JPH08239601A - Underwater antifouling coating material - Google Patents

Abstract

PURPOSE: To obtain a new excellent underwater antifouling coating material which has a low toxicity and provides a long-lasting antifouling effect. CONSTITUTION: This coating material contains pyridine-triphenylborane as a first antifouling component and at least one compd. selected from among 2-methylthio-4-t-butylamino-6-cyclopropylamino-s-triazine, diiodomethyl-p- tolylsulfone, 2, 4, 6-trichlorophenylmaleimide, zinc dimethyldithiocarbamate, and 2,4,5,6-tetrchloroisophthalonitrile as a second antifouling component. When applied to an underwater construction, the material exhibits excellent antifouling effects, long preventing the growth of aquatic organisms. The antifouling effect and its persistence of the material are far superior to those of a coating material contg. either one of the above-mentioned two antifouling components. Since these components are hardly toxic to humans, animals, and marine animals, the material can be used safely.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an underwater antifouling paint having low toxicity and long-lasting antifouling effect, and is particularly useful for ships, aquaculture nets, set nets, excavators for seabed oil fields, seabed bases, and buoys. It is used to paint structures such as power plant waterways, bridges, etc., and is suitable for preventing the adhesion of aquatic organisms that grow on the surface of the underwater parts of these structures. Toxic underwater antifouling paint. Therefore, the present invention can be widely used in the fields of chemical industry, shipbuilding industry, fishnet manufacturing industry, and the like.

[0002]

2. Description of the Related Art Conventionally, various underwater antifouling paints have been developed,
It is also in practical use. Pyridine-triphenylborane (hereinafter referred to as “Compound A”) used as the first antifouling active ingredient in the underwater antifouling coating composition of the present invention is known as an antifouling compound (US Pat. No. 3211679). Pyridine-triphenylborane is also known as an antifouling agent for underwater constructions in combination with 3- (3,4-dichlorophenyl) -1,1-dimethylurea (JP-A-6-220362).

2-Methylthio-4-t-butylamino-used as the second antifouling active ingredient in the coating composition of the present invention.
6-cyclopropylamino-s-triazine (hereinafter,
“Compound B”) is known as an algaecide (Japanese Patent Publication No. 62-33202).

Further, diiodomethyl paratolyl sulfone (hereinafter referred to as "compound C"), zinc dimethyldithiocarbamate (hereinafter referred to as "second compound") which can be used as the second active ingredient.
"Compound D") and 2,4,5,6-tetrachloroisophthalonitrile (hereinafter referred to as "Compound E") are known as antiseptic and antifungal agents (antibacterial and antifungal encyclopedia 149).
P., P. 143, p. 158, August 22, 1986, published by The Society of Antibacterial and Antifungal Society of Japan).

Furthermore, 2,4,6-trichlorophenylmaleimide (hereinafter referred to as "compound F") is known as an aquatic organism repellent (JP-A-56-164106).

On the other hand, aquatic organisms such as barnacles, squirts, serpra, mussels, mussels, hemlock worms, hornworts, and sea lions attach to the surface of underwater structures and grow to cause various damages. For example, when aquatic organisms adhere to the hull of a ship and grow, the speed of the ship decreases and fuel consumption increases. Further, when aquatic organisms adhere to water or an underwater structure such as a port facility fixed on the surface of water, individual functions of these devices cannot be sufficiently exerted. further,
It is also known that, when attached to aquaculture nets or stationary nets, the mesh may cause fish to die.

Conventionally, in order to prevent aquatic organisms from adhering to and growing on an underwater structure, an organic tin compound has been frequently used as an active ingredient in an underwater antifouling paint. However, since this organotin compound pollutes the environment, its use is prohibited.

[0008]

From the above, it is desired to develop a new underwater antifouling paint which can be used safely and can maintain an excellent antifouling effect for a long period of time.

[0009]

Means for Solving the Problems The inventors of the present invention have made earnest studies to develop an underwater antifouling coating composition that meets the above-mentioned needs. As a result, a coating composition containing the compound A as a first antifouling active ingredient and as a second antifouling active ingredient in combination with at least one of the compounds BF is safe. It has been found that it is an underwater antifouling paint that has an excellent antifouling effect and lasts.

That is, the gist of the present invention is that
Pyridine-triphenylborane as the first active ingredient and 2-methylthio-4-t-butylamino-6-
At least 1 selected from cyclopropylamino-s-triazine, diiodomethyl paratolyl sulfone, 2,4,6-trichlorophenylmaleimide, zinc dimethyldithiocarbamate and 2,4,5,6-tetrachloroisophthalonitrile. An underwater antifouling paint comprising two compounds as a second active ingredient.

