JPH0978006A - Underwater antifouling paint - Google Patents

Abstract

(57) [Summary] [Objective] To provide an underwater antifouling paint using a quaternary ammonium salt polymer as a vehicle resin in order to avoid the use of organic tin. A vinyl copolymer having 5 to 60 mol% of repeating units corresponding to a vinylpyridinium salt quaternized with an alkyl halide having 4 or more carbon atoms or an aralkyl halide, and the balance being a repeating unit corresponding to another ethylenically unsaturated monomer. An underwater antifouling paint that uses as a vehicle resin.

Description

Detailed Description of the Invention

BACKGROUND OF THE INVENTION The present invention relates to an underwater antifouling paint containing a quaternary ammonium salt polymer as a vehicle resin.

There is a demand for the development of an antifouling paint that does not contain organic tin, because of concern about the influence of the antifouling paint containing organic tin as an antifouling component on the ecosystem. As a kind of such antifouling paint,
Antifouling paints using quaternary ammonium salt polymers have been proposed.

For example, Japanese Patent Application Laid-Open No. 53-124538 discloses that a dialkylaminoalkyl (meth) acrylate copolymer is quaternized and used as a vehicle for an antifouling paint, so that the elution rate of an antifouling agent such as organic tin can be moderated. It is disclosed that it can be controlled. As can be seen from the fact that the antifouling performance depends on the antifouling agent such as organic tin added, the antifouling activity of the quaternary ammonium salt polymer of this type used as the vehicle resin itself is low.

Pyridinium salts such as cetylpyridinium chloride are known to have a strong bactericidal action. Japanese Patent Publication No. 6-19069 of the present applicant describes an antifouling coating film forming composition comprising a quaternary ammonium salt polymer containing a pyridinium salt and a crosslinking agent. This is because cross-linking imparts water resistance to the coating film that can withstand long-term immersion in water. However, cross-linking must be carried out at room temperature because baking or heat curing cannot be performed on an object to be coated such as a large ship. However, if it can be cured at room temperature, the storage stability of the paint will be lost, so there is the inconvenience of having to use two liquids.

The present inventors have surprisingly found that certain pyridinium salt polymers have sufficient antifouling activity on their own,
It has been discovered that a coating film having water resistance that can withstand long-term immersion in water can be formed without being crosslinked by a crosslinking agent.

DISCLOSURE OF THE INVENTION The present invention provides 5 to 60 mol% of a repeating unit corresponding to a vinylpyridinium salt quaternized with an alkyl halide having 4 or more carbon atoms or an aralkyl halide, and the rest is an ethylenically unsaturated monomer other than that. Provided is an underwater antifouling coating material containing a vinyl copolymer composed of corresponding repeating units as a vehicle resin.

[0007] vinyl copolymer comprising vinyl pyridinium salt corresponding repeating units of the described invention of the preferred embodiment is vinylpyridine (2-, 3- or 4
-Vinyl pyridine and 4-pinyl pyridine are easily commercially available) 5-60 mol% and the remaining amount of other ethylenically unsaturated monomer are copolymerized by a conventional method, and then a quaternizing agent is reacted. Can be manufactured.

Examples of the copolymerizable monomers are methyl (meth) acrylate, ethyl (meth) acrylate and n-
(Meth) acrylic acid alkyl ester such as propyl (meth) acrylate, n-butyl (meth) acrylate, t-butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate; styrene, α-methylstyrene, vinyltoluene, ( There are other monomers such as (meth) acrylamide, (meth) acrylonitrile, vinyl acetate, vinyl propionate, vinyl chloride. A small proportion of hydroxyalkyl (meth) acrylate such as 2-hydroxyethyl (meth) acrylate or 2-hydroxypropyl (meth) acrylate may be included. The polymerization can be performed by a solution polymerization method according to a conventional method.

The amount of vinyl pyridine in the monomer mixture is directly proportional to the antifouling activity of the copolymer after quaternization and inversely proportional to the water resistance. The range of 5 to 60 mol% is a range in which both are properly balanced.

Quaternization is carried out by n-butyl chloride, hexyl chloride, octyl chloride, decyl chloride,
Using an alkyl chloride having 4 or more carbon atoms such as dodecyl chloride, tetradecyl chloride and cetyl chloride, and corresponding bromide and iodide, and an alkyl halide or aralkyl halide such as benzyl chloride, benzyl bromide and benzyl iodide, by a conventional method. It can be carried out.

