JPH0812906A - Coating composition - Google Patents

Abstract

PURPOSE:To obtain a coating compsn. which is nonpollutant and excellent in the prevention of attachment of harmful marine organisms by incorporating ground shells of bivalves or snails, a natural substance not affecting the environment at all, into a coating compsn. CONSTITUTION:Shells of bivalves (e.g. conch shells, abalones, or scallops) or snails are sorted, stripped of the outer skis, washed, dried, crushed with a ball mill, etc., pref. to an average particle size of serveral mm or lower, and incorporated into a coating compsn. pref. in a concn. of 1-50wt.%. The obtd. compsn. is applied to fishing nets for raising or fixing, materials such as floats or ropes for fishing nets, or underwater parts of a ship, thereby enabling the avoidance or prevention of attachment of harmful marine organisms (e.g. corn barnacle or moss animals) effectively for a long term.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION The present invention relates to a fish net for aquaculture or stationary, a material such as a float or a rope used for the fish net,
A coating composition that avoids or prevents the attachment of marine pests to submerged submerged parts of ships, parts that come into contact with seawater such as offshore structures and seawater introduction pipes, and is completely harmless to the environment and has a long-term effect. Regarding things.

[0002]

2. Description of the Related Art Fish nets for aquaculture or stationary, a bottom of a ship that is submerged in the sea, a part of a marine structure that is submerged in seawater, a part that comes into contact with seawater such as a seawater inlet pipe used for cooling water, etc. Since it is immersed in the sea for a long time, marine algae, barnacles, cerpra, bryozoans, molluscs, and other marine pests are heavily attached to the sea, which impedes economic operation and requires a lot of labor and effort to maintain them. The current situation is that it costs money.

Various studies and proposals have been made as measures against this, but conventionally, organotin polymers including organotin have been widely used. However, since organotin compounds are highly toxic to the environment and particularly have a high potential to accumulate in the environment, they are designated as Class 1 Specified Chemical Substances or Class 2 Specified Chemical Substances, their use in ship bottom paints is restricted, and fishnet antifouling is used. The use of agents has become banned.

Therefore, cuprous oxide, which has been used as a non-tin-based antifouling agent for a long time, has come to be widely used again. However, cuprous oxide is eluted in seawater to form copper ions or copper compounds. As a result, it may adversely affect the environment. For this reason, it does not contain heavy metals,
Alternatively, the advent of a low-pollution pest control agent having a low concentration of heavy metals has been desired, and various organic agents have been proposed.

For example, many compounds such as tetramethylthiuram disulfide, tetrachloroisophthalonitrile and zinc dimethyldithiocarbamate have been used, but a compound satisfactory in terms of antifouling property has not yet been found. It was never done. Further, the effects on the environment when these synthetic chemical substances are released into the environment have not been clarified yet, and it cannot be said that they are safer than organotin.

[0006]

In view of such circumstances, the present invention uses a natural product that has no influence on the environment,
It is an object of the present invention to provide a coating composition which is pollution-free and has a good ability to prevent adhesion to marine pests.

[0007]

Means for Solving the Problems As a result of intensive studies, the present inventors have conducted extensive studies for the purpose of providing a coating composition for controlling the adhesion of marine pests by a method that has no effect on the environment. It has been found that a coating composition containing a crushed product of a bivalve or conch shell has an action of repelling or preventing adhesion to marine pests.

Bivalves and snails naturally decompose after death.
These shells do not particularly contain physiologically active substances and do not adversely affect toxicity or the environment, but there are examples where the dried and crushed shells are used as Chinese herbs, fungicides and preservatives. . However, it is not theoretically substantiated, and thus has never been applied to paints. The present inventors have for the first time discovered the surprising fact that the adhesion of marine pests can be prevented by using bivalves and snails that are present in the sea and have no toxicity.

The bivalves and conchs used in the present invention include, for example, sharks, mussels, moss mosses, moss moss, holly mussels, pearl oysters, pearl oysters, abalone, clams, mussels, mussels, ) Turban shells, lamellae, snails, mametanis, centipedes, kawainas, uminina, mussels, mussels, mussels, bears, mussels, mussels, mussels, mussels, mussels, snails , Mussels, barnacles,
Scissors, mussels, lobsters, proboscis, damselfly, mussels, snails, snails, pseudonids, snails, mussels, mussels, bamboo shoots, pearl oysters, snails, snails, mussels Genus, pearl oysters, blue snails, mussels, mussels, mussels, mussels, pearl mussels, scallops, sea mussels, sea mussels, mussels, mussels,
Scribbles, oysters, pearl oysters, moss snails, moss snails, mussels, mussel,
Cockleups, clams, marsdales, clams, clams, mussels, mussels, mussels, snails, Trimodidae, mussels, snails, liquor snails, snails, giant snails , Beetle beetles, lichens, and nautilus.