Next, the chemical names and structural formulas of the compounds used as the antifouling active ingredient in the antifouling paint of the present invention are shown. Compound A: Pyridine-triphenylborane (complex) Compound B: 2-methylthio-4-t-butylamino-6
-Cyclopropylamino-s-triazine Compound C: diiodomethyl paratolyl sulfone

Compound D: zinc dimethyldithiocarbamate Compound E: 2,4,5,6-tetrachloroisophthalonitrile Compound F: 2,4,6-trichlorophenylmaleimide

Although the compound A has excellent antifouling and antialgal activity by itself, the sustainability of the antifouling effect is insufficient by itself. On the other hand, Compounds B to F have low antifouling and antialgal activities, which are so low as to be practically independent. However, surprisingly, when compound A is combined with any one of compounds B to F in a coating composition, the antifouling activity is synergistically improved, and the antifouling effect has a residual effect. It was discovered that

Further, the underwater antifouling paint of the present invention will be described in detail. To prepare the antifouling coating composition of the present invention, compound A used as the first active ingredient is mixed with at least one of compounds BF used as the second active ingredient by a conventional means, and then, Appropriately, the resulting mixture is incorporated into a coating composition to be antifouling. As means for mixing these active ingredient compounds, these active ingredient compounds are respectively dissolved and mixed in a common organic solvent, or when there is no common solvent, these compounds are mixed in powder form as a pulverizer. For example, a method of mechanically pulverizing and mixing with an atomizer or the like can be used. To the solution of the active ingredient compound thus obtained or the powder mixture of the active ingredient compound, an organic solvent for coating material, a surfactant, a coating resin, a pigment and other necessary components are added and uniformly mixed. This makes it possible to formulate an antifouling paint.

The paint resin which can be used in the underwater antifouling paint of the present invention is a film-forming resin for forming a coating film on the surface of a substrate, which is usually used in conventional underwater antifouling paints. The same resin as the existing resin can be used. For example, as the resin, vinyl chloride-vinyl acetate copolymer, vinyl chloride-
Vinyl isobutyl ether copolymer, styrene-butadiene copolymer, chlorinated rubber resin, chlorinated polypropylene resin, petroleum resin, alkyd resin, acrylic resin, phenol resin, synthetic rubber, epoxy resin, silicone Examples thereof include rubber, silicone resin, Teflon resin, and rosin resin.

In the underwater antifouling coating composition of the present invention, the first active ingredient, compound A, and the second active ingredient, compound B, are used.
It is suitable that the total amount of any one of the compounds (1) to (F) is 0.1 to 350 parts by weight, preferably about 1 to 150 parts by weight, based on 100 parts by weight of the coating resin.

The mixing weight ratio of the compound A and at least one of the compounds B to F is not particularly limited, but can be in the range of 1: 1 to 90, preferably 1: It can range from 1 to 1: 2.

In the underwater antifouling paint of the present invention, if necessary, a coloring pigment or colorant such as titanium white, red iron oxide, carbon, cyan blue, cyanine green or the like, or an extender pigment such as talc, barita or zinc white. Etc. can be blended. Further, water or an organic solvent can be added in order to adjust the viscosity of the paint. The type of organic solvent used is not particularly limited as long as it can dissolve or disperse the coating resin and other components to be blended.

Examples of such organic solvents include alcohols (methyl alcohol, ethyl alcohol, n-propyl alcohol, isopropyl alcohol, n-butyl alcohol, ethylene glycol, benzyl alcohol, etc.), aromatic hydrocarbons (benzene, toluene,
Xylene, ethylbenzene, chlorobenzene, cumene,
Methylnaphthalene etc.), halogenated hydrocarbons (chloroform, carbon tetrachloride, dichloromethane, chloroethylene, trichlorofluoromethane, dichlorodifluoromethane etc.), ethers (ethyl ether, ethylene oxide, dioxane, tetrahydrofuran etc.), ketones (acetone) , Methyl ethyl ketone, cyclohexanone, methyl isobutyl ketone, etc.), esters (ethyl acetate, butyl acetate, ethylene glycol acetate,
Amyl acetate etc.), Nitriles (acetonitrile, propionitrile, acronitrile etc.), Sulfoxides (dimethyl sulfoxide etc.), Alcohol ethers (ethylene glycol monomethyl ether, ethylene glycol monoethyl ether etc.), Amines (ethylamine, dimethyl) Amine, triethylamine, isobutylamine, etc.), aliphatic or alicyclic hydrocarbons (n-
Hexane, cyclohexane, etc., industrial gazoline (petroleum ether, solvent naphtha, etc.) and petroleum fractions (paraffins, kerosene, gas oil, etc.) and the like.

Further, the underwater antifouling coating composition of the present invention is mixed with a surfactant for the purpose of emulsification, dispersion, wetting, foaming and spreading during formulation. As such a surfactant,
Examples thereof are given below, but the present invention is not limited to these examples.

(A) Nonionic surfactants such as polyoxyethylene alkyl ethers, polyoxyethylene alkyl esters, polyoxyethylene sorbitan alkyl esters, sorbitan alkyl esters, etc. (b) Anionic surfactants such as alkylbenzenes Sulfonates, alkyl sulphosuccinates, alkyl sulphates, polyoxyethylene alkyl sulphates,
(C) cationic surfactants, such as laurylamine as alkylamines, stearyltrimethylammonium chloride, alkyldimethylbenzylammonium chloride, and (d) amphoteric surfactants, such as betaine-type compounds. Sulfate