JPS58134005A - Aquatic antifouling agent - Google Patents

Abstract

PURPOSE:To provide an aquatic antifouling agent containing tetrachloroisophthalonitrile and a tributyltin polymeric compund as active components, having low toxicity and environmental pollution, and exhibiting excellent effect to prevent the adhesion of a wide variety of aquatic fouling life compared with the separate use of each component. CONSTITUTION:The agent contains tetrachloroisophthalonitrile and a tributyltin polymeric compund as active components. The ratio of the components is selected arbitrary according to the required antifouling effect and economicity, etc. The tributyltin polymeric comound is obtained, e.g. by reacting (A) a tributyltin compound with (B) a homopolymer or mutual copolymer of triorganotin salts of an unsaturated carboxylic acid such as (meth)acrylic acid, maleic acid, etc. or its copolymer with a copolymerizable unsaturated compound such as vinyl chloride, vinyl acetate, styrene, etc. The above active comoonents are dispersed and kneaded together with a spreader, solvent, pigment, filler, etc. with a ball mill, etc. to obtain the objective agent.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a long-acting underwater antifouling agent for preventing the adhesion of aquatic fouling organisms to objects such as zero-launch and one-boat vessels, fishing nets, and various underwater structures.

Conventionally, fishing nets, particularly fishing nets and fixed nets, are heavily contaminated with aquatic fouling organisms that are kept in the water for long periods of time, resulting in various problems. That is, the JIl breeding net is used for seaweeds such as 1. osa, blue laver, and cut-shaped Fujibbo, serpura, 7. Ktj nets accumulate and accumulate, impairing water circulation and causing oxygen deficiency, which harms the survival of farmed fish, so much so that Ktj nets have to be replaced every few weeks, especially when the sessile organisms are at their peak. Considering various factors such as the labor, time, and negative effects of this re-netting KFi on farmed fish, it is a considerable loss. Therefore, preventing the adhesion of water-polluting organisms is an important task.

In addition, prevention of adhesion to the bottom of ships and various other underwater facilities is one of the important solutions for maintaining their functions sufficiently and economically.

In order to prevent the adhesion of these aquatic fouling organisms, various antifouling gJJ components have been proposed. Copper compounds and organic tin compounds are generally used. Practically effective examples include trialkyltin compounds and trialkyltin compounds.

However, this organotin compound generally has strong mollusc properties;
Products containing it can cause injury to those who handle it carelessly.

In view of these current circumstances, the inventors of the present invention have developed a product that is less toxic to the human body and to mollusks than the organotin compounds that are currently commonly used, and that has recently become popular with society. The present invention was completed as a result of intensive research to develop a low-toxicity, low-pollution underwater antifouling agent in consideration of environmental pollution.

The present inventors screened many compounds, found effective compounds based on the results of sea immersion testing, and also pursued the effects of phase fJJ in order to effectively prevent the adhesion of a wide variety of aquatic fouling organisms. This led to the invention. That is, the present invention provides tetrachloroisotucuronitrile and
It is an underwater antifouling agent containing a ligutyltin polymer compound as an ingredient, and exhibits an excellent phase Ill effect against a wide range of underwater fouling organisms. It was discovered that it has an excellent anti-adhesion effect.

As the tributyltin polymer compound used as an active ingredient in the present invention, triorgantin salt monomers of unsaturated carboxylic acids such as acrylic acid, methacrylic acid, maleic acid, and itaconic acid are synthesized, and the monomers of these monomers are Copolymerization or mutual copolymers and copolymers with unsaturated compounds having copolymerizability such as vinyl monide, vinyl acetate, vinylidene chloride, alkyl esters of acrylic acid or methacrylic acid, styrene, vinyltoluene, etc. Examples include high-value alkyd resins, and high-value molecular compounds obtained by reacting the carboxyl groups of acrylic resins with triglytin compounds.

The blending ratio of tetrachloroiso7-trilonitrile and tributyltin polymer compound of the present invention is not particularly specified, but can be blended in any ratio from the viewpoint of antifouling performance and economical efficiency.
゛In producing the underwater antifouling agent of the present invention, tetrachloroinctalonitrile and tributyltin polymer compound are fractionally kneaded together with a spreading agent, a solvent, and optionally a pigment, a filler, etc. using a conventional method such as a ball mill. do it.

Examples of the spreading agent include natural resins, oil-based resins, and synthetic resins, but preferred are polybutene, acrylic resin, rosin vinyl, and chlorinated rubber.

Hereinafter, the present invention will be explained in detail with reference to Example b Production Example! Synthesis of tributyltin polymer compound Tributyltin methacrylate (350 g) and methyl methacrylate (150 g)
2. g of benzoyl peroxide was dissolved in 500 g of xylene and used as a polymerization initiation catalyst. ．． When 5 g of the copolymer was added and polymerized for 7 hours at 90 to 110°C, the number average molecule of a pale yellow viscous copolymer was 1.
According to gel permeation chromatography, 17
,000.

