JPH0565435A - Pigment for preventing adhesion of aquatic life - Google Patents

Abstract

PURPOSE:To obtain the subject pigment having chemical, electrical, physical and physiological composite repelling action against aquatic life by using two or more kinds of metal powder having different ionization tendencies in a state supported on a water-absorbing resin. CONSTITUTION:Two or more kinds of metal powder having different ionization tendencies, preferably copper powder 2 and silver powder 3, are supported on a water-absorbing resin (preferably polyvinyl alcohol 5) and used as essential components for the objective pigment to be kneaded into a paint or fiber raw material for preventing the adhesion of aquatic line such as barnacle and sea mussel to ship bottom, port facilities, fish preserve, etc. The polyvinyl alcohol preferably has a saponification degree of >=98.5mol% and a polymerization degree of <=1,000.

Description

Detailed Description of the Invention

[0001]

[Object of the Invention]

BACKGROUND OF THE INVENTION The present invention can be used by kneading with a paint or a fiber raw material applied to prevent adhesion of aquatic organisms such as barnacles and mussels to ship bottoms, harbor facilities, and cages. Regarding pigments.

[0002]

BACKGROUND OF THE INVENTION Barnacles, mussels, etc. adhere to and live on seawater such as ships and various port facilities, or fishing facilities such as fishing nets and cages. It causes deterioration of sex. For this reason, fibers containing paints and repellent substances that have been applied to the ship bottom to prevent the adhesion of these aquatic organisms have been developed. However, the effect of controlling aquatic organisms by them has not always been satisfactory, and in addition, since many of these paints and the like contain tin compounds, the elution and diffusion of these compounds causes the surrounding marine area to be affected. The pollution of marine life is also pointed out. Under such circumstances, the present applicant has already confirmed that the inclusion of several kinds of substances in the paint component and the fiber component has repellent effect for each.

[0003]

[Technical Items Attempted to Develop] The present invention has been made in view of such a background, and if it is used by mixing it with an existing paint or fiber raw material, it is chemically, electrically, physically or physiologically used. This is an attempt to develop a pigment that exhibits a comprehensive repellent effect.

[0004]

[Constitution of the invention]

[Means for Achieving the Object] That is, the first invention of the present application is a pigment for preventing adhesion of aquatic organisms, wherein two or more kinds of metal powders having different ionization tendencies are contained in a pigment component in a state of being supported by a water-absorbent resin. It is characterized by being included.

In addition to the above requirements, the second invention of the present invention is characterized in that the two or more kinds of metal powders having different ionization tendencies are copper powder and silver powder. It consists of

Furthermore, the third invention of the present application, the pigment for preventing adhesion of aquatic organisms, is characterized in that copper powder and carbon black are contained in the pigment component in a state of being supported by a water-absorbent resin. Is.

Furthermore, the pigment for preventing adhesion of aquatic organisms, which is the fourth invention of the present application, is characterized in that, in addition to the above-mentioned requirements, the water-absorbent resin is polyvinyl alcohol.

In addition to the above requirements, the polyvinyl alcohol according to the fifth invention of the present application has a saponification degree of 98.5 mol% or more and a polymerization degree of 1000 or less. It is characterized by being.

In addition to the above requirements, the sixth aspect of the present invention is the pigment for preventing adhesion of aquatic organisms. The polyvinyl alcohol has a saponification degree of 78.5 to 81.5 m.
It is characterized by having a degree of polymerization of 1500 or more in ol%. The above objects are achieved by these inventions.

The present invention will be specifically described below. First, in the present invention, the two or more kinds of metal powders having different ionization tendencies are powders obtained by selecting any two or more kinds of metals from the ionization series shown below. Li>Cs>K>Ba>Sr>Ca>Na>Mg> Be
>Al>Mn>Zn>Cr>Fe>Cd>Co>Ni>
Sn>Pb>(H)>Sb>Cu>Hg>Ag>Pt>
Au Among these combinations, the most preferable combination of metals is copper and silver in view of the effect of preventing adhesion of aquatic organisms and economy. Incidentally, two or more kinds of metal powders having different ionization tendencies are mixed in the electrolyte to form a battery and generate a local current. This point will be specifically described in the section of action. It should be noted that any metal not listed in the above-mentioned ionization series may be used.