For use as a vehicle resin for paints, the copolymer has a number average molecular weight of 2,000 to 100,000.
It is preferably 0, particularly preferably in the range of 5,000 to 40,000.

The pyridinium salt polymer thus obtained is then made into a paint by a conventional method.

The antifouling paint composition of the present invention may contain the following conventional components added to the antifouling paint. (1) Antifouling agent: metal powder or flake of copper, zinc, nickel, etc .; oxides, hydroxides, halides and other salts of copper, zinc, etc., especially cuprous oxide and copper rhodanide; bactericidal organic compounds, For example, metal carboxylates such as copper naphthenate and copper stearate, metals such as zinc dimethyldimethyldithiocarbamate and bisdimethyldithiocarbamoyl zinc ethylene bisdithiocarbamate (Na,
K, Zn, Pb, Cu, Fe, Ni, Mg, Se) dithiocarbamates; thiuram disulfides such as tetramethylthiuram disulfide; phthalylsulfathiazole, sulfaetidol, sulfanilide pyridine, sulfamethoxine, N, N'-dimethyl-N '
-Sulfamides such as phenyl-N-fluorodichloromethylthiosulfamide; pyrroles such as gliodin, fenthizole and polycide, imidazoles; thioxanes such as terazol, asterol and myron, thioxanthones; nicarbazine, 3,4,5-tris Bromosalicylanilide, N-trichloromethylmercaptophthalimide, 3,5-dinitrobenzamide, 2,4,6
-Imidones and amides such as trichloromaleimide and N-fluorodichloromethylthiophthalimide; 2-methylthio-4-t-butylamino-6-cyclopropylamino-s-triazine, 2,4,5,6-tetrachlorophthalonitrile , N, N'-dimethyldichlorophenylurea, 4,5-dichloro-2-n-octyl-3-
(2H) Isothiazoline, 2-pyridinethiol-1-
Zinc oxide salt, 2,3,5,6-tetrachloro-4-
There are known antifouling agents such as sulfur-containing or halogen-containing organic compounds such as methylsulfonylpyridine, 3-iodo-2-propylbutylcarbamate, and diiodomethylparatolylsulfone, pesticides, pharmaceuticals, and bactericides. (2) Plasticizer: phthalate ester plasticizer such as dioctyl phthalate, dimethyl phthalate, dicyclohexyl phthalate; aliphatic dibasic acid ester plasticizer such as diisobutyl adipate and dibutyl sebacate; diethylene glycol dibenzoate, pentaerythritol alkyl ester Glycol ester plasticizer such as;
Phosphate ester plasticizers such as tricresyl phosphate and trichloroethyl phosphate; epoxy plasticizers such as epoxidized soybean oil and octyl epoxy stearate; organotin plasticizers such as dioctyl tin laurate and dibutyl tin laurate; other trimellits Examples include trioctyl acid and triacetylene. (3) Pigments: extender pigments such as precipitated barium sulfate, talc, clay, chalk, silica white, alumina white, titanium white, bentonite; titanium oxide, zircon oxide, basic lead sulfate, tin oxide, carbon black, graphite, There are coloring pigments such as red iron oxide, chrome yellow, quinacridone, phthalocyanine green, and phthalocyanine blue. (4) Solvent: toluene, xylene, ethylbenzene, cyclopentane, octane, peptane, cyclohexane,
Hydrocarbons such as white spirit; ethers such as dioxane, tetrahydrofuran, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol dimethyl ether, ethylene glycol monobutyl ether, ethylene glycol dibutyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether;
Butyl acetate, propyl acetate, benzyl acetate, esters such as ethylene glycol monomethyl ether acetate and ethylene glycol monoethyl ether acetate; ketones such as ethyl isobutyl ketone and methyl isobutyl ketone; alcohols such as n-butanol and propyl alcohol is there. (5) Other additives: rosin, monobutyl phthalate,
Organic monobasic acids such as monooctyl succinate, camphor, castor oil, etc. The composition of the present invention can be prepared by a method known per se in the technical field of paint production. A known machine such as a ball mill, a hebrew mill, a roll mill or a sand grind mill can be used for the blending. The antifouling paint of the present invention is used for ships such as tankers, ferries, fishing boats,
It is useful as an antifouling paint for underwater structures, fish nets, water pipes, etc. for steel ships, wooden ships, FRP ships, etc.

In the following Production Examples, Examples and Comparative Examples, "parts" and "%" are based on weight.

