JPS6216231B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to storage-stable antifouling coating compositions. In recent years, polymeric organotin compounds containing organotin groups in their molecules have been used as excellent antifouling agents to prevent marine organisms from adhering to fishing nets and ship bottoms. It is also known to use a copper compound (for example, cuprous oxide, copper rhodan) in combination with this polymeric organotin compound to obtain a ship bottom paint having even higher antifouling performance. However, antifouling paints made by mixing copper or copper compounds with high-molecular organotin compounds gradually increase in viscosity during storage, and in severe cases gel, resulting in stringiness, deviations in the designed film thickness, and film thickness defects. It causes uniformity and uncoating, which reduces the value of the product. Furthermore, paints that have thickened or gelled in this manner often show a decrease in antifouling performance. As a result of intensive research, the present inventors have found that if a specific ether compound is added during the production of tri-organotin-containing polymers or copolymers or when formulating paints, excellent storage stability can be achieved even in the presence of copper or copper compounds. They found that it can be obtained and completed the present invention. That is, the present invention provides that (a) at least one
A triorganotin-containing polymer or copolymer having a group of - COOSnR ₃ (in the formula, R represents an alkyl group, a cycloalkyl group, or a phenyl group) and (b) an antifouling agent containing copper or a copper compound as a main component. In the paint, a cyclic ether compound and/or a compound having two or more ether groups in the molecule is added to the triorganotin-containing polymer or copolymer or at the time of blending the antifouling paint. This is an antifouling paint composition with storage stability. Examples of the ether compound added to the antifouling paint composition of the present invention include tetrahydrofuran, tetrahydropyran, dioxane, dimethyldioxane, dioxolane, dimethyldioxane, trioxane, ethylene glycol dimethyl ether, ethylene glycol diethyl ether, propylene glycol dimethyl ether, propylene Glycol diethyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, dimethoxymethane, diethoxymethane, 1,1-dimethoxyethane,
1,1-diethoxyethane, 1,1-dimethoxypropane, 1,1-diethoxypropane, 2,2
-dimethoxypropane, 2,2-diethoxypropane, trimethoxymethane, triethoxymethane, 1,1,1-trimethoxyethane, 1,1,
Examples include 2-trimethoxyethane. One or more types of these ether compounds can be added. In the present invention, the triorganotin-containing polymer or copolymer has at least one group in the molecule.
Polymers or copolymers having COOSnR ₃ (R is an alkyl, cycloalkyl, or phenyl group), such as JP-B No. 40-21426, JP-B No. 44-9579, JP-A-46-13392, and JP-B No. 49-20491 A triorganotin-containing copolymer and an unsaturated acid obtained by copolymerizing a triorganotin salt of a polymerizable unsaturated basic acid or a polybasic acid with a polymerizable unsaturated monomer, which are described in the publication No. A homopolymer of a triorganotin salt of Examples include triorganotin-containing copolymers obtained by reacting a triorganotin compound with a high acid value vinyl resin obtained by copolymerization. Here, the triorganotin group in the triorganotin-containing polymer or copolymer of the present invention includes cases where the organic group is an alkyl group having 1 to 8 carbon atoms, a cycloalkyl group, or a phenyl group. Examples include an alkyltin group, a tricycloalkyltin group or a triphenyltin group. The polymerizable unsaturated basic acids used in the above methods include acrylic acid, methacrylic acid, and vinylbenzoic acid, and the polymerizable unsaturated polybasic acids include maleic acid, itaconic acid, and their acid anhydrides. Examples of the polymerizable unsaturated monomers used in the copolymerization include methyl methacrylate, butyl methacrylate, cyclohexyl methacrylate, phenyl methacrylate, ethyl acrylate, butyl acrylate, octyl acrylate, dodecyl acrylate, cyclohexyl acrylate, and phenyl acrylate. Acrylic compounds such as acrylate and hydroxyethyl acrylate, vinyl chloride, vinylidene chloride, acrylonitrile, methacrylonitrile,
Vinyl compounds having a functional group such as vinyl acetate, vinyl butyrate, butyl vinyl ether, octyl vinyl ether, dodecyl vinyl ether, and lauryl vinyl ether, and vinyl hydrocarbons such as ethylene, butadiene, and styrene are exemplified. One type or two or more types of polymerizable unsaturated monomers may be used. Other copper or copper compounds constituting the antifouling paint of the present invention include metallic copper, copper alloy, cuprous oxide,
Copper rhodan, copper phosphide, copper rosinate, copper naphthenate, copper hydroxide, etc., especially cuprous oxide,
Rodan copper is preferred. The content of each component in the antifouling paint of the present invention is 5 to 50% by weight of triorganotin-containing polymer or copolymer and 10 to 70% by weight of copper or copper compound, based on the total solid content of the paint.