Further, in order to obtain such a local current between the two kinds of metals, it is not always necessary to combine the metals, but a combination of the metal and the non-metal having conductivity may be used. .. Among these combinations, the most preferable combination is copper powder and carbon black in consideration of the effect of preventing adhesion of aquatic organisms and economy.

Next, as the water-absorbent resin, polyvinyl alcohol, sodium polyacrylate, methylcellulose, carboxymethylcellulose, polyethylene oxide, polyvinylpyrrolidone, acrylic acid amide, gelatin, glue, casein, polypeptide, starch, cellulose, dextrin, Examples thereof include water-soluble resins such as albumin, soybean protein, gum arabic, gum tragacanth, funori, agar, and sodium alginate, but are not limited thereto.

In addition to these, saponified vinyl acetate-methyl acrylate copolymer, vinyl alcohol-acrylic acid salt copolymer, acrylic acid-acrylic acid ester copolymer, polyacrylonitrile-based saponified product, starch-acrylonitrile A super absorbent resin such as a graft copolymer or a starch-acrylic acid copolymer may be applied.

Incidentally, the action of the water-absorbent resin is that it absorbs seawater and gels in a state of carrying carbon black with two or more kinds of metals or copper powders having different ionization propensities, and between two or more kinds of metals or copper powder. The electron e ⁻ can be transferred between the carbon black and the carbon black, and at the same time, the water absorbent resin itself has a function of preventing adhesion of aquatic organisms due to slimming.
These points will be described in detail in the section of the operation of the invention.

Among the water-absorbent resins, particularly polyvinyl alcohol, the degree of polymerization and the degree of saponification can be easily adjusted, and the life of the anti-adhesion effect can be adjusted by adjusting these.

Table 1 shows Gosenol manufactured by Nippon Synthetic Chemical Co., Ltd., which has various grades of polyvinyl alcohol depending on the combination of the degree of polymerization and the degree of saponification, among the products that are currently on the market and easily available. In the table, the degree of polymerization L indicates a degree of polymerization of 1000 or less, and M indicates a degree of polymerization of 1000.
.About.1500 and H means a degree of polymerization of 1500 or more, and in the table, the degree K of saponification is indicated by K.
1.5 mol%), A is a partially saponified type (86.5-8)
9.0 mol%), G is a completely saponified type (98.4-9)
7.7 mol%) and N are completely saponified (99.0 to 1)
00 mol%) is meant.

[0017]

[Table 1]

Considering the life of the adhesion preventing effect of aquatic organisms and manufacturing problems, the most suitable polyvinyl alcohol for use in the present invention in Table 1 is the polymerization degree L.
(Polymerization degree 1000 or less), Saponification degree N (99.0-10)
It has a degree of polymerization of H (degree of polymerization of 15
00 or more), saponification degree K (78.5 to 81.5 mol)
%) Position is the next most appropriate position. That is, the degree of saponification is large and the degree of polymerization is small, or the degree of saponification is small,
Polyvinyl alcohol having a high degree of polymerization is preferred for application to the present invention.

In Table 1, polyvinyl alcohol in the region around the upper left corner centering on the degree of polymerization L and the degree of saponification K is easily dissolved in water, and therefore the effect of preventing adhesion does not last long,
Further, polyvinyl alcohol in the area around the lower right corner centering on the degree of polymerization H and the degree of saponification N has the drawbacks that it is very difficult to dissolve in water and difficult to powder.

Next, the structure of the pigment for preventing adhesion of aquatic organisms according to the present invention will be described, and the manufacturing method thereof will be briefly described. As shown in FIG. 1, the anti-adhesion pigment 1 has a form in which copper powder 2, silver powder 3 or carbon black 4 is carried on a water absorbent resin. That is, first, what is shown in FIGS. 1 (a) and 1 (b) is one in which copper powder 2 and silver powder 3 or carbon black 4 are covered with polyvinyl alcohol 5 which is a water-absorbent resin and carried, respectively. In (c) and (d), copper powder 2 and silver powder 3 or copper powder 2 and carbon black 4 are covered together with polyvinyl alcohol 5 and carried.

