JPH0480269A - Antifouling coating composition - Google Patents

Abstract

PURPOSE:To obtain the title composition excellent in storage stability by mixing a specified copolymer metal salt with a specified compound which can coordinate therewith and a cuprous oxide or copper rodanide and/or ZnO. CONSTITUTION:A vehicle resin comprising a copolymer metal salt comprising 5-80wt.% repeating units of the formula (wherein R<1> is CH3 or R<2>; R<2> is H or alkoxycarbonyl; A is a pendant group terminated with an acid ion; M is a transition metal element; L is a monobasic organic acid ion; and m is the valence of the metallic element M) and 95-20wt.% repeating units derived from another ethylenically unsaturated monomer and having an average molecular weight of 2,000-100,000 [e.g. a compound prepared by copolymerizing ethyl acrylate with 2-ethylhexyl acrylate and acrylic acid and reacting the obtained copolymer with naphthenic acid or copper (II) hydroxide] is mixed with an amine, an organic acid or an alcohol which can coordinate therewith (e.g. octanol) in an amount to give a coordination number of at least one and cuprous oxide or copper rodanide and/or ZnO (e.g. cuprous oxide).

Description

[Detailed description of the invention] ■Distortion ball group The present invention relates to an antifouling coating composition.

Main departure! Antifouling paints using a trialkyltin polymer compound as a vehicle are known. This antifouling paint is excellent in that it suppresses the elution amount of the antifouling agent to the minimum level that maintains antifouling properties, and elutes a constant amount over 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, releasing a tin compound, and the vehicle becomes water-soluble, causing the paint film to wear away. This reduces the seawater frictional resistance of ships and contributes to fuel cost savings.

The vehicle resin of this self-polishing paint is, for example, a copolymer of tributyltin (meth)acrylate and a comonomer containing no free carboxyl groups. However, due to concerns about the impact of trialkyltin on the ecosystem,
It is desired to develop a vehicle resin for self-polishing antifouling paints to replace trialkyltin polymer compounds.

The present inventors proposed, in Japanese Patent Application No. 123124/1983, as a resin that satisfies such demands, for example, by adding (meth)acrylic acid to a divalent or higher heavy metal instead of the above-mentioned tributyltin (meth)acrylate copolymer. We proposed a metal-containing resin having repeating units in the form of salts bound to other monobasic organic acids through ionic bonds. However, such polymeric metal salt resins have poor storage stability because they react with cuprous oxide and copper rhodan contained in antifouling paints, causing gelation and precipitation. The same is true even if the paint contains metal oxide pigments such as zinc oxide.

Honko dish summer supervisor! The present invention was first filed by the inventors in Japanese Patent Application No. 61-113124.
By adding at least one coordination position of an amine, an organic acid, or an alcohol capable of coordinating to the metal salt resin to the antifouling paint composition containing the polymeric metal salt resin disclosed in No. 1, etc., cuprous oxide or rhodan We succeeded in controlling the reactivity with copper and/or zinc oxide and increasing the storage stability of the paint.

Therefore, in the present invention, A, as a vehicle resin, (a) Formula % Formula % (In the formula, R1 is a hydrogen atom, a methyl or an alkoxycarbonyl group, R2 is a hydrogen atom or an alkoxycarbonyl group, and A has an acid ion at the terminal. In the pendant group, M is a transition metal element, L is a monobasic organic acid ion, and m is the valence of the metal element M.

20 to 80% by weight of repeating units represented by; (b)
A copolymer metal salt containing 80 to 20% by weight of repeating units corresponding to ethylenically unsaturated monomers having no pendant acid groups and having a number average molecular weight of 2,000 to 100,000; An antifouling coating composition characterized in that it contains at least one position of an amine, an organic acid or an alcohol capable of being coordinately bonded to a polymeric metal salt, and CO cuprous oxide or copper rhodan oxide and/or zinc oxide. .

By complexing the copolymer metal salt with an amine, an organic acid, or an alcohol, reactivity with copper and zinc compounds is blocked, and an antifouling paint composition with excellent storage stability can be obtained.