Production Example 2 Synthesis of triglytin polymerized product Tributyltin methacrylate 325g, methyl methacrylate 12
5g and butyl acrylate 50g xylene 500g
15g of benzoyl peroxide as a polymerization initiation catalyst dissolved in gK
is added and polymerized for 8 hours at 80 to 100°C to obtain a 50% xylene solution of a pale yellow viscous copolymer. The number average molecule J1 of this copolymer is 2LO00 according to gel persion chromatography.

Example 1 Fishing net antifouling agent Example 1 (a) Polymer solution of Production Example 1 87% Tetrachloroisophthalonitrile 5 Acrylic resin (
50% xylene liquid) 16% by weight solvent naphtha
71Example 1(b) Polymer solution of Production Example 1 12111% by weight Tetochloroisophthalonitrile 4 Acrylic resin (
5 (15 xylene liquid) 16 solvent toner 7 sa
68 Example 1 (C) Polymer solution of production fl+2 8% by weight tetrachloroiso7talonitrile 6 acrylic resin (
50% xylene liquid) 2G solvent naphtha
46 pseudocumen 2
0 Example 1 (di'' Polymer solution of Production Example 1 4% by weight tetrachloroiso7talonitrile, 4tetraethylthiclam disulfide 4% coulometric acrylic resin (50% xylene liquid) 20 Solvent naphtha
68 Example 1 (e) Polymer solution of Production Example 1 166% by weight Tetrachloroiso7talonitrile 4 Acrylic resin (50
% xylene liquid) 12 solvent naphtha
68 Comparative Example 1 Polymer solution of Production Example 1 16 coul% acrylic resin (50% xylene liquid) 16 sole pentona 7 sa
68 Comparative Example 2.

Tetrachloroiso71I', lonitrile 6-@
1% acrylic resin (!$096 xylene liquid) 1
Each of the fishing net antifouling agents of Examples and Comparative Examples was added to one section made of polyethylene (
Knotless) Net (400 denier from 60 wood) 3 (IC1l
After dipping and air-drying the coating on X50Qll, it was kept in the sea at a depth of 1m in Toba Bay, Mitsuka Prefecture, for 6 months from April 1980 to October 1980, and the adhesion of fouling organisms was investigated every month. . The results are shown in Table @1.

In the table, ratings A, B, C, and D indicate the degree of adhesion of fouling organisms. O A: No fouling organisms attached B: Slight amount of fouling organisms attached C: Fouling organisms attached to the cultivation net As such, it is no longer suitable for use.

D: Fouling organisms are significantly attached.

-Margin below- Table 1 From the results shown in Table 1, it has become clear that the antifouling agent for fishing nets of the present invention exhibits an excellent antifouling effect for a long period of time. Also,
It has been found that the antifouling agent for fishing nets of the present invention has good adhesion to the net and has excellent practical properties without impairing the flexibility of the net.

Example 2 Ship bottom antifouling agent Example 2 (a) Polymer solution of Production Example 1 40 m rut % tetrachlorointutalonitrile 5 wt % cuprous zinc
35 valve pattern
5 Talc 5 Xylene
10 Example 2 (b) Polymer solution of Preparation Example 2 4011j Amount % Tetrachloroiso7trilonitrile 5L1 (-oxidized steel 35 Petal
5 Talc 5 Xylene
10 Practical Example 2 (C) Polymer of Production Example 1: Liquid 40 Tetrachloroisophthalonitrile 10 Cuprous oxide
・30 talc
5 Xylene 10 Example 2 (d) Polymer solution of Production Example 2 40 Weight pseudo-tetoxychloroin 7 Talonitrile 10 Cuprous oxide
3゜bengara
5 Talc 5 Xylene 10 Comparative Example 1 Polymer solution of Production Example 1 40 m% cuprous oxide 35 Bengara 5 Talc 5 Xylene
15 ratio φ〈Example 2 Polymer solution of Production Example 2 40% cuprous oxide 35 valve pattern
5 Talc S-xylene
Each of the ship bottom antifouling agents of 15 or more Examples and Comparative Examples was coated on an acrylic plate (10cIRX 30QR
) dry coating film d! After applying with an applicator to a thickness of 100 microns and air drying, it was applied to a depth of 1 m in Kiitanabe City, Wakayama Prefecture.
Submergence was carried out in the sea for one year from April 1980 to April 1980, and the presence of fouling organisms was confirmed every three months. The results are shown in 2nd:&. Note that both evaluation vehicles are the same as Inukajogai 1.

one or less margin one 4! J　　　　　　　Table

Claims (1)

[Claims] An underwater antifouling agent characterized by containing tetrachloroiso7talonitrile and a tributyltin polymer compound as active ingredients.