JPS62243663A - Prevention of coloring of antifouling coating material - Google Patents

Abstract

PURPOSE:To prevent coloring of an antifouling coating material, by adding a small amount of zinc carbonate or insoluble basic zinc salt to an antifouling coating material containing manganese ethylenebisdithiocarbamate as an antifouling active component. CONSTITUTION:(A) Manganese ethylenebisdithiocarbamate and (B) zinc carbonate or insoluble basic zinc salt, e.g., basic zinc carbonate, etc., in an amount of 0.1-10.0mol% based on the component (A) are added to a vehicle component, uniformly blended and dispersed to carry out the aimed method for preventing coloring.

Description

DETAILED DESCRIPTION OF THE INVENTION FIELD OF INDUSTRIAL APPLICATION The present invention relates to a method for preventing staining of antifouling paints.

BACKGROUND ART Ships, waterway walls, buoys, cooling heat exchange pipes, and seawater structures are coated with antifouling paints to prevent aquatic organisms from adhering to them. For example, most of the resistance to the speed of a ship is due to the friction of the parts that are in contact with seawater, and most of this resistance is said to be due to the adhesion of seawater organisms. This increased resistance results in increased speed and fuel consumption, creating a significant economic burden. Furthermore, in cooling pipes, this results in problems with heat conduction and the like. Operations are then stopped at regular intervals to remove these deposits and repaint. In order to prevent these stains, various antifouling active ingredients are added to paints. Specifically, copper compounds such as cuprous oxide and copper naphthenate, organotin polymers bound with organotin compounds and tin compounds such as triphenyltin compounds, organic compounds such as organosulfur compounds and dithiocarbamates, etc. Sulfur compounds etc. are widely used. Among these, organic tin compounds and their polymers are widely used, but they are highly toxic to humans and livestock, and environmental pollution has become a problem, so regulations and alternatives are required. As an alternative to this, dithiocarbamate compounds have recently been used as antifouling active ingredients. These dithiocarbamate compounds include zinc ethylenebisdithiocarbamate, manganese ethylenedithiocarbamate, zinc-coordinated manganese ethylenebisdithiocarbamate, zinc propylenebisdithiocarbamate, zinc dimethyldithiocarbamate, etc. Are known. All of these are used as active ingredients in antifouling paints, but manganese ethylene bisdithiocarbamate has the most stable active power and is widely used because it can last for a long time.

Problems to be Solved by the Invention However, when antifouling paints containing manganese ethylene bisdithiocarbamate as an antifouling active ingredient are applied to various parts of ships, buoys, fishing nets, etc., they turn yellowish or brownish. The paint film changes color to a blackish color such as light brown-brown or brownish-brown, and in some cases, the paint film may change to a blackish-brown color.

On the other hand, when antifouling paints containing zinc ethylenebisdithiocarbamate, zinc-coordinated manganese ethylenebisdithiocarbamate, or zinc dimethyldithiocarbamate as antifouling active ingredients are used, no change in the coating film is observed. . Such changes in the coating film are something that coating companies most want to avoid, and methods for preventing such changes in the coating film are in demand.

Means for Solving the Problem The present invention provides an antifouling paint containing manganese ethylenebisdithiocarbamate as an antifouling active ingredient, in which zinc carbonate or an insoluble basic zinc salt is blended with manganese ethylenebisdithiocarbamate. It is related to the method of
As a result, even after applying a paint containing manganese ethylene bisdithiocarbamate to various parts, there is no change in the paint film, no deterioration of the physical properties of the paint film, and antifouling effects. is also completely harmless. The present invention involves adding 0.1 to 10 mol% of zinc carbonate or insoluble basic zinc salt to manganese ethylenebisdithiocarbamate. Specific examples of the insoluble basic zinc salt include basic zinc carbonate, basic zinc chloride, basic zinc sulfate, etc., all of which are insoluble precipitates. Further, preferable effects can also be obtained by adding water-soluble zinc salts such as zinc sulfate, zinc chloride, zinc nitrate, zinc acetate, zinc hydroxide, etc. to the zinc carbonate or insoluble basic zinc salt of the present invention.

