JPH01223178A - Solvent-based underwater antifouling agent - Google Patents

Abstract

PURPOSE:To provide the subject antifouling agent composed of a material produced by dissolving or dispersing a water-insoluble film-forming resin and a specific quaternary nitrogen compound in a solvent, safe to fishes, shellfishes and human body, having persistency and effective in preventing the adhesion of shellfishes and seaweeds to the surface of fishing net, ship bottom, etc. CONSTITUTION:The objective antifouling agent is composed of a composition produced by dissolving or dispersing (A) a water-insoluble film-forming resin (preferably acrylic resin, urethane resin, vinyl acetate resin, epoxy resin, vinyl chloride resin, polyester resin, melamine resin, urea resin, styrene resin, etc.) and (B) a quaternary nitrogen compound of formula I [two of R1-R3 are 1-2C alkyl and the remaining one is 14-34C alkyl or group of formula II (R is 14-30C alkyl); phi is phenyl] in (C) a solvent (preferably an aliphatic hydrocarbon, aromatic hydrocarbon, ketone, alcohol, etc., having a boiling point of <=200 deg.C).

Description

[Detailed description of the invention] [Industrial application field]

The present invention relates to a solvent-based underwater antifouling agent, and more particularly to a solvent-based underwater antifouling agent for preventing shellfish and algae from adhering to the surfaces of objects that are constantly immersed in seawater, such as fishing nets and ship bottoms. be.

[Conventional technology]

(Background) Objects immersed in water such as fishing nets, ship bottoms, buoys, and buoys that are in contact with seawater for long periods of time inevitably attract aquatic organisms such as shellfish, seaweed, and bryozoans. As a result, the resistance on ships increases dramatically, leading to a sharp increase in fuel consumption.Furthermore, in fishing nets, for example, aquaculture nets, aquaculture fish die due to lack of oxygen due to clogging of the nets, and the growth of parasites is promoted. Furthermore, fixed nets have caused problems such as increased resistance during hauling and decreased durability, which has puzzled operators. . Similar problems are also seen in the sinking of buoys used for aquaculture nets and buoys used to navigate navigation routes. (Problems with the Prior Art) Therefore, an antifouling treatment method has been developed in which an object is treated with an antifouling composition containing an organic tin compound such as a trialkyltin compound or a triphenyl anchor compound from cocoons that have been harvested for about 20 years. However, these organic tin compounds not only are difficult to decompose, but also have the disadvantage of being extremely toxic to fish and humans, and therefore pose a major social problem in terms of pollution. In addition, these organotin compounds have a unique odor and can be impregnated into fishing nets.
There are also problems with labor conflicts, such as workers complaining of discomfort, getting sick, or getting headaches or dizziness during drying work. In particular, the Central Pollution Control Council's Chemical Substances Expert Committee, which has focused on environmental pollution caused by heavy metal compounds such as TBTO (tributyl tin oxide), has recently advocated banning or voluntary regulation of the use of such chemical substances as pollution prevention measures. What has been decided is noteworthy. In order to solve the above-mentioned problems with organic tin compounds, a water-based underwater antifouling agent has already been developed and provided, which uses an aqueous resin emulsion as a binder and contains a cationic surfactant as an antifouling agent as a main component. . However, because the total number of carbon atoms in the cationic surfactant component of the antifouling agent is small,1 for example, in areas with high water temperatures such as off the coast of southern Kyushu, the elution of the antifouling agent component becomes extremely rapid, and the antifouling effect is rapidly lost. It has its drawbacks. In order to improve the above-mentioned drawbacks of cationic surfactant-based antifouling materials, it is effective to increase the total number of carbon atoms in the antifouling agent component, but when the total number of carbon atoms increases, it becomes insoluble in water and dissolves. Since a solvent is inevitably required, it is no longer possible to create a water-based underwater antifouling agent.

[Problem to be solved by the invention]

In view of the above circumstances, an object of the present invention is to provide a solvent-based underwater antifouling agent that is safe for fish and shellfish and the human body, and is long-lasting.

[Means to solve the problem]

(Summary) That is, 1. The present invention is characterized in that it is a composition in which a water-insoluble film-forming resin and a quaternary nitrogen compound (CI) represented by the following general formula are dissolved or dispersed in a solvent as main components. It is a solvent-based underwater antifouling agent. (Space below) [General formula] [In formula 1, two of R1-R3 represent an alkyl group having 1 to 2 carbon atoms, and the remaining one represents a higher alkyl group having 14 to 34 carbon atoms or a general formula. Formula R-CI-C)I2-H (wherein R is a higher alkyl group having 4 to 30 carbon atoms), and φ represents a phenyl group]. (Quaternary nitrogen compound) The composition of the present invention contains the above general formula (
A water-insoluble film-forming resin of a quaternary nitrogen compound having the structure I), and a solvent for the former two or a solvent as a dispersion medium, but the substituent R1 of the quaternary nitrogen compound ~
One of R3 is a higher alkyl group having 14 to 34 carbon atoms or a general formula. R-CI-CH2-(RIIC14-311(F)alkyl)H, and the remaining two furkyl groups are preferably lower alkyl groups having 1 to 2 carbon atoms. Number of carbon atoms is less than 14 or R-CH-CH
If the total number of carbon atoms in the 2- group is less than 17, the elubility of H into water will be strong. H If the total number of carbon atoms is 37 or more, or if the remaining lower alkyl group has 3 or more carbon atoms, the dissolution properties will be poor and the effects of the present invention cannot be fully exhibited. Among the above quaternary compounds (I), compounds in which R1 to R3 are all higher alkyl groups can be obtained by quaternizing a tertiary alkylamine with benzyl chloride in a conventional manner. Compound (I), in which two of R1-R3 are lower alkyl groups and one is a hydroxyalkyl group, is a compound (2) (Shimoyama) that is a reaction product of a secondary alkylamine and a furkyl epoxide. Obtained by conventional quaternization with chloride. (Solvent) Compound (I) in the present invention is usually dispersed or dissolved in a solvent and blended with a solution or dispersion of a water-insoluble film-forming resin that serves as a binder. The solvent here preferably has a boiling point of 200°C or lower, such as aliphatic or alicyclic hydrocarbons such as n-hexane and methylcyclohexane. Aromatic hydrocarbons such as xylene and toluene, acetone,
Aliphatic ketones such as methyl ethyl ketone and methyl isobutyl ketone; alkyl ethers such as methyl cellosolve, methyl cellosolve, butyl cellosolve, and dioxane;
Esters such as ethyl acetate, cellosolve acetate, butyl acetate, lower aliphatic alcohols such as methanol, ethanol, propatool, i-propatool, butanol, aliphatic nitrogen-containing compounds such as dimethylformamide, fats such as dimethylsulfoxide Group sulfur-containing compounds. Examples include aliphatic halogen compounds such as perchlorethylene and 1,1.1-trichloroethane, but are not limited to these, and the above solvents may be used freely depending on the situation as long as they are compatible. Can be mixed. Further, the solvent can be blended in any proportion to the main ingredient of the antifouling agent, and is not particularly specified. (Water-insoluble film-forming resin) The water-insoluble film-forming resin acts as a carrier for the main ingredient of the antifouling agent or as a binder for the antifouling object.The properties required for the resin are as follows: In addition to being insoluble in water (seawater) and having the property of dissolving or dispersing in solvents,
The purpose is to form a film that adheres to the object as the solvent evaporates, but the solvent for dissolving or dispersing this resin is naturally the same as the solvent for dissolving or dispersing the antifouling agent main ingredient, or is mutually compatible. It is preferable that it has solubility. Examples of suitable resins include acrylic resin, urethane resin, vinyl acetate resin, Evoquin resin, vinyl chloride resin, polyester resin, melamine resin, urea resin, styrene resin, styrene-butadiene copolymer latex, and polyethylene resin. Homopolymers and copolymers such as polypropylene resins and phenol resins, and blends thereof can be exemplified, but these are, of course, merely illustrative. Note that the resin may be optionally supplemented with a qq agent such as trialkyl phosphate or diphenyl ether. Auxiliary agents such as anti-aging agents, antioxidants, light-resistant agents, and ozone-resistant agents may be included. (Formulation) The blending amounts of the antifouling main agent, resin, and solvent in the solvent-based underwater antifouling agent according to the present invention can vary widely depending on the purpose.
The amount of solvent must be at least an amount that gives the composition a viscosity that allows it to be applied, sprayed, or immersed.What is more important is the ratio of the resin (solid content) to the main antifouling agent (solid content). , this ratio is usually between 1:10 and l:l
is within the range of (Application method) The antifouling agent of the present invention is applied to objects such as fishing nets and ship bottoms by coating, spraying, or dipping methods. In the case of fishing nets, the solid content of one bottle of antifouling agent should be about 10 to 40% of the weight of the net, and for the bottom of ships, buoys, buoys, etc., the solid content should be about 2 to 20 g per lrn'. Apply, spray or dip.

[Effect]

The solvent-based underwater antifouling agent of the present invention not only suppresses the adhesion and proliferation of aquatic organisms in seawater, but also does not have an adverse effect on cultured fish and shellfish such as cultured fish and shellfish. To provide an extremely effective and safe underwater antifouling means, which is highly safe and does not cause acute poisoning or inertial poisoning due to accumulation even if ingested by the human body.

【Example】

The embodiments and effects of the invention will be described below with reference to Examples and Comparative Examples, but each example is of course for illustration only and does not imply any limitation or restriction on the idea of the invention. 1 to 5 and l to 2 Polyethylene (HiZEX) fishing nets were immersed in a solvent-based underwater antifouling agent composition and a control antifouling agent (composition) with the formulations shown in Table 1 below, and then left in the air for 2 days after being lifted. After drying in the sun to completely volatilize the solvent, it was submerged off the coast of Goto, Nagasaki Prefecture, and the state of adhesion of aquatic organisms was observed for 5 months. The results are also shown in Table 2. The evaluation criteria in Table 2 are as follows. O: No or very little biofouling. 0: Biofouling is clearly observed, but there is no practical problem. Δ: There is considerable biofouling, which poses a practical problem. ×: The amount of attached biomass is very large. As shown in Table 2, it can be seen that the antifouling agent of the present invention has an excellent long-lasting effect compared to that of the comparative example. (Left below) Table 1 Table 2 Honmarindox Se (trade name of a solvent-type organic tin antifouling agent manufactured by K.I. Kasei)

【Effect of the invention】

As explained above, the present invention can contribute to the rationalization and development of fishing, shipping, and other industries by providing a solvent-based underwater antifouling agent that is safe and sustainable for seafood and the human body. .

Claims (1)

[Scope of Claims] 1. Solvent-based underwater defense characterized by being a composition in which a water-insoluble film-forming resin and a quaternary nitrogen compound (I) represented by the following general formula are dissolved or dispersed in a solvent. Staining agent. General formula ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ ------- (I) [In addition, two of R_1 to R_3 in the formula have 1 or more carbon atoms.
2 alkyl groups, and the remaining one has 14 to 3 carbon atoms.
4 higher alkyl group or general formula ▲ There are numerical formulas, chemical formulas, tables, etc. ▼ (in the formula, R is a higher alkyl group having 14 to 30 carbon atoms), and φ represents a phenyl group]. 2 The water-insoluble film-forming resin is acrylic resin, urethane resin, vinyl acetate resin, epoxy resin, vinyl chloride resin, polyester resin, melamine resin, urea resin, styrene resin, styrene, butadiene copolymer latex,
The underwater antifouling agent according to claim 1, which is one or more resins selected from polyethylene resin, polypropylene resin, and phenol resin. 3. The solvent is selected from aliphatic hydrocarbons, aromatic hydrocarbons, ketones, alcohols, alkyl ethers, alkyl esters, aliphatic nitrogen-containing compounds, aliphatic sulfur-containing compounds, and aliphatic halogen-containing compounds with a boiling point of 200°C or less. The underwater antifouling agent according to claim 1, which is one or more kinds of solvents. 4 The ratio of the antifouling agent base agent to the resin in the composition is 1:10 to
The underwater antifouling agent according to claim 1, wherein the ratio is 1:1.