JP2857717B2 - Antifouling paint composition - Google Patents

Description

Description: TECHNICAL FIELD The present invention relates to an antifouling paint composition.

BACKGROUND OF THE INVENTION Antifouling paints using a trialkyltin polymer compound as a vehicle are known. This antifouling paint is excellent in that the elution amount of the antifouling agent is suppressed to a minimum level for maintaining the antifouling property, and a certain amount is eluted for a long period of time. In this paint, the trialkyltin polymer compound used as a vehicle is hydrolyzed in a slightly alkaline atmosphere of seawater to release the tin compound, and the vehicle becomes water-soluble and the coating film is consumed.
As a result, the unevenness of the coating film becomes smooth, which reduces the seawater frictional resistance of the ship and contributes to a reduction in fuel cost.

The vehicle resin of the self-polishing paint is, for example, a copolymer of tributyltin (meth) acrylate and a comonomer containing no free carboxyl group. However, there is a need for the development of a self-polishing type antifouling paint vehicle resin instead of a trialkyltin polymer compound because of concerns about the effects of trialkyltin on ecosystems.

The present inventors have proposed in JP-A-62-57464 and the like, instead of the above tributyltin (meth) acrylate copolymer, for example, a divalent or higher-valent heavy metal to (meth) acrylic acid as a resin satisfying such a demand. A metal-containing resin having a repeating unit in the form of a salt bound to another monobasic organic acid by an ionic bond has been proposed. However, such a polymer metal salt resin has poor storage stability because it reacts with cuprous oxide and copper rhodan contained in the antifouling paint to cause gelation and precipitation. The same applies when the paint contains a metal oxide pigment such as zinc oxide.

SUMMARY OF THE INVENTION The present invention is directed to an antifouling coating composition containing a polymer metal salt resin disclosed by the present inventors in Japanese Patent Application Laid-Open No. 62-57464 or the like, and an aromatic compound capable of coordinating to the metal salt resin. By adding at least one coordination amount of an aromatic nitro compound, a urea compound, a nitrile, an organic sulfur compound, or a phenol, the reactivity with cuprous oxide or rhodan copper and / or zinc oxide is controlled, and the storage stability of the paint is controlled. Successfully increased. Accordingly, the present invention provides: A. a vehicle resin comprising: (Wherein, R ¹ is a hydrogen atom, a methyl or alkoxycarbonyl group, R ² is a hydrogen atom or an alkoxycarbonyl group,
A is a pendant group whose terminal is an acid ion, M is a transition metal element, L is a monobasic organic acid ion, and m is the valence of the metal element M. (B) contains 95 to 20% by weight of a repeating unit corresponding to an ethylenically unsaturated monomer having no pendant acid group, and has a number average molecular weight of 2,000 to 100,000. B. at least one coordination amount of an aromatic nitro compound, urea compound, nitrile, organic sulfur compound, or phenol capable of coordinating with the copolymer metal salt; and C. cuprous oxide Alternatively, the present invention relates to an antifouling coating composition containing rhodan copper and / or zinc oxide.

By complexing the copolymer metal salt with an aromatic nitro compound or the like, reactivity with a copper or zinc compound is blocked, and an antifouling paint composition having excellent storage stability can be obtained.

Preferred Embodiments The copolymer metal salt resin of the present invention can be produced by various methods, but a method of first producing a copolymer having a corresponding pendant acid group, and then converting this to a high molecular weight metal salt is preferred. preferable.

The copolymer having a pendant acid group is produced by radical polymerization of an ethylenically unsaturated monomer having an acid group and an ethylenically unsaturated monomer having no acid group in a solution by a conventional method. Can be.

Examples of the monomer having a carboxyl group as an acid group include acrylic acid, methacrylic acid, and the like, and a hydroxy group-containing monomer such as monoalkyl maleate, monoalkyl itaconate, and 2-hydroxyalkyl (meth) acrylate. And half-esters with dibasic carboxylic acids such as phthalic acid, succinic acid, and maleic acid.