Although the copolymer metal salt resin of the present invention can be produced by various methods, first a copolymer having a corresponding pendant acid group is produced, and then this is mixed with a polymeric metal. The method of making it into a salt is preferred.

A copolymer having pendant acid groups can be produced by radical polymerizing an ethylenically unsaturated monomer having an acid group and an ethylenically unsaturated monomer having no acid group in a solution using a conventional method. I can do it.

Examples of monomers having carboxyl groups as acid groups include acrylic acid, methacrylic acid, and hydroxy group-containing monomers such as maleic acid monoalkyl esters, itaconic acid monoalkyl esters, and 2-hydroxyalkyl (meth)acrylates. and half esters of dibasic carboxylic acids such as phthalic acid, succinic acid, and maleic acid.

As a monomer having a sulfonic acid group as an acid group, p-
Examples include styrene sulfonic acid and 2-methyl-2-acrylamidopropanesulfonic acid.

Examples of monomers having a phosphoric acid group as an acid group include acidophosphoxypropyl methacrylate, 3-chloro-2-acidophosphoxypropyl methacrylate, and acidophosphoxyethyl methacrylate.

Examples of monomers without pendant acid groups include ethylene,
Hydrocarbons such as propylene, styrene, α-methylstyrene, vinyltoluene, t-butylstyrene; methyl (
meth)acrylate, ethyl(meth)acrylate, n
-Butyl (meth)acrylate, 2-ethylhexyl (
Alkyl (meth)acrylates such as meth)acrylate; 2-hydroxyethyl (meth)acrylate, hydroxypropyl (meth)acrylate, hydroxybutyl (
Hydroxyalkyl (meth) such as meth)acrylates
Acrylates; amides such as acrylamide and methacrylic acid amide; (meth)acrylonitrile; vinyl esters such as vinyl acetate and vinyl propionate; and vinyl chloride.

The metal to form a salt with the copolymer having pendant acid groups is selected from transition metal elements, ie elements of groups 3A to 7A, 8 and IB of the long periodic table. Among them, cobalt, nickel, copper, zinc and manganese are preferred.

The polymeric metal salt of a copolymer having pendant acid groups and a transition metal is a copolymer having pendant acid groups or an alkali metal salt thereof, and at least an equivalent amount of a metal oxide, hydroxide, chloride, or sulfide. produced by simultaneously reacting a metal compound, such as a basic carbonate, with at least an equivalent amount of a monobasic organic acid, or by reacting a copolymer having pendant acid groups with a metal salt of a monobasic organic acid. can do. As another method, a monomer in which a monomer having an acid group and a monobasic organic acid are ionically bonded to the same metal atom is prepared in advance, and the metal salt monomer is combined with a monomer having no acid group. It can also be produced by polymerization.

Examples of monobasic organic acids used here 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, Examples include monocarboxylic acids such as dichlorophenoxyacetic acid, benzoic acid, and naphthoic acid; monosulfonic acids such as benzenesulfonic acid, p-)luenesulfonic acid, dodecylbenzenesulfonic acid, naphthalenesulfonic acid, and p-phenylbenzenesulfonic acid.

A preferred method for producing the polymeric metal salt is the method disclosed by the present inventors in JP-A-63-128008. This method involves simultaneously reacting a metal salt of a low-boiling basic acid and a high-boiling basic acid to a copolymer having pendant acid groups, and reacting the copolymer pendant acid ion and the high-boiling basic acid to the same metal atom. This is a method for obtaining a polymeric metal salt in which ions are ionically bonded. For example, by subjecting a pendant acid group-containing copolymer copper hediacetate to a thermal reaction with naphthenic acid, a polymeric metal salt in which pendant acid ions and naphthenic acid ions of the copolymer are ionically bonded to copper atoms can be obtained.

When a compound serving as a ligand is added to the thus-obtained fest containing the polymeric metal salt resin, the resin is complexed.

