JPS61176671A - Anti-fouling paint composition - Google Patents

Abstract

PURPOSE:To provide the titled composition effective to prevent the staining and adhesion of coating film with microorganisms for a long period, and useful for the coating of ship, etc., by using a compound selected from copper salt of a dibasic acid such as terephthalic acid, in combination with a metal salt of a lower alkylene bisdithiocarbamic acid as active components. CONSTITUTION:The objective composition is produced by using (A) a compound selected from the copper salt of terephthalic acid, isophthalic acid, maleic acid and fumaric acid and (B) a metal salt of a lower alkylene bisdithiocarbamic acid as active components, and compounding the components at a ratio of preferably 1:9-9:1.

Description

Detailed Description of the Invention (Industrial Field of Application) The present invention relates to an antifouling paint composition, and more particularly, the present invention relates to an antifouling paint composition containing a compound selected from copper salts of terephthalic acid, isophthalic acid, maleic acid, and maaric acid. The present invention relates to an antifouling coating composition containing a metal salt of lower alkylene bisdithiogerbamic acid as an active ingredient.

(Prior art) Industrial equipment such as instruments and devices in hot and humid places or underwater, communication and transportation pipes, ship hulls, cooling and heat exchange pipes,
Rafts, buoys, inner surfaces of aquariums, underwater structures, etc. are infested with aquatic organisms such as bacteria, fungi, molds, insects, microorganisms, and molluscs, which can cause enormous damage.
The removal, repair, repainting, etc. are causing a great deal of damage.

For example, especially in ships, an increase in the resistance of the ship's hull by several percent causes a reduction in speed and fuel efficiency, resulting in extremely large losses, and also impedes heat transfer in cooling water heat exchange pipes.

The nest operation is then stopped at regular intervals to remove these deposits.

Conventionally, in order to prevent these stains, inorganic metal compounds such as copper, mercury, and tin, as well as organic compounds such as organic tin, organic chlorine compounds, and organic sulfur compounds, have been mixed into paints and applied to the desired areas. It's here.

All of them have drawbacks such as being highly toxic to humans and animals, causing environmental pollution, and not being sufficiently effective over a long period of time when used as a paint composition.

Among these, organic copper compounds, such as 8-oxyquinoline copper,
Copper dimethyldithiocarbamate, copper terephthalate, etc.
It is known to be used as an active ingredient in antifouling paints. In particular, dibasic salts such as the copper salt of terephthalic acid are
- Oxyquinoline It is said that copper is more stably retained than copper, so the effect is sustained over a long period of time, making it a preferred ingredient. Copper salts such as terephthalic acid are described in Japanese Patent Publication No. 47-42483 and Japanese Patent Publication No. 47-31606.

(Problems to be Solved by the Invention) However, the effects of these copper salts as single agents are not satisfactory, and for this reason, they are mixed with other copper agents, but they are not sufficient, especially Adherent microorganisms grow under harsh conditions, especially in seawater, and this is not completely satisfactory. It is desired that the effects of the copper salt of terephthalic acid, which is a dibasic acid, continue to be effective.

(Means for Solving the Problems) The present inventor conducted an antifouling effect test by blending various compounds with copper salts of dibasic acids such as terephthalic acid, and found that lower alkylene bisdithiocarbamic acid It has been found that metal salts prevent contamination and adhesion of microorganisms to paint films, and maintain stable effects over an extremely long period of time.

The compound selected from copper salts of terephthalic acid, isophthalic acid, faric acid, and maleic acid used in the present invention can be produced by known methods.For example, water-soluble salts and water-soluble copper salts of these dibasic acids can be used. They can be easily produced by reacting them, and they can be either anhydrous or hydrated. Metal salts of lower alkylene bisdithiocarbamic acids include heavy metal salts of ethylene bisdithiocarbamic acid and brobylene bisdithiocarbamic acid such as zinc, manganese, and copper, and metal salts such as zinc or copper. Examples include manganese ethylenebisdithiocarbamate, bisdimethyldithiocarbamoylzinc ethylenebisdithiocarbamate, and cuprous substituted metal salts of ethylenebisdithiocarbamate.The coating composition of the present invention includes, as a vehicle component, animal oil, vegetable oil, natural fat,
Those used in known paints such as acrylic resin and vinyl resin can be used. Naturally, pigments, extender pigments, spreading agents, fixing agents, assimilation inhibitors, and other auxiliary components can be appropriately added to the coating components. The active ingredient content of the present invention in the paint is:
It can be blended as desired, but preferably 1 to
I can do 50%. The dibasic acid copper acid and the metal salt of lower alkylene bisdithiocarbamate of the present invention are preferably blended in a ratio of 1:9 to 9:1.
These active ingredients may be crushed in advance and added to the paint components, or after being added, they may be crushed, kneaded, and stirred in a vehicle.

Furthermore, it is of course possible to use the antifouling paint composition as an active ingredient of the present invention by mixing other known antifouling agent components.

(Examples and effects of the invention) Example 1 10 parts of copper terephthalate, 10 parts of zinc ethylene bisdithiocarbamate finely pulverized to 3μ or less, 15 parts of talc
30 parts of pine resin, 15 parts of acrylic resin, and 20 parts of xylene were kneaded, mixed, and stirred and dispersed to prepare a paint.

Example 2 10 parts of copper terephthalate salt, 10 parts of copper-coordinated manganese ethylene bisdithiocarbamate finely pulverized to 3μ or less,
15 parts of talc, 30 parts of pine resin, 15 parts of acrylic resin, and 20 parts of xylene were kneaded, mixed, and stirred to form a paint.

Example 3 7 parts of isophthalic acid salt, 13 parts of zinc-coordinated manganese ethylene bisdithiocarbamate finely pulverized to 3μ or less,
Knead, mix, and stir 15 parts of titanium white, 25 parts of pine resin, 20 parts of methyl isobutyl ketone, and 20 parts of xylene.
It was made into paint.

Example 4 5 parts of copper fumarate salt, 10 parts of finely ground copper-coordinated manganese ethylene bisdithiocarbamate, 20 parts of titanium oxide, 10 parts of talc, 10 parts of vinyl chloride resin, 20 parts of methyl isobutyl ketone, 25 parts of xylene The parts were kneaded, mixed, and dispersed to make a paint.

Example 5 12 parts copper maleate salt, 8 parts finely ground bisdimethyldithiocarbamoylethylene bisdithiocarbamate zinc
15 parts of titanium white, 25 parts of pine resin, 20 parts of methyl isobutyl ketone, and 20 parts of xylene were kneaded, mixed and dispersed to obtain a paint.

Example 6 5 parts of copper terephthalate, 5 parts of finely ground bisdimethyldithiocarbamoylethylene bisdithiocarbamate zinc, 20 parts of titanium white, 25 parts of pine resin, 15 parts of acrylic resin, and 20 parts of xylene were kneaded and mixed. 1 was dispersed to form a paint.

Test Example The test piece was a tin plate (undercoated with anti-corrosion paint).
The sample antifouling paint (15cn x 10aa) prepared in the example was applied twice with a brush, and the coated test piece was
The survey was carried out at a depth of 1.5 meters at Umi Elementary School (Katsuura Port, Wakayama Prefecture).

The results are shown in the table below.

1) Judgment criteria (-) No fouling organisms ±) Less than 5% of attached organisms (+) 75% to 20% 〃 (++) II 20% to 50% 〃(++
+) # 50% or more 2) Regarding Comparative Examples (1) Regarding Comparative Example I, 15 parts of copper terephthalate, 10 parts of talc, and 5 parts of titanium oxide.

Data prepared with 20 parts of pine resin, 25 parts of acrylic resin, and 25 parts of xylene (2) Regarding Comparative Example 2, 10 parts of copper terephthalate, 8-
Oxyquiculin copper 10 parts, talc 10 parts, titanium oxide 5 parts
(3) For Comparative Example 3, 15 parts of copper-coordinated manganese ethylene bisdithiocarbamate, 10 parts of talc, and 5 parts of titanium oxide were added.
Paint prepared with 20 parts of rosin, 25 parts of acrylic resin, and 25 parts of xylene.

Claims (1)

[Claims] An antifouling paint composition characterized in that it simultaneously contains a compound selected from copper salts of terephthalic acid, isophthalic acid, maleic acid, and fulric acid and a metal salt of lower alkylene bisdithiocarbamic acid as active ingredients.