JPS6019944B2 - Antifouling paint composition with storage stability - Google Patents

Description

[Detailed description of the invention] The present invention relates to storage-stable antifouling coating compositions.

In recent years, high-molecular organotin compounds having organotin groups in their molecules have been used as excellent antifouling agents to prevent marine organisms from adhering to fishing nets and ship bottoms. In addition, by using a copper compound (for example, suboxide steel, Rodan copper) in combination with this polymeric organotin compound,
Furthermore, it is also known that a ship bottom paint has a high degree of antifouling performance. However, antifouling paints made by mixing high-molecular organotin compounds with steel or steel compounds gradually increase in viscosity during storage, and in severe cases gel, resulting in stringing, deviations in the designed film thickness, and film thickness defects. This may cause uniformity or inability to paint.
The value of the product is lost. Furthermore, paints that have become thickened or gelled in this manner often show a decline in antifouling performance. As a result of extensive research, the present inventors have discovered that by adding a small amount of chelator to the triorganotin-containing copolymer or when formulating the paint, excellent storage stability can be obtained even in the presence of copper or copper compounds, The invention has been completed.

That is, the present invention provides an antifouling paint containing {a} a tri-organotin-containing copolymer and 'b- steel or a steel compound, in which a small amount of the 'c} chelator is added to the tri-organotin-containing copolymer. A storage-stable antifouling paint composition characterized in that it is added to or added to the paint formulation.

Examples of the chelator added in the antifouling paint composition of the present invention include ethylenediaminetetraacetic acid, nitrilotriacetic acid, diminodiacetic acid, cyclohexanediaminetetraacetic acid, glycol ether diamine tetraacetic acid, and ethyl ether diamine. Tetraacetic acid, dihydroxyethylglycine, acetylacetone ethylenediimine, zinc thiocyanate, sodium thiocyanate, potassium thiocyanate, magnesium thiocyanate, 2,3-dimercaptopropanol,
Examples include diethyldithiocarbamic acid, sodium salt of diethyldithiocarbamic acid, zinc salt of diethyldithiocarbamic acid, calcium salt of diethyldithiocarbamic acid, thiourea, thiocarbazide, thioglycolic acid, and phenanthroline.

One or more of these compounds can be added. Further, examples of the tri-organotin-containing copolymer constituting the antifouling paint component of the present invention include:
26 and Jiko Sho 44-1957 Publication,
A triorganotin-containing copolymer obtained by copolymerizing a triorganotin salt of a polymerizable unsaturated basic acid or a polybasic acid with a polymerizable unsaturated monomer, ■ Polymerizable unsaturated basic acid Examples include triorganotin-containing copolymers obtained by reacting a triorganotin compound with a high acid value vinyl resin obtained by copolymerizing an acid or a polybasic acid with a polymerizable unsaturated monomer.

Here, the triorganotin group in the triorganotin-containing copolymer of the present invention includes cases where the organic group is an alkyl group or a cycloalkyl group having 1 to 8 carbon atoms, that is, a trialkyltin group, a tricycloalkyl group, Examples include alkyltin groups.

In addition, the polymerizable unsaturated basic acids used in the above methods 1 to 2 include acrylic acid, methacrylic acid, Q-
Examples of the polymerizable unsaturated polybasic acids include cyanoacrylic acid, crotonic acid, and vinylbenzoic acid; examples of the polymerizable unsaturated polybasic acids include itaconic acid and citraconic acid; and examples of the polymerizable unsaturated monomers used in the copolymerization include methyl methacrylate and butyl. Methacrylate, cyclohexyl methacrylate, phenyl methacrylate, ethyl acrylate, butyl acrylate, octyl acrylate, dodecyl acrylate,
hexyl acrylate, phenyl acrylate,
Acrylic compounds such as hydroxyethyl acrylate,
Vinyl compounds with functional groups such as vinyl chloride, vinylidene chloride, acrylonitrile, methacrylonitrile, pinyl acetate, vinyl phthylate, butyl vinyl ether, octyl vinyl ether, dodecyl vinyl ether, lauryl vinyl ether, ethylene, butadiene, styrene, etc. vinyl hydrocarbons. One type or two or more types of polymerizable unsaturated monomers may be used. Examples of other copper or steel compounds constituting the antifouling paint of the present invention include metallic copper, copper alloys, box oxidized steel, Rodan copper, phosphide steel, copper rosinate, naphthenic acid steel, and hydroxide steel. Among these, suboxide steel and Rodan copper are particularly preferred. The content of each component in the antifouling paint of the present invention is 5 to 5% by weight of the triorganotin-containing copolymer and 10 to 7% by weight of the copper or steel compound, based on the total solid content of the paint. Something can happen.

The amount of the chelator added to the antifouling paint of the present invention is 0.01 to 10.0 parts by weight per 100 parts by weight of the triorganotin-containing copolymer (as solid content). parts by weight, preferably 0.1 to 3
Parts by weight.

It may be added in advance during the production of the tri-organotin-containing copolymer, it may be added immediately after production, or it may be added at the stage of forming a coating. The antifouling coating composition of the present invention thus obtained can maintain long-term storage stability.

This completely eliminates defects caused by increased viscosity, such as poor pouring during paint mixing, deviations in designed film thickness after mixing paint, and deterioration in paintability such as uneven film thickness. and maintain product value. It is also possible to always exhibit excellent antifouling performance. The antifouling paint composition of the present invention obtained in this way can be directly dissolved in an organic solvent or mixed with pigments, carriers, plasticizers, paint conditioners, and other resins (such as methyl methacrylate, butyl methacrylate, and butyl methacrylate). Acrylate polymers) and mold-soluble substances (e.g., low-molecular-weight polybutene, chlorinated paraffin) as a mold elution regulator (retardant or accelerator), used in ship bottom antifouling paints along with tri-organotin compounds and diluents if necessary. .