Components that serve as such ligands are amines, alcohols, and organic acids.

The ligand compounds that can be used in the present invention are not limited to monodentate ligands. - It is also possible to use more than one dish-shaped ligand with several identical or different coordinating atoms in the molecule. Furthermore, the basic organic acid ion forming the polymeric metal salt, such as glycine, may have an atomic group serving as another ligand.

Examples of compounds that can be used as ligands include primary, secondary and tertiary alkylamines such as mono- and tri-n-propylamine, cyclic alkylamines such as piperidine, piperazine, ethylene diamine, etc. Alkylene diamines, alkanolamines such as 7-, di-, and triethalamines; alcohols such as butyl alcohol, octyl alcohol, and geraniol; glycols such as ethylene glycol; acetic acid, propionic acid, benzoic acid, lactic acid, malic acid. , carboxylic acids such as citric acid, tartaric acid, and glycine. For use as a vehicle in antifouling paints, components may also be selected in which the ligand itself acts as an antifouling agent. The configuration of these ligands is at least one coordination per atom of the central metal and at most up to a saturated coordination amount, thereby making it possible to obtain the desired stable paint. However, as long as coating film defects such as cracks and blisters do not occur during immersion in seawater, it is acceptable to add more than the saturated position. The amount that can be used at this time varies depending on the type of ligand, but is up to n-1)X4, where n is the coordination number.

The polymeric metal salt resin of the present invention contains 5 to 80% by weight of repeating units (a) containing metal-bonded pendant acid groups;
It preferably contains 20 to 70% by weight, and 95 to 20M%, preferably 80 to 30% by weight of other ethylenically unsaturated monomer repeating units (b). If the repeating unit (a) is too large, the coating film will wear out quickly and will be consumed in a short period of time, while if it is too small, self-polishing action cannot be expected. In addition, the number average molecular weight of the resin is 2.000
~100,000.

Preferably it is 4,000 to 40,000. If the molecular weight is too low, film-forming properties will be poor, while if the molecular weight is too high, it will be difficult to form into a coating or the hydrolyzability of the coating will be reduced.

Further, the resin of the present invention has a metal bonded to it of 0.3 to 2
It is preferable to design the content to be 0% by weight, preferably 0.5 to 15% by weight.

The present invention will be explained in detail below with reference to production examples and examples. In these, "parts" and "1%" are based on weight unless otherwise specified.

Preparation Example 1 of Pendant 4 Varnish 120 parts of xylene and 30 parts of n-butanol were added to a four-hole flask equipped with a stirrer, a reflux condenser, and a dropping funnel.
Keep at 110-120°C. To this ethyl acrylate 6
A mixed solution consisting of 0 parts of acrylic acid, 25 parts of 2-ethylhexyl acrylate, 15 parts of acrylic acid, and 2 parts of azobisisobutyronitrile was added dropwise over a period of 3 hours, and the temperature was maintained at the same temperature for 2 hours after the addition.

The solid content of the obtained varnish was 39.8%, and the solid acid value was 20.
It was 0 mgKOH/g.

Production Example 2 To the same flask as Production Example 1, 100 parts of xylene and n
- Charge 20 parts of butanol and maintain at 100-110°C. To this, 25.7 parts of acrylic acid, 57 parts of ethyl acrylate
．． A mixed solution consisting of 8 parts of methyl methacrylate, 16.5 parts of azobisisobutyronitrile, and 3 parts of azobisisobutyronitrile was added dropwise over a period of 1 hour, and the temperature was maintained at the same temperature for 2 hours after the addition. The resulting varnish had a solid content of 39.6%, a resin solid content, and an acid value of 200 mgK.
It was OH/g.

Production Example 3 To the same flask as Production Example 1, 100 parts of xylene and n
- Charge 20 parts of butanol and maintain at 100-110°C. To this was added 4 parts of a mixed solution consisting of 7.7 parts of methacrylic acid, 64.4 parts of methyl methacrylate, 28 parts of 2-ethylhexyl acrylate, and 3 parts of azobisisobutyronitrile.
It takes time to drop the solution, and after dropping, it is kept at the same temperature for 2 hours.

