki mussel a Byssus B Dispersed droplets B1 Dispersed droplet B2 Dispersed droplet E Tourmaline F flask M Metal powder P plate S Porous fine powder T　　　　　　　　　　Adhesion prevention material U Algae V Beaker

Claims (4)

[Claims] 1. A material for preventing adhesion of aquatic organisms, characterized in that the paint component contains tourmaline. 2. A material for preventing adhesion of aquatic organisms, characterized in that the paint component contains tourmaline, and also contains one or more metals and/or polyvinyl alcohol. 3. The material for preventing adhesion of aquatic organisms according to claim 1 or 2, wherein the tourmaline is supported alone or together with one or more metals on a water-absorbing resin. 4. The material for preventing adhesion of aquatic organisms according to claim 1 or 2, wherein the tourmaline is supported alone or together with one or more metals in a porous fine powder.