The method for producing the anti-adhesion pigment of each embodiment will be described below by taking a combination of copper and silver (FIGS. 1 (a) and 1 (c)) as an example. In principle, the manufacturing method is the same in the case of a combination of two or more kinds of metals having different ionization tendencies other than the combination of copper and silver or the combination of copper and carbon black.

First, in the anti-adhesion pigment of the form shown in FIG. 1A, copper powder 2 and silver powder 3 are dispersed in different aqueous solutions of polyvinyl alcohol 5. After that, the copper powder 2 and the silver powder 3 are taken out, respectively, and heated and dried to form the particles in which the surfaces of the copper powder 2 and the silver powder 3 are covered with the polyvinyl alcohol 5, respectively. An anti-adhesion pigment 1 having the form shown is obtained. It should be noted that the polyvinyl alcohol 5 mixed with the copper powder 2 and the silver powder 3 may be used as the adhesion preventing pigment 1 as it is. Incidentally, when such a pigment is mixed in the paint, the anti-adhesion pigment 1 having the form shown in FIG. 1 (a) is present in the paint.

Furthermore, in the anti-adhesion pigment of the form shown in FIG. 1 (c), copper powder 2 and silver powder 3 are dispersed together in polyvinyl alcohol 5, or copper powder 2 and silver powder 3 are mixed in advance. Then, this is dispersed in polyvinyl alcohol 5. Then, the particles coated with the polyvinyl alcohol 5 together with the copper powder 2 and the silver powder 3 are taken out from the polyvinyl alcohol 5, and the particles are heated and dried to obtain the adhesion preventing pigment 1. In the above production, when the copper powder 2 and the silver powder 3 are mixed and dispersed in the polyvinyl alcohol 5, an appropriate dispersing device such as a porcelain ball mill or a centrifugal grind mill is used.

[0024]

According to the present invention, when a paint containing an anti-adhesion pigment is applied to, for example, the bottom of a ship, and the applied surface comes into contact with seawater, the adhesion of each of the forms shown in FIGS. In the preventive pigment, the repellent effect by accelerating the elution of metal ions, the repellent effect by the generated current, and the repellent effect by the modification of seawater components act synergistically to exert the repellent effect of aquatic organisms. If polyvinyl alcohol is included in the pigment,
Furthermore, the self-cleaning effect of the water-absorbent resin is exerted, and the life of the adhesion preventing effect can be adjusted by adjusting the saponification degree and the polymerization degree as described above. Each of these effects will be specifically described below.

<Repellent effect by promoting elution of metal ions>
The metal partially elutes as metal ions in the electrolyte solution,
The balance of Me⇔Me ^{n +} + ne ⁻ is maintained. However, in the same electrolyte solution, if there is a chemical substance with a smaller ionization tendency or a higher electron accepting property than this metal,
This substance receives the electron e ⁻ emitted from the metal, and a series of reactions such as giving electrons to chlorine ions in seawater to generate chlorine gas proceed, so that Me⇔M
progression to the right is promoted equilibrium collapses of ^- e n ^{+ +} ne. Therefore, the elution of metal ions into the electrolyte solution is promoted, and the metal ions are continuously supplied, so that the metal ions exert a continuous repellent effect on aquatic organisms.

Particularly when the metal is copper, Cu↔Cu ²⁺ + 2e ⁻ due to the presence of silver or carbon black.
The reaction proceeds to the right, and the repellent effect of aquatic organisms due to copper ions is continuously exerted.

In the anti-adhesion pigment of the form shown in FIGS. 1 (a) and 1 (b), the polyvinyl alcohol covers the copper and the metal or carbon black having a smaller ionization tendency than the copper. The movement of electrons is controlled by the probability that copper and a metal or carbon black, which has a smaller ionization tendency than copper, meet each other. On the other hand,
In the anti-adhesion pigments of the forms shown in (c) and (d), since copper and a metal having a smaller ionization tendency than copper or carbon black are carried on the same polyvinyl alcohol,
As soon as polyvinyl alcohol absorbs seawater, the electrons move immediately to facilitate the elution of copper ions. Incidentally, in FIGS. 1 (c) and 1 (d), copper powder 2 and silver powder 3 are used.
Are described separately from each other, but the copper powder 2 and the silver powder 3 may be in contact with each other. An alloy of copper and silver, for example, may be used as an example of such a contact form.