The solid content of the obtained varnish was 39.8%, and the solid content acid value was 5.
It was 0 ■KOH/g.

11' of gold varnish @ Production example 4 To a four-hole flask equipped with a stirrer, reflux condenser, and decanter, add 100 parts of the varnish of Production example 1, 20 parts of naphthenic acid, and hydroxide! 7 parts of 1i1(II) were added, the temperature was raised to 120°C and kept at the same temperature for 2 hours, and the water (2.5g
) was distilled off. The solid content of the obtained green varnish A is 51
3%, and the viscosity was 2.2 poise. A portion of Varnish A was taken, the resin was precipitated with white spirit, and the copper content was determined to be 6.8% by fluorescent X-ray method.

Production Example 5 100 parts of the varnish from Production Example 2, 25.9 parts of zinc acetate (ff), 40.3 parts of oleic acid, and 120 parts of xylene were placed in the same flask as Production Example 4, heated to 120°C, and reacted. Acetic acid produced as the process progresses is distilled off together with f4. The reaction continued until no acetic acid was detected in the distilled solvent. The solid content of the obtained varnish B was 55.3%,
The viscosity was R-3.

Production Example 6 To the same flask as in Production Example 4, add 100 parts of the varnish of Production Example 3, 7.4 parts of copper(II) propionate, 10 parts of naphthenic acid, and 20 parts of deionized water, and heat to 100°C. Propionic acid produced as the reaction progressed was distilled off together with water. The reaction continued until no water or propionic acid distilled out. The solid content of the obtained varnish C was 52.3%,
The viscosity was P.

Examples and comparative examples Copolymer metal salt varnishes A and B of Production Examples 4 to 6.

C, various ligand compounds, cuprous oxide or copper rhodan, a metal oxide pigment, and a solvent were mixed in the proportions shown in Table 1, and an antifouling paint composition was obtained by a conventional method.

(Margin below) table (Part 1) varnish ■Shojiba 1191 units Oftar dodecyl alcohol Mono-n-propylamine di-n-propylamine tri-n-propylamine Takizake 1 Toro L door cuprous oxide rodin copper 雛-U door Hengara titanium dioxide zinc oxide □1 匪 11 ri xylene Methyl isobutyl ketone Total (part) table (Part 2) Varnish.

Arrangement hardware □ 0 machido ophthaltri n-propylamine octatoolamine isononanoic acid ethylene glycol acetic acid benzoic acid belly filth (dish Y cuprous oxide Rodan copper □ IL mouth red iron oxide titanium oxide zinc oxide disease - elbow (Plate Y xylene methyl isobutyl ketone meter (parts) ■ Surface varnish with acetate ethylene diamine (Plate Y) xylene methyl isobutyl Ketone meter (part) 1 (part 3) -] J1 state - Dan sweet 0.5 m - 11 lights 1 -
After sealing it in a glass container, it was stored at 50°C for one month. Table 2 shows the results of examining the state of the paint after storage.

(Margin below)

Claims (2)

[Claims] (1) A, vehicle resin: (a) Formula ▲ Numerical formula, chemical formula, table, etc. ▼ (In the formula, R^1 is a hydrogen atom, methyl or alkoxycarbonyl group, R^2 is a hydrogen atom or 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, m is the valence of the metal element M.) 5 to 80% by weight of repeating units; (b) Contains 95-20% by weight of repeating units corresponding to other ethylenically unsaturated monomers, and has an average molecular weight of 2,000-2,000%
100,000, B, at least one coordination amount of an amine, organic acid or alcohol capable of coordinating to the copolymer metal salt; C, cuprous oxide or copper rhodan and/or Or an antifouling paint composition characterized by containing zinc oxide. (2) The antifouling paint composition according to item 1, wherein the metal element M is nickel, cobalt, copper, zinc, or manganese.