Examples of the monomer having a sulfonic acid group as an acid group include p
-Styrene sulfonic acid, 2-methyl-2-acrylamidopropanesulfonic acid and the like.

Examples of the monomer having a phosphoric acid group as an acid group include acid phosphoxypropyl methacrylate, 3-chloro-2-acidophosphoxypropyl methacrylate, and acid phosphoxyethyl methacrylate.

Examples of the monomer having no pendant acid group include hydrocarbons such as ethylene, propylene, styrene, α-methylstyrene, vinyltoluene, and t-butylstyrene; methyl (meth) acrylate, ethyl (meth) acrylate, n Alkyl (meth) acrylates such as -butyl (meth) acrylate and 2-ethylhexyl (meth) acrylate; hydroxyalkyl (such as 2-hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, and hydroxybutyl (meth) acrylate (Meth) acrylates; amides such as acrylamide and methacrylamide; (meth) acrylonitrile; vinyl esters such as vinyl acetate and vinyl propionate;
There are vinyl chloride and the like.

The metal to form a salt with the copolymer having a pendant acid group is a transition metal element, that is, 3A to 3P in the long-period periodic table.
Selected from group 7A, 8 and 1B elements. Among them, cobalt, nickel, copper, zinc and manganese are preferred.

A polymer metal salt of a copolymer having a pendant acid group and a transition metal is a copolymer having a pendant acid group or an alkali metal salt thereof, and at least an equivalent of a metal oxide, hydroxide, chloride, or sulfide. It is produced by simultaneously reacting a metal compound such as a basic carbonate and at least an equivalent of a monobasic organic acid, or by reacting a metal salt of a monobasic organic acid with a copolymer having a pendant acid group. be able to. As another method, a monomer having an acid group and a monobasic organic acid ion-bonded to the same metal atom is prepared in advance, and the metal salt monomer is used together with a monomer having no acid group. It can also be produced by polymerization.

Examples of monobasic organic acids used herein include acetic acid, propionic acid, butyric acid, lauric acid, stearic acid, linoleic acid, oleic acid, naphthenic acid, chloroacetic acid, fluoroacetic acid, abietic acid, phenoxyacetic acid, valeric acid, Monocarboxylic acids such as dichlorophenoxyacetic acid, benzoic acid, and naphthoic acid; and monosulfonic acids such as benzenesulfonic acid, p-toluenesulfonic acid, dodecylbenzenesulfonic acid, naphthalenesulfonic acid, and p-phenylbenzenesulfonic acid.

One preferred method for producing the polymer metal salt is the method disclosed by the present inventors in JP-A-63-128008. The method is to simultaneously react a metal salt of a low-boiling monobasic acid and a high-boiling monobasic acid to a copolymer having a pendant acid group,
This is a method of obtaining a polymer metal salt in which a pendant acid copolymer ion and a high-boiling monobasic acid ion are ion-bonded to the same metal atom. For example, by reacting a pendant acid group-containing copolymer copper hediacetate with naphthenic acid by heating, a polymer metal salt in which pendant acid ions and naphthenate ions of the copolymer are ion-bonded to copper atoms can be obtained.

A component serving as a ligand of the central metal atom can be added to the solution of the polymer metal salt resin thus obtained to form a complex.

Examples of such a ligand component include aromatic nitro compounds, amines, nitriles (cyano compounds), phenols, and organic sulfur compounds.

The ligand compound that can be used in the present invention is not limited to a monodentate ligand. Bidentate or higher ligands having the same or different coordination atoms in one molecule can also be used.