% by weight. The amount of the ether compound added to the antifouling paint of the present invention is 0.1 to 100 parts by weight, preferably 10 to 50 parts by weight, per 100 parts by weight of the triorganotin-containing polymer or copolymer (as solid content). It is. The ether compound may be added in advance during the production of the triorganotin-containing polymer or copolymer, or may be added immediately after production, or 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 thickening, such as poor pouring during paint formulation, deviations in designed film thickness after paint formulation, and poor paintability due to uneven film thickness. can be eliminated and product value can be maintained. Moreover, it is also possible to always exhibit excellent antifouling performance. The antifouling paint composition of the present invention thus obtained can be dissolved as is in an organic solvent or mixed with pigments, carriers,
Plasticizers, paint conditioners, other resins (e.g. methyl methacrylate/butyl methacrylate/butyl acrylate polymers) and poorly soluble substances (e.g. low molecular weight polybutenes, chlorinated paraffins) toxin elution regulators (retardants or accelerators) ), if necessary, other antifouling agents (e.g., tri-organotin compounds such as tributyltin fluoride, tributyltin oxide, triphenyltin fluoride, organic compounds such as thiuram disulfide, dimethyl dithiocarbamate), diluents, and ship bottom antifouling agents. Used in paint. The present invention will be explained below with reference to Production Examples, Examples, and Test Examples. In each example, the middle part is part by weight, and % is weight %.
shall be shown. Production example of triorganotin-containing copolymer Production example A: In a 1-flask equipped with a thermometer and a stirrer, 130 g of tributyltin methacrylate, 70 g of methyl methacrylate, and 1.5 g of benzoyl peroxide.
Then, 200 g of xylene was polymerized at 85 to 90°C for 8 hours. The obtained tributyltin-containing copolymer solution has a viscosity (25℃) of 820 cps, and the heating residue is
It was 49.8%. Production Example B Using the same equipment as Production Example A, 120 g of tributyltin methacrylate, 60 g of methyl methacrylate, 2-
75~20g of ethylhexyl methacrylate, 1.5g of azobisisobutyronitrile and 200g of xylene
Polymerization was carried out at 80°C for 8 hours. The obtained tributyltin-containing copolymer solution had a viscosity (25° C.) of 780 cps, and its heating residue was 49.9%. Production Example C In the same apparatus as Production Example A, 60 g of tetrahydrofuran was added to 130 g of tributyltin methacrylate, 70 g of methyl methacrylate, 1.5 g of benzoyl peroxide, and 140 g of xylene, and the mixture was heated at 85 to 90°C.
Time polymerization was carried out. The obtained tributyltin-containing copolymer solution had a viscosity (25° C.) of 760 cps, and its heating residue was 49.8%. Production Example D In one flask equipped with a thermometer, stirrer, addition funnel and reflux dehydrator, 27.5 g of methacrylic acid, 60 g of methyl methacrylate, 20 g of 2-ethylhexyl acrylate, 1.5 g of benzoyl peroxide,
Add 100g of dioxane and 100g of xylene and heat to 85~
Polymerization was carried out at 90°C for 8 hours. Next, bis(tributyltin) oxide was added dropwise at 85 to 90°C over 1 hour, and after stirring for 2 hours, reflux dehydration was performed at 100 to 110°C under reduced pressure for 1 hour. The obtained tributyltin copolymer solution had a viscosity (25°C) of 680 cps and a heating residue of 49.9%. Examples 1 to 8 A copper compound and an ether compound were added to the solution of the triorganotin-containing copolymer obtained in Production Examples A to D (however, a copper compound and an ether compound were added to the solution of the triorganotin-containing copolymer obtained in Production Examples A to D (however, the copolymer compound obtained in Production Examples C and A ship bottom antifouling paint was prepared by blending pigment, dispersant (hydrogenated castor oil-amide type), and solvent in the proportions shown in Table 1. Comparative Examples 1 to 2 A solution of a triorganotin-containing copolymer containing no ether compound (i.e., the copolymer solution obtained in Production Examples A and B) was used, and a copper compound, a pigment,
A ship bottom antifouling paint was manufactured by blending a dispersant (hydrogenated castor oil-amide system) and a solvent in the proportions shown in Table 1. . Note that the values in Table 1 are parts by weight.

【table】

[Table] Storage stability test Each of the antifouling paints obtained in Examples 1 to 8 and Comparative Examples 1 to 2 was placed in two round metal cans with a capacity of 200 ml, and one of the cans was placed in an air oven at 50°C. The other one was left at room temperature for 6 months, and the change in viscosity of each was examined. The viscosity was measured in a constant temperature bath at 25°C. The results are shown in Table 2.

【table】

【table】

Claims (1)

[Claims] 1 (a) At least one group in the molecule - COOSnR ₃
(in the formula, R represents an alkyl group, a cycloalkyl group, or a phenyl group) and (b) an antifouling paint containing copper or a copper compound as a main component, in which a cyclic ether compound is used. and/or a compound having two or more ether groups in the molecule is added to the triorganotin-containing polymer or copolymer or at the time of formulating the antifouling paint. Stain paint composition.