<Repelling Effect by Generated Current> In the situation where the elution of copper ions is promoted as described above, the side of the metal (for example, silver) in which the electrons emitted by the ionization of copper have a smaller ionization tendency than copper , And gives electrons to chlorine ions in seawater to generate chlorine. Such an action is a kind of battery action, and an electric current is flowing between two or more kinds of metals having different ionization tendencies.
This current acts as a repellent for aquatic life. Further, chlorine and the like generated on the side of the metal having a small ionization tendency that serves as an anode also repels aquatic organisms.

In this effect as well, similar to the repellent effect by promoting the elution of metal ions, the generation of electric current is as shown in FIG.
In the anti-adhesion pigments of the forms shown in (a) and (b), the anti-adhesion pigments of the forms shown in FIGS. 1 (c) and (d) are dominated by the probability that copper and a metal having a greater ionization tendency than copper will meet. Then, as soon as polyvinyl alcohol absorbs seawater, electrons move and current is generated.

<A repellent effect due to modification of seawater component> The current generated as described above modifies the seawater component by electrolysis or the like. In addition, chlorine and the like generated on the metal side, which has a smaller ionization tendency to serve as an anode, is also dissolved in the seawater component, so that the composition of the surrounding seawater changes. Due to such changes in the seawater environment, it becomes inconvenient for aquatic organisms to carry out physiological phenomena, and as a result, aquatic organisms can be repelled.

<Self-cleaning effect of polyvinyl alcohol> When polyvinyl alcohol absorbs seawater,
The surface is slimy and aquatic organisms are physically difficult to attach due to the slime. In addition, FIG.
In the anti-adhesion pigment of each form (d), polyvinyl alcohol is gradually self-polished, whereby the elution rate of copper ions is suppressed and gradually diffused into seawater, and the repellent effect can be sustained. ..

Further, the saponification degree of polyvinyl alcohol is 9
8.5 mol% or more or 78.5 to 81.5 mol%, and correspondingly the degree of polymerization is 1000 or less or 1500
In the case of the above, the repellent effect can be maintained for a long time, and the adhesion preventing pigment can be easily produced.

[0033]

EXAMPLES Mitsui Mining & Smelting Co., Ltd. production of copper powder as a different metal ionization tendency (MF-D ₃ average particle diameter 13Myu)
And Fukuda Metal Foil Powder Co., Ltd. silver powder Silcoat Agc-
B was applied. As the carbon black, DONA CARBO manufactured by Dainippon Ink and Chemicals, Inc. was applied. Further, polyvinyl alcohol is Goshenol GM-14 (saponification degree G, degree of polymerization M) manufactured by Nippon Synthetic Chemical Industry Co., Ltd. in Examples 1 to 4, and Gosenol KH-17 manufactured by the same in Example 5.
(Saponification degree K, degree of polymerization H), and in Example 6, Goshenol NL-05 (saponification degree N, degree of polymerization L) manufactured by the same company was used, respectively.

Example 1 Gohsenol GM-14-1
Two 0% aqueous solutions were prepared, 1 part of copper powder was mixed with 9 parts of one aqueous solution, 1 part of silver powder was mixed with 9 parts of the other aqueous solution, and these were dried with stirring. Is ground with a coffee mill and a ball mill. The particles thus crushed are sieved to obtain a particle size of 100 μm.
Hereinafter, the anti-adhesion pigment of Example 1 is used.

<Example 2> 1 of Gohsenol GM-14
Two 0% aqueous solutions were prepared, 1 part of copper powder was mixed with 9 parts of one aqueous solution, 1 part of carbon black was mixed with 9 parts of the other aqueous solution, and these were dried with stirring. Grind things with a coffee mill and a ball mill. The thus pulverized product is sieved to have a particle size of 100 μm or less to obtain the anti-adhesion pigment of Example 2.

<Example 3> 1 of Gohsenol GM-14
Prepare a 0% aqueous solution and add 1 part of copper powder to 18 parts of this aqueous solution.
Parts and 1 part of silver powder were mixed and dried with stirring, and then pulverized with a coffee mill and a ball mill. The powder thus crushed is sieved to obtain a particle size of 100.
The anti-adhesion pigment of Example 3 was made to have μ or less.