In the present invention, a crushed product is obtained from the shell of these bivalves and conch, but the manufacturing method thereof is not particularly limited. Usually, after selecting bivalves and conch shells, removing the outer skin and washing, mortar, stone mill,
The particles may be pulverized with a pulverizer such as a ball mill, a hammer mill, and a crusher until the average particle diameter is usually several mm or less, more preferably a finer particle diameter. In the above washing, after washing with water, it is dried in the sun for a long period of time or subjected to an appropriate heat treatment, and an electrical method is used.
It is desirable to carry out a heating and baking treatment at a temperature of 00 ° C. or higher to almost completely remove the organic substances and facilitate the subsequent pulverization treatment.

The crushed product of bivalves and conch shells thus obtained is completely non-toxic, and when released into the environment, it naturally decomposes and does not pollute the ocean. Moreover, it shows a repellent effect with a very wide spectrum against marine pests, especially against large algae such as barnacles, serpla, squirts, bryozoans, stag beetles, and algae.
Exhibits a strong repellent effect equivalent to or better than cuprous oxide and tin compounds.

Therefore, a coating composition containing this kind of pulverized product can be designed as a non-toxic paint for preventing adhesion of marine pests, which is due to inhalation toxicity at the time of coating work and coating film in the sea. It is an epoch-making, eco-friendly paint that can eliminate the toxicity of fish after it is destroyed. It can also be added to an underwater pest control paint containing an existing known drug. In this case, since the content of the above drug can be reduced,
The toxicity is greatly reduced, and the paint has a lower toxicity than conventional paints.

As described above, the coating composition of the present invention is characterized by using a crushed product of a bivalve or conch shell as an active ingredient which repels or prevents the adhesion of marine pests. The amount of the above-mentioned pulverized product used can be appropriately set depending on the form of the coating material, purpose of use, and the like. Generally, 0.1 to 90% by weight in all paint components,
It is preferable to set it to 1 to 50% by weight.
As the film-forming material applied to this coating composition, those conventionally used can be widely used. Further, the method for producing the coating composition is not particularly limited, and it can be produced by a method that has been conventionally used in the technical field of coating production.

Among the film-forming products, particularly as a resin vehicle, vinyl chloride resin, vinyl acetate resin, chlorinated rubber resin, chlorinated polyethylene resin, chlorinated polypropylene resin, acrylic resin, styrene-butadiene resin,
Resins soluble in organic solvents such as polyester resin, epoxy resin, epoxy ester resin, polyamide resin, petroleum resin, silicone resin, wax, paraffin, rosin ester, rosin resin, tin, copper, zinc A resin containing a metal element such as tellurium, silicon, or germanium in its side chain can be used alone or in combination.

Other resin vehicles include, for example, acrylic emulsion resin, epoxy emulsion resin,
Vinyl acetate emulsion resin, epoxy ester resin,
Water-soluble resins such as polyester resins, alkyl vinyl copolymer resins, alkyd resins, urethane-modified polyester resins and urethane acrylic resins can also be used, and as disclosed in JP-A-60-500452. Various hydrolyzable resins and the like can also be used.

In addition to these resin vehicles, if necessary, conventionally known agents such as cuprous oxide, rhodan copper, dithiocarbamate type agents, and carbamers.
Drug, maleimide drug, isothiazolone drug,
Various antifouling agents known in the antifouling paint industry such as tetrachloroisophthalonitrile may be appropriately added.
When these agents are used in combination, they are not completely non-toxic, but they have lower toxicity than conventional agents alone, and a synergistic effect of antifouling performance can be expected. Further, a plasticizer such as silicone oil, polybutene, liquid paraffin, or tricresyl phosphite may be added. As other additives, a color pigment, an extender pigment, a solvent and the like can be contained at an arbitrary ratio.

[0017]

INDUSTRIAL APPLICABILITY In the present invention, by using a crushed product of a bivalve or conch shell as an active ingredient that repels or prevents the attachment of marine pests, it exhibits an excellent antifouling effect and, in the prior art, It is possible to provide a coating composition having high practical value, which is nontoxic and has no adverse effect on the environment.

[0018]

EXAMPLES Next, the outline of the present invention will be described with reference to Examples of the present invention and Comparative Examples. However, the present invention is not limited to these examples, and paints for controlling general marine pests are provided. The present invention can be carried out according to the prescription. The blending ratios in the following coating compositions are by weight unless otherwise specified. Further, crushed products A-1 to A-5 of bivalve or conch shells used in the examples.
Is produced by the following Production Examples 1 to 5.

Production Example 1 The shells of turban shells were washed with water and then heat-treated at 400 ° C. for 2 hours to completely remove organic substances. After that, pulverize with a ball mill to an average particle size of 1 μm
-1 was produced.

Production Example 2 Abalone shells were washed with water, dried in the sun for 2 years, then immersed in lye for 3 days, and further dried in the sun for 6 months. Then, the maximum particle size of this shell is several mm in a mortar.
The pulverized product A-2 was manufactured by pulverizing until it became.

Production Example 3 "HYCEA-S" manufactured by Kaiho Co., Ltd.
It was set to 3. After washing the oyster shell with water and drying it,
This is a product obtained by electrically heating and baking to about 1,000 ° C., and then pulverizing.