Production of Vehicle Resin Production Example 1 75 parts of xylene and 20 parts of n-butanol are added to a flask equipped with a stirrer, a nitrogen introducing tube, and a dropping funnel and kept at 90 ° C. 4-vinyl pyridine 11 parts, methyl methacrylate 55 parts, n-butyl methacrylate 34 parts, t-
A mixed solution of 1.2 parts of butylperoxy-2-ethylhexanoate was added dropwise over 4 hours, and after 30 minutes, 5 parts of xylene and 0.2 parts of t-butylperoxy-2-ethylhexanoate were added in 30 minutes. After dripping, the temperature was maintained for 90 minutes after the dropping to obtain a varnish A. Vinyl pyridine 11 mol% in the copolymer

Production Example 2 A flask similar to that of Production Example 1 was charged with 75 parts of xylene and 20 parts of n-butanol and kept at 90 ° C. A mixed solution of 21 parts of 4-vinylpyridine, 46 parts of methyl methacrylate, 33 parts of isobutyl acrylate and 1.2 parts of t-butylperoxy-2-ethylhexanoate was added dropwise over 4 hours, and after 30 minutes, 5 parts of xylene. , T-butylperoxy-2-ethylhexanoate (0.2 parts) was added dropwise over 30 minutes, and after the addition, varnish B was obtained by maintaining the same temperature for 90 minutes.
21 mol% vinyl pyridine in the copolymer

Production Example 3 75 parts of xylene and 20 parts of n-butanol were added to the same flask as in Production Example 1 and kept at 90 ° C. A mixed solution of 42 parts of 4-vinylpyridine, 20 parts of methyl methacrylate, 23 parts of isobutyl acrylate, 15 parts of styrene, and 1.2 parts of t-butylperoxy-2-ethylhexanoate was added dropwise over 4 hours, and then 30 minutes. After xylene 5 parts, t-
0.2 part of butyl-2-ethylhexanoate was added dropwise over 30 minutes, and after the addition, the temperature was maintained for 90 minutes to obtain a varnish C. Vinylpyridine 43 mol% in the copolymer

Production Example 4 To a flask similar to that of Production Example 1 was added 75 parts of xylene and 20 parts of n-butanol, and the temperature was kept at 90 ° C. To this, 21 parts of 2-vinyl pyridine, 46 parts of methyl methacrylate, 33 parts of isobutyl acrylate, t-butyl peroxy-2-
A mixed solution of 1.2 parts of ethyl hexanoate was added dropwise over 4 hours, and after 30 minutes, 5 parts of xylene and 0.2 parts of t-butylperoxy-2-ethylhexanoate were added over 30 minutes, and after the addition, The temperature was maintained for 90 minutes to obtain Varnish D. 21 mol% vinyl pyridine in the copolymer

Production Example 5 (Varnish for Comparative Example) 75 parts of xylene and 20 parts of n-butanol were added to the same flask as in Production Example 1 and kept at 90 ° C. 4 parts of a mixed liquid of 2 parts of 4-vinylpyridine, 40 parts of methyl methacrylate, 43 parts of n-butyl acrylate, 15 parts of styrene and 1.2 parts of t-butylperoxy-2-ethylhexanoate.
After 30 minutes, 5 parts of xylene and 0.2 part of t-butylperoxy-2-ethylhexanoate were added dropwise over 30 minutes, and after the addition, the temperature was maintained at the same temperature for 90 minutes to obtain a varnish E. . 2 mol% vinyl pyridine in the copolymer

Production Example 6 (Comparative Varnish) To the same flask as in Production Example 1, 75 parts of xylene and 20 parts of n-butanol were added and kept at 90 ° C. A mixed solution of 63 parts of 4-vinylpyridine, 20 parts of methyl methacrylate, 17 parts of isobutyl acrylate and 1.2 parts of t-butylperoxy-2-ethylhexanoate was added dropwise thereto over 4 hours, and after 3 hours, 5 parts of xylene. , T-butylperoxy-2-ethylhexanoate (0.2 parts) was added dropwise over 30 minutes, and after the addition, the temperature was maintained at the same temperature for 90 minutes to obtain a varnish F.
65 mol% of vinyl pyridine in the copolymer

Production Example 7 105 parts of 100 parts of varnish A and 6 parts of benzyl chloride were added.
A varnish G was obtained by heating at 0 ° C. for 2 hours.

Production Example 8 100 parts of varnish B and 13 parts of benzyl chloride were added to 105 parts.
The varnish H was obtained by heating at 0 ° C. for 2 hours.