Example 4 1 of Gohsenol GM-14
Prepare a 0% aqueous solution and add 1 part of copper powder to 18 parts of this aqueous solution.
Parts and 1 part of carbon black are mixed and dried while being stirred, and then ground with a coffee mill and a ball mill. The thus pulverized product is sieved to have a particle size of 100 μm or less to obtain the anti-adhesion pigment of Example 4.

Example 5 1 of Gohsenol KH-17
Prepare a 0% aqueous solution and add 1 part of copper powder to 18 parts of this aqueous solution.
Parts and 1 part of silver powder were mixed and dried with stirring, and then pulverized with a coffee mill and a ball mill. The powder thus crushed is sieved to obtain a particle size of 100.
The anti-adhesion pigment of Example 5 is made to have μ or less.

Example 6 1 of Gohsenol NL-05
Prepare a 0% aqueous solution and add 1 part of copper powder to 18 parts of this aqueous solution.
Parts and 1 part of silver powder were mixed and dried with stirring, and then pulverized with a coffee mill and a ball mill. The powder thus crushed is sieved to obtain a particle size of 100.
The pigment for preventing adhesion of Example 6 is set to have a value of μ or less.

[0040]

The present invention has the constitution as described above, and the following is obtained by a marine test using paints mixed with the anti-adhesion pigment of each example or contained in fibers as follows. The effect was confirmed. In the marine test, 20 parts of the anti-adhesion pigment of each example was kneaded with 30 parts of acrylic resin paint and applied to a test plate, and 20 parts of the anti-adhesion pigment of each example was melted nylon. The mixture was kneaded into 100 parts of 6 and pelletized into a predetermined shape, which was melt-extruded with an extruder at about 200 to 220 ° C., cooled, and then reheated to about 100 ° C. and stretched. Fibers, which are made up of 60-strand ropes, are each submerged in the sea for a certain period of time to observe the aquatic organisms, especially the algae adhesion state. The results are shown in Table 2 for paints and Table 3 for fibers.

In addition to algae, there are aquatic animals such as mussels and other shellfish as aquatic organisms. However, since these aquatic animals breed when the spores of algae adhere to the bottom of the ship, etc., algae grow on the test plate. When attached, spores are likely to be attached, and therefore shellfish are easily propagated. On the contrary, when algae is not easily attached, it can be determined that spores are not attached and shellfish and the like are not easily propagated.

[0042]

[Table 2]

[0043]

[Table 3]

Tables 2 and 3 show the results of Examples 1 to 1 in comparison with blanks coated with paints without anti-adhesive pigments according to the invention or with ropes consisting of fibers without anti-adhesive pigments according to the invention. In all of the six cases, the timing of algae attachment is late, and it is clearly recognized that the pigment for preventing attachment of aquatic organisms according to the present invention has a repellent effect on aquatic organisms.

[Brief description of drawings]

FIG. 1 is a skeleton explanatory view showing various examples of the pigment for preventing adhesion of aquatic organisms of the present invention.

[Explanation of symbols]

 1 Anti-adhesion pigment 2 Copper powder 3 Silver powder 4 Carbon black 5 Polyvinyl alcohol

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁵ Identification code Internal reference number FI Technical display location C09C 3/10 PBX 6904-4J C09D 5/14 PQJ 6904-4J

Claims (6)

[Claims] 1. A pigment for preventing adhesion of aquatic organisms, wherein two or more kinds of metal powders having different ionization propensities are contained in a pigment component in a state of being supported by a water absorbent resin. 2. The pigment for preventing adhesion of aquatic organisms according to claim 1, wherein the two or more kinds of metal powders having different ionization tendencies are copper powder and silver powder. 3. A pigment for preventing adhesion of aquatic organisms, characterized in that copper powder and carbon black are contained in a pigment component in a state of being supported by a water absorbent resin. 4. The pigment for preventing adhesion of aquatic organisms according to claim 1, 2 or 3, wherein the water-absorbent resin is polyvinyl alcohol. 5. The pigment for preventing adhesion of aquatic organisms according to claim 4, wherein the polyvinyl alcohol has a saponification degree of 98.5 mol% or more and a polymerization degree of 1000 or less. 6. The polyvinyl alcohol has a saponification degree of 78.5 to 81.5 mol% and a polymerization degree of 1500.
The above is the pigment for preventing adhesion of aquatic organisms according to claim 4.