Examples of compounds that can be used as ligands include aromatic nitro compounds such as nitrobenzene, cyano compounds such as isophthalonitrile, urea, thiourea, N- (3,
4-dichlorophenyl) -N "-methoxy-N" -methylurea, N- (3,4-dichlorophenyl) -N ", N"-
Substituted ureas such as dimethyl urea, hydroquinone, hydroquinone monomethyl ether, nonylphenol,
Phenols such as BHT; thiophenes and derivatives thereof; para-toluenesulfonic acid n-propyl ester; mercaptobenzothiazole; dimethyldithiocarbamate; and sulfur-containing compounds such as benzeneisothiocyanate. For use as a vehicle in antifouling paints, it is also possible to select a component which itself acts as an antifouling agent. The amount of these ligands is at least one coordination amount per atom of the central metal and at most up to the saturation coordination amount, whereby an intended stable paint can be obtained. However, as long as it does not cause a coating defect such as a crack or a blister while immersed in seawater, it may be added in an amount exceeding the coordination amount. The amount that can be used at this time depends on the type of ligand, but is up to (n-1) × 4 where n is the number of coordinations.

The polymer metal salt resin of the present invention contains 5 to 80% by weight of a repeating unit (a) containing a pendant acid group bonded to a metal,
It preferably contains 20 to 70% by weight and 95 to 20% by weight, preferably 80 to 30% by weight, of the other ethylenically unsaturated monomer (b). If the number of repeating units (a) is too large, the coating film is consumed at a high speed and is consumed in a short period of time. Conversely, if the number of repeating units (a) is too small, a self-polishing effect cannot be expected. The number average molecular weight of the resin is 2,000 to 100,000, preferably 4,000 to
40,000. If the molecular weight is too low, the film-forming property is inferior. On the other hand, if the molecular weight is too high, it becomes difficult to prepare a coating or the hydrolyzability of the coating film decreases.

In addition, the resin of the present invention has a metal bonded thereto of 0.3 to 20.
It is preferably designed to contain 0.5% to 15% by weight.

Hereinafter, the present invention will be described in detail with reference to Production Examples and Examples. In these, "parts" and "%" are based on weight unless otherwise specified.

Production of Resin Varnish Containing Pendant Acid Group Production Example 1 To a four-necked flask equipped with a stirrer, a reflux condenser and a dropping funnel, 120 parts of xylene and 30 parts of n-butanol were added.
Keep at ~ 120 ° C. A mixture of 60 parts of ethyl acrylate, 25 parts of 2-ethylhexyl acrylate, 15 parts of acrylic acid and 2 parts of azobisisobutyronitrile was added dropwise over 3 hours, and the mixture was kept at the same temperature for 2 hours after the addition. Hold. The obtained varnish had a solid content of 39.8% and an acid value of the solid content of 200 mgKOH / g.

Production Example 2 100 parts of xylene and n were placed in the same flask as in Production Example 1.
-Charge 20 parts butanol and keep at 100-110 ° C. A mixture of 25.7 parts of acrylic acid, 57.8 parts of ethyl acrylate, 16.5 parts of methyl methacrylate, and 3 parts of azobisisobutyronitrile was added dropwise over 1 hour, and the mixture was kept at the same temperature for 2 hours after the addition. . The solid content of the obtained varnish was 39.6%, and the acid value of the resin solid content was 200 mgKOH / g.

Production Example 3 Into the same flask as in Production Example 1, 100 parts of xylene and n
-Charge 20 parts butanol and keep at 100-110 ° C. To this 7.7 parts of methacrylic acid, 64.4 parts of methyl methacrylate,
A mixed solution consisting of 28 parts of 2-ethylhexyl acrylate and 3 parts of azobisisobutyronitrile is added dropwise over 4 hours, and after the addition, the mixture is kept at the same temperature for 2 hours. The varnish obtained had a solid content of 39.8% and an acid value of the solid content of 50 mgKOH / g.