Production Example 9 100 parts of varnish C and 25 parts of benzyl chloride were added to 105 parts.
The varnish I was obtained by heating at ℃ for 2 hours.

Production Example 10 100 parts of varnish D and 13 parts of benzyl chloride were added to 105 parts.
A varnish J was obtained by heating at ℃ for 2 hours.

Production Example 11 100 parts of varnish B and 14 parts of n-butyl bromide were added to 10 parts.
The varnish K was obtained by heating at 5 ° C. for 2 hours.

Production Example 12 100 parts of varnish B and 26 parts of cetyl chloride were added at 105 ° C.
After heating for 2 hours, a varnish L was obtained.

Production Example 13 (Comparative Varnish) Varnish M was obtained by heating 100 parts of varnish E and 3 parts of cetyl chloride at 105 ° C. for 2 hours.

Production Example 14 (Comparative Varnish) 100 parts of varnish F and 78 parts of cetyl chloride were treated at 105 ° C.
It was heated for 2 hours to obtain Varnish N.

Production Example 15 (Varnish for Comparative Example) 55 parts of xylene and 40 parts of n-butanol were added to the same flask as in Production Example 1 and kept at 90 ° C. To this, 41 parts of N- (2-methacryloyloxyethyl) -N, N, N-trimethylammonium chloride, 26 parts of methyl methacrylate, 33 parts of isobutyl acrylate, 1.2 parts of t-butylperoxy-2-ethylhexanoate. Was added dropwise over 4 hours, and after 30 minutes, xylene 5 parts, t-
0.2 part of butylperoxy-2-ethylhexanoate was added dropwise over 30 minutes, and after the addition, the temperature was maintained at the same temperature for 90 minutes to obtain a varnish O. Quaternary ammonium unit 2 in the copolymer
1 mol%

Production Example 16 (Comparative Varnish) 55 parts of xylene and 40 parts of n-butanol were added to the same flask as in Production Example 1 and the temperature was kept at 90 ° C. This contained 44 parts of N- (3-methacryloyloxypropyl) -N, N, N-trimethylammonium chloride, 26 parts of methyl methacrylate, 30 parts of isobutyl acrylate, 1.2 parts of t-butylperoxy-2-ethylhexanoate. Was added dropwise over 4 hours, and after 30 minutes, 5 parts of xylene, t
-Butylperoxy-2-ethylhexanoate 0.2
Part was dropped for 30 minutes, and after the dropping, the temperature was kept for 90 minutes to obtain a varnish P. 28 mol% of quaternary ammonium salt unit in the copolymer

Production Example 17 (Comparative Varnish) Varnish Q was obtained by heating 100 parts of varnish and 10 parts of methyl bromide at 105 ° C. for 2 hours.

Manufacture of Paints Examples 1 to 8 and Comparative Examples 1 to 6 Each component was dispersed with a disper in the formulation shown in Table 1 to manufacture paints.

[0033]

[Table 1]

Examples 9 to 15 and Comparative Examples 7 to 11 Varnishes G to L and M to Q were used as they were as coating materials.

Antifouling test A coating plate obtained by previously applying a tar epoxy coating to a sandblasted 9 × 28 cm steel plate and subjecting it to rust-proofing is coated with the coating composition of Examples 1-28 and Comparative Examples 1-6 to dry film thickness. A test plate was prepared by coating so as to have a thickness of about 150 μm.

The paints of Examples 9 to 14 (varnishes G to L) and Comparative Examples 7 to 11 (varnishes M to Q) were applied to a 9 × 28 cm polyvinyl chloride resin plate so that the dry film thickness was about 100 μm. Test plate was prepared.

These test plates were immersed in the sea at the Seaside Research Laboratory, Nippon Paint Co., Ltd., Tamano City, Okayama Prefecture, and the antifouling property over time was evaluated by the area (%) on which organisms adhered. The results are shown in Tables 2, 3 and 4.

[0038]

[Table 2]

[0039]

[Table 3]

[0040]

[Table 4]

Claims (2)

[Claims] 1. Vinyl comprising 5 to 60 mol% of a repeating unit corresponding to a vinylpyridinium salt quaternized with an alkyl halide having 4 or more carbon atoms or an aralkyl halide, the balance being a repeating unit corresponding to another ethylenically unsaturated monomer. An underwater antifouling paint containing a copolymer as a vehicle resin. 2. The underwater antifouling coating composition according to claim 1, further comprising an antifouling agent.