Production Example 4 The scallop shells were washed with water and then heat-treated at 300 ° C. for 24 hours to completely remove organic substances. Then, it was pulverized by a ball mill to an average particle size of 3 μm to produce a pulverized product A-4.

Production Example 5 Clam shells are collected and those having a thickness of 5 mm or more are selected,
After washing this shell with water, it was dried in the sun for 3 years. After that, a crushed product A-5 was produced by crushing with a hammer mill to an average particle size of 5 μm.

Examples 1 to 7 Production Examples 1 to 5 as crushed products of bivalve or conch shells
The pulverized products A-1 to A-5 produced in 1. were used, and the pulverized products A-1 to A-5 were mixed with the other paint components in proportions shown in Tables 1 to 3 (parts by weight)
Were mixed with each other and dispersed by a stirring type dispersing machine using glass beads to prepare 7 kinds of antifouling paints.

In Tables 1 to 3, the vehicle resin "VcVe copolymer" is a vinyl chloride-vinyl ether copolymer and the "SB copolymer" is a styrene-butadiene copolymer. Also, "rosin WW" as one type of vehicle resin is a 60% by weight solution, and "polyamide wax" as one type of additive component is a 20% by weight xylene solution. Furthermore, "TET disulfide" as a drug component is tetraethyl thiuram disulfide.

Comparative Examples 1 and 2, without using a crushed product of bivalves or conch shells, the other paint components were mixed in the blending ratio (parts by weight) shown in Table 3 and stirred with a glass bead. 2 kinds of antifouling paints were prepared by dispersing with a disperser.

An antifouling property test was conducted on each of the antifouling paints of Examples 1 to 7 and Comparative Examples 1 and 2 in the following manner. The results are as shown in Table 4 below. In addition, in the same table, as a reference example, the result of performing the same test as above without forming an antifouling coating film on the test steel plate is also shown for reference.

<Anti-fouling test> Each anti-fouling paint was applied to a test steel plate having a size of 10 cm x 20 cm, which was previously coated with a commercially available anti-corrosion paint, so that the dry film thickness was 60 to 80 µm. It was dried for one day to form an antifouling coating film. The test steel plate on which the antifouling coating film was formed in this way was immersed in the sea in Aioi City, Hyogo Prefecture, at a depth of 2 m in the sea for 24 months using the test raft, and the adhesion of marine pests over time. The area and attached species were visually observed. In Example 7, the adhered area after 12 months decreased after 18 months. This is because the organisms once attached due to the silicone rubber used as the vehicle resin spontaneously peeled off over time. To come.

[0029]

[Table 1]

[0030]

[Table 2]

[0031]

[Table 3]

[0032]

[Table 4]

Examples 8 to 12 Production Examples 1 to 5 as crushed bivalve or conch shells
The pulverized products A-1 to A-5 produced in 1. were mixed with other coating components at the compounding ratios (parts by weight) shown in Tables 5 and 6 below, and stirred using a disperser. By dispersing, 5 types of antifouling agents for fishnets were prepared.

In Tables 5 and 6, "VcVe copolymer", "SB copolymer", "rosin WW", "polyamide wax" and "TET disulfide" are shown in Table 1.
~ The same as in Table 3. The "N-substituted dichloromaleimide" as a drug component is N- (2,6-diethylphenyl) -2,3-dichloromaleimide.

Comparative Example 3 Without using a crushed product of bivalves or conch shells, the other coating components were mixed in the mixing ratio (parts by weight) shown in Table 6 and dispersed by stirring with a disperser. An antifouling agent for fishnet was prepared.

An antifouling property test was conducted on each of the antifouling agents for fishnets of Examples 8 to 12 and Comparative Example 3 as described below. The results are as shown in Table 7 below.
In addition, in the same table, for reference, the result of performing the same test as the above without performing antifouling treatment on the fishnet is shown in Reference Example 2.
Was also described.

<Antifouling test> An antifouling agent for each fishnet was dip-coated on a polyethylene fishnet, and the fishnet thus treated for antifouling was fixed on an iron frame of 40 cm x 60 cm. It was left to stand still for 5 months at a water depth of 2 m from a raft for aquaculture in the sea of Ura, and the adhering area of marine pests and adhering species were visually observed with time.

[0038]

[Table 5]

[0039]

[Table 6]

[0040]

[Table 7]

As is clear from the results shown in Tables 4 and 7, the coating composition of the present invention has a high antifouling effect in both the antifouling paint and the fishnet antifouling agent. It can be seen that the pulverized product of bivalve or conch shells as an active ingredient is a novel coating composition that makes full use of the characteristic that it is completely harmless to the environment and can be widely used for various underwater immersion products. .

Front Page Continuation (72) Inventor Hiroshi Suhara 3-16-5-2 Shimoochiai, Yono City, Saitama Prefecture

Claims (1)

[Claims] 1. A coating composition comprising a crushed product of a bivalve or conch shell as an active ingredient which repels or prevents the attachment of marine pests.