Production of Polymer Metal Salt Varnish Production Example 4 To a four-necked flask equipped with a stirrer, a reflux condenser, and a decanter, 100 parts of the varnish of Production Example 1, 20 parts of naphthenic acid, and 7 parts of copper (II) hydroxide were added. The temperature was raised to 120 ° C. and maintained at the same temperature for 2 hours, during which water (2.5 g) generated was distilled off. The obtained green varnish A had a solid content of 51.3% and a viscosity of 2.2 poise. A portion of varnish A was taken, the resin was precipitated with white spirit, and the copper content was determined by fluorescent X-ray method to be 6.8%.

Production Example 5 In the same flask as Production Example 4, varnish 100 of Production Example 2 was added.
Parts, 25.9 parts of zinc (II) acetate, 40.3 parts of oleic acid, and 120 parts of xylene, and heated to 120 ° C., and acetic acid produced as the reaction proceeds was distilled off together with the solvent. The reaction was continued until no acetic acid was detected in the solvent distilled off. The varnish B thus obtained had a solid content of 55.3% and a viscosity of RS.

Production Example 6 In the same flask as in Production Example 4, varnish 100 of Production Example 3
And 7.4 parts of copper (II) propionate, 10 parts of naphthenic acid and 20 parts of deionized water were added and heated to 100 ° C., and propionic acid generated as the reaction proceeded was distilled off together with water. The reaction was continued until no more water and propionic acid distilled. The varnish C thus obtained had a solid content of 52.3% and a viscosity of P.

Production Example 7 In the same flask as in Production Example 4, varnish 100 of Production Example 3
Parts, manganese (II) acetate 8.1 parts and 2,4-dichlorophenoxyacetic acid 7.8 parts were charged, heated to 70 ° C., and acetic acid formed was distilled off under reduced pressure. After completion of the reaction, xylene 95 parts was added. The varnish D thus obtained had a solid content of 56.3% and a viscosity of U.

Examples and Comparative Examples Ratios of the copolymer metal salt varnishes A to D of Production Examples 4 to 7, various ligand compounds, cuprous oxide or rhodan copper, metal oxide pigments and solvents shown in Table 1. And an antifouling paint composition was obtained by a conventional method.

(Note) Urea compound A: N, N-dimethyl-N'-phenylurea Urea compound B: N- (3,4-dichlorophenyl) -N "-
Methoxy-N "-methylurea Urea compound C: N- (3,4-dichlorophenyl) -N",
N ″ -Dimethylurea Sulfur compound: 3,3,4,4, -tetrachlorotetrahydrothiophene-1,1-dioxide Storage stability test of paint and storage results After sealing in a glass container, it was stored for one month at 50 ° C. The results of examining the paint condition after storage are shown in Table 2.

──────────────────────────────────────────────────続 き Continued on the front page (72) Inventor Masayuki Matsuda 19-17 Ikedanakamachi, Neyagawa-shi, Osaka Japan Paint Co., Ltd. (58) Field surveyed (Int.Cl. ⁶ , DB name) C09D 5/14- 5 / 16,133 / 00-133/1 6

Claims (2)

(57) [Claims] (1) A. The vehicle resin is represented by the following formula (a): (Wherein, R ¹ is a hydrogen atom, a methyl or alkoxycarbonyl group, R ² is a hydrogen atom or an alkoxycarbonyl group,
A is a pendant group whose terminal is an acid ion, M is a transition metal element, L is a monobasic organic acid ion, and m is the valence of the metal element M. And (b) 95 to 20% by weight of a repeating unit corresponding to another ethylenically unsaturated monomer and having a number average molecular weight of 2,000 to 100,000.
B. at least one blending amount of an aromatic nitro compound, urea compound, nitrile, organic sulfur compound, or phenol capable of coordinating with the copolymer metal salt; An antifouling paint composition comprising copper oxide or copper rhodan and / or zinc oxide. 2. The method according to claim 1, wherein the metal element M is nickel, cobalt,
2. The antifouling coating composition according to claim 1, which is copper, zinc or manganese.