The antifouling paint of the present invention can use a wide variety of conventionally known vehicle components, ie, animal oils, vegetable oils, natural oils and fats, acrylic resins, vinyl resins, etc. used as paint components. It goes without saying that pigments, extender pigments, spreading agents, fixing agents, anti-caking agents, and other auxiliary components can be optionally blended into the coating components.

The antifouling component of the present invention is prepared by sufficiently mixing the zinc carbonate or insoluble basic zinc salt of the present invention into a slurry of manganese ethylene bisdithiocarbamate, and then mixing and dispersing the dried product in a vehicle. Alternatively, a good product can be obtained by directly and simultaneously adding the antifouling active ingredient of the present invention and zinc carbonate or an insoluble basic zinc salt to a vehicle component, mixing and dispersing them. In any case, it is important that manganese ethylene bisdithiocarbamate and zinc carbonate or insoluble basic zinc salt are thoroughly and uniformly mixed and dispersed in the coating components.

In addition, hexamethylenetetramine, thiourea, paraform, etc., which are stabilizers for manganese ethylenebisdithiocarbamate, may be simultaneously blended with these active ingredients.

In addition to the antifouling component of the present invention, known antifouling components such as copper compounds such as cuprous oxide, organic tin compounds, organic chlorine compounds, and other pesticidal components may be mixed as needed. Of course, this is also a preferred method.

Next, the present invention will be specifically explained using Examples and Test Examples.

Specific Examples Example 1 For manganese ethylene bisdithiocarbamate, 0
．． 2 mol %, 5.0 mol % and 10.0 mol % of zinc carbonate and basic zinc carbonate were blended and thoroughly dispersed, and 15 parts of the mixture was mixed with the other components shown in Table 1 in a roll mill. The mixture was dispersed to obtain an antifouling paint. As a control, one containing 5.0 mol% zinc oxide was used.

Table 1 Storage example 2 5.5% for manganese ethylenebisdithiocarbamate
A combination of 0 mol% basic zinc chloride salt, 3.0 mol% zinc carbonate and 0.5 mol% zinc sulfate heptahydrate, 3.0 mol% basic zinc carbonate and 0.5 mol% zinc sulfate heptahydrate. 10 parts of a mixture of 5 mol% zinc sulfate, heptahydrate, and the like were mixed and dispersed, respectively, and thoroughly mixed with the other components shown in Table 2 in a roll mill to prepare an antifouling paint.

Table 2 Test Example 1 The antifouling paint prepared in Examples 1 and 2 was applied twice on a 1010 x 15 tin plate (undercoated with anti-rust paint), and the test pieces were tested immediately after application, 20 hours later, and After 48 hours, the state of discoloration of the coating film was investigated. The results are shown in Table 3.

Table 3 Note) ◎ Yellow-brown, △ Light brown-brown, X Brown-brown Test Example 2 A test piece coated in the same manner as Test Example 1 was immersed in seawater.
After 1 month and 6 months, the state of adhesion of the paint film and the change in color of the paint film were investigated, and the results are shown in Table 4.

Table 4 *1 Coating: With 4 films 2) “Situation Judgment No iL Beni (-)
No sessile organisms on the test piece±) 5% or less of sessile organisms attached (+)
// 5-20% 〃(10+) ”
20-50% 〃(+++) 750% or more 〃※2 Changes: ◎Yellow-brown, △Pale brown-brown, I couldn't see it.

Claims (1)

[Scope of Claims] An antifouling paint containing manganese ethylenebisdithiocarbamate as an antifouling active ingredient, with a ratio of 0.0% to manganese ethylenebisdithiocarbamate.
A method for preventing discoloration of an antifouling paint, characterized by containing 1 to 10.0 mol% of zinc carbonate or an insoluble basic zinc salt.