The present invention will be explained below with reference to Production Examples, Examples, and Test Examples.

In each example, the middle part indicates parts by weight, and % indicates weight %. Production Example of Tri-Organotin-Containing Copolymer Production Example A In a 1-flask equipped with a thermometer and a lamp, 12 g of tri-n-butyltin methacrylate, 50 g of methyl methacrylate, 30 g of butyl vinyl ether, and 1.0 g of penzoyl peroxide. Thioglycolic acid 0.0% after 20 females. Polymerization was carried out at 85-90° C. for 8 hours.

The obtained tri-n-butyltin-containing copolymer solution has a viscosity (
2500) has a specific ps of 70, and its heating residue is 49.9
%Met. Production Example B 200 g of tri-n-butyltin methacrylate, 90 g of methyl methacrylate, log of butyl acrylate, and 1. 7 xylene 30 female
After polymerization for 8 hours at 5 to 80 qo, phenanthroline 1. 0 was added.

The obtained tri-n-butyltin-containing copolymer solution has a viscosity (
25oo) has a specific ps of 90, and its heating residue is 49.7
%Met. Production Example C In Production Example A, 0.0% thioglycolic acid was added. 2 instead of place
3-dimercaptopropanol 0. Polymerization was carried out in exactly the same manner as in Production Example A except for the addition of the following.

The obtained tri-n-butyltin-containing copolymer solution has a viscosity (
25qo) has a nutritional ratio ps, and its heating residue is 49.6%
Met. Production Example D In Production Example A, 0.0% thioglycolic acid was added. Polymerization was carried out in exactly the same manner as in Production Example A, without adding any salt.

The obtained tri-n-butyltin-containing copolymer solution has a viscosity (
2500) had a specific ps of 66, and the heating residue was 49.8%. Production Example E Polymerization was carried out in exactly the same manner as Production Example B except that 1.5 g of phenanthroline was not added.

The obtained tri-n-butyltin-containing copolymer solution has a viscosity (
250C) with a specific ps of 85 and a heating residue of 49.6%. Production Example F Using the same equipment as in Production Example A, 195 g of tri-n-butyltin methacrylate, 90 g of methyl methacrylate, 15 g of butyl acrylate, and 1.0 g of benzoyl peroxide were added. The string and 300 g of xylene were polymerized at 80 to 900 C for 8 hours.

The obtained tri-n-butyltin-containing copolymer solution has a viscosity (
25qo) and a ratio ps of 55, and the heating residue was 49.8%. Production Example G In the same apparatus as Production Example A, 2,3-dimercaptopropanol 2 was added to 130 g of bis(tri-n-butyltin)itaconate, 60 g of methyl methacrylate, log octyl acrylate, 2.0 g of azobisisobutyronitrile, and 200 g of xylene. Add .0g and 75-80qo
Time polymerization was performed.

The obtained tri-n-butyltin-containing copolymer solution has a viscosity (
2yo) had a specific ps of 115, and the heating residue was 49.8%. Examples 1 to 10 A copper compound and a chelator were added to the solution of the triorganotin-containing copolymer obtained in Production Examples A to G (however, a copper compound and a chelator were added to the solution of the triorganotin-containing copolymer obtained in Production Examples A to C and G). A ship bottom antifouling paint was produced by blending pigments and solvents in the proportions shown in Table 1.

Comparative Examples 1 to 3 Using solutions of triorganotin-containing copolymers that do not contain chelators (i.e., copolymer solutions obtained in Production Examples D to F),
A copper compound, a pigment, and a solvent were blended with this in the proportions shown in Table 1 to produce a ship bottom antifouling paint.

Note that the values in Table 1 are parts by weight.

Table 1 (Note 1) Symbol (a) and others in the table indicate the following.

(Illusion: Added at the time of manufacturing or immediately after manufacturing ■: Added to paint formulation 1) Each was placed in a type metal can, and the viscosity at 2 mm was measured using a B type viscometer.

Thereafter, the round cans were sealed and stored indoors at room temperature avoiding direct sunlight for 6 months, and then the viscosity was measured in the same manner as above to examine storage stability. The results are shown in Table 2.0 Antifouling test A sandblasted mild steel plate (300 x 100 x 2 sails) was coated with commercially available ship bottom No. 1 paint twice, and the total dry film thickness was 1
It was set to 00m.

This was coated with Examples 1 to 10 and Comparative Examples 1 to 3, and after being stored at room temperature for 5 months, each coating was applied so that the dry film thickness was 100 peaks. After drying each coated plate at room temperature for one week,
An immersion test was conducted in Owase Bay, Mie Prefecture, and observations were made periodically. The results are shown in Table 2. 2 (Note) The symbols in the table indicate the following.

○ mark: Adhesion of marine animals and plants △ mark: 〃 Adhesion, less than 20% × mark: 〃
There is adhesion, 20 purple or more

Claims (1)

[Claims] 1. In an antifouling paint whose main components are (a) a triorganotin-containing copolymer and (b) copper or a copper compound, a small amount of (c) a chelator is added to the triorganotin-containing copolymer or blended into the paint. An antifouling paint composition having storage stability characterized by being added to.