JPH01268610A - Aquatic antifouling agent - Google Patents

Abstract

PURPOSE:To provide a non-pollutive aquatic antifouling agent, by containing as an antifouling component a novel metal ionomer produced by crosslinking an olefinic polymer having carboxyl groups at the side chains with a metal selected from Ib group metals as a crosslinking atom for the ionomer resin. CONSTITUTION:An olefinic polymer having carboxyl groups at the side chains (e.g., an ethylene/alpha,beta-unsaturated carboxylic acid random or block copolymer such as ethylene/acrylic acid copolymer) is crosslinked through at least one kind of metal (e.g., gold, silver or copper, preferably silver or copper) selected from Ib group metals to provide an aquatic antifouling agent wherein the content of the metal atoms is 1-10wt.%, particularly 3-7wt.%. The antifouling agent needs no anxiety for environmental pollution and can prevent the pollution caused by the adhesion of aquatic pollutive organisms such as algae and shellfish over a long period.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to an underwater antifouling material. More details,
The present invention relates to an underwater antifouling material containing a novel metal ionomer as an antifouling component.

Prior Art W6 algae such as green algae, brown algae, and diatoms, as well as contaminant organisms such as sea squirts, acupuncture, serpula, oysters, and bryozoans, are found on the bottom of ships,
It adheres to the surface of fishing nets or underwater structures, causing various types of damage. For example, a decrease in ship speed due to an increase in frictional resistance,
Clogged fishing nets obstruct the flow of seawater, resulting in poor growth of farmed fish and corrosion of underwater structures.

Various antifouling paints are used to prevent the attachment of contaminant organisms, and many of them contain tri-organotin compounds as the antifouling component. However, antifouling paints containing, for example, tributyltin compounds or triphenyltin compounds as antifouling components have problems such as being highly toxic to the human body during operation and not having long-term antifouling performance.

In recent years, antifouling paints have been developed that use nonmetallic compounds as antifouling ingredients, such as salitelanilide derivatives, thiuram disulfide compounds, and halogenated phthalimide compounds, but these are bactericidal agents and organic tin compounds are not. However, it has the problem of environmental pollution and does not have long-term antifouling performance.

An open problem to be solved: To provide an underwater antifouling material that is free from concerns about environmental pollution and has antifouling performance for a long time.

SUMMARY OF THE INVENTION The present invention provides that the carboxyl group in the side chain is cross-linked through at least 1, (51) metal atoms selected from the Nib group of the periodic table, and the content of the metal atoms is 1 to 10.
The present invention provides an underwater antifouling material characterized by containing an olefin polymer of wt%.

Effects of the Invention According to the present invention, there is no need to worry about environmental pollution, and contamination due to adhesion of aquatic contaminants such as seaweed and shellfish can be prevented for a longer period than before.

Detailed Description of the Invention Examples of the olefin polymer having a carboxyl group in the side chain used in the present invention include ethylene/acrylic acid copolymer, ethylene/methac+JkrR copolymer,
Ethe1/one such as ethylene/ethacrylic acid copolymer, ethylene/itaconic acid copolymer, ethylene/maleic acid copolymer, ethylene/fumaric acid copolymer, etc., and α,β-unsaturated carboxylic acid Random or block copolymers of ethylene and monoesters of dicarboxylic acids, such as ethylene/methyl hydrogen maleate copolymers, ethylene/methyl hydrogen fumarate copolymers, ethylene/methyl hydrogen fumarate copolymers, etc. Block copolymers; random or block copolymers of maleic anhydride, which is not a carboxylic acid but has the same chemical reactivity, and ethylene; α-olefins such as polyethylene, polypropylene, polybutene, propylene-ethylene copolymers, etc. There are copolymers in which the above-mentioned carboxylic acids, such as α,β-unsaturated carboxylic acids, are graft-modified using known methods.

The MFR of the above-mentioned carboxyl group-containing olefin polymer is 1 to 100 (1/10 min, preferably 5 to 5
00f/10 minutes. The carboxyl group content is 1.5 to 45% by weight, preferably 10 to 400 to 40% by weight. The metal atoms selected from group Ib of the periodic table used in the present invention are gold, silver, and steel. Among these, silver and copper are preferred, and copper is particularly preferred. Compounds of Group Ib metals in the periodic table include inorganic compounds such as hydroxide compounds, carbonate compounds, nitric acid compounds, and sulfuric compounds, and organic compounds such as formic acid compounds, oxalic acid compounds, and acetic acid compounds. Preferred are hydroxide and carbonate compounds that are non-corrosive to equipment.

The olefin polymer having a carboxyl group in the side chain can be crosslinked via at least one of the metal atom-containing compounds using a known mechanical or chemical melt mixing method. It is also possible to mix Vi. For example, α
, α- containing β-unsaturated carboxylic acid as a constituent component
A predetermined amount of metal compound is added to the carboxylic acid content of the olefin copolymer, and then
- Perform melting@cross-wire treatment using a kneading device such as plastomill.

The content of four gold atoms in the olefin polymer in which the side chain carboxyl groups are crosslinked through at least one metal atom selected from Group Ib of the Periodic Table as described above is 1 to 10.
Preferably, it is % weight by weight (vrts). If the content is less than the lower limit of this range, the antifouling property will not be sufficient, and if the content exceeds the upper limit, problems will occur in terms of moldability. The content of the metal atoms is more preferably 3 to 7 wt*. In addition, the proportion of carboxyl groups actually acting on the amount of added metal atoms is 2 moles of carboxyl groups when the cation is a divalent metal atom, and 1 mole of a metal atom with a monovalent cation. Suppose it interacts with carboxyl groups.

Therefore, it is preferable to use a crosslinked product which acts on the crosslinking reaction by 50% or more, preferably 80% or more of the amount of carboxyl groups that should originally act with respect to the amount of metal atoms added. If the amount of carboxyl groups that should originally act in the crosslinking reaction is small relative to the amount of metal atoms added, the antifouling performance will decrease, and in the past, during forming such as spinning,
A problem arises in that the degree of crosslinking reaction changes and processing becomes unstable.

It is possible to add various additives to the antifouling material of the present invention to improve its performance. Examples include acid inhibitors, pigments, carbon, dyes, and if necessary, pond antifouling agents.

The antifouling material of the present invention can be extruded using a general-purpose extruder, cooled and stretched, and then spun or molded to produce filaments, threads, films, and pipes with excellent antifouling properties. It is also possible to use the above-mentioned molded product made of other materials with the antifouling material of the present invention coated on the outside.

Experimental Examples Example 1 Add 7.5 wt% of hydroxide steel as a metal crosslinking agent to the pellets of ethylene/acrylic acid copolymer. 50m diameter twin screw kneading extruder (L/D=
5) at a temperature of 240° C. and a feed rate of 5 oAiI/hour for crosslinking. As a result of infrared analysis of the extruded kneaded product, there was an absorption peak at 1580i1 indicating an ion absorption band, and it was confirmed that ions were cross-linked.

A knotless net (from 30 pieces of 600 denier) was made from this resin as a monofilament (drawn yarn), and 13 strands were stretched vertically and horizontally in a frame of 50 crn x 50 m, and placed in Karatsu Bay, Nagasaki Prefecture. An immersion test was conducted to evaluate the stain resistance. The results are shown in Table 1.

Example 2 The crosslinking agent was changed to silver carbonate, and the amount added was also 10.7 wt% (
7.7 wt% as steel metal atoms), Example 1
A crosslinked product was obtained in the same manner as in the above method, and its antifouling properties were evaluated.

Comparative Example 1 According to Example 1, 0.5 wt% ethylene/
A steel strip bridge made of acrylic acid copolymer was produced, and its antifouling properties were evaluated in the same manner as in Example 1.

Comparative Example 2 A zinc metal atom, which is generally known as a crosslinking metal atom in ionomer resins, was used, and the addition needle was also set at 3.3 wt% (the zinc hydroxide compound was 4.9 wt%), and the same method as in Example 1 was carried out. A crosslinked product was obtained and its antifouling property was evaluated.

Comparative Example 3 The antifouling properties of high-density polyethylene (Mitsubishi Yuka Co., Ltd.: EY-40L) were evaluated as an object for evaluating antifouling properties.

What percentage of the area of 50cm x 50a* is the stain resistance evaluation?
The adhesion of marine animals and plants was evaluated based on the following criteria.

○ mark 2 Marine animals and plants are not attached Δm; 5% or less adhesion X mark; 5 to 20% I XX mark: 20 to 50% O

Claims (1)

[Claims] (1) An olefin polymer in which the carboxyl group in the side chain is crosslinked via at least one metal atom selected from Group Ib of the Periodic Table, and the content of the metal atom is 1 to 10 wt%. An underwater antifouling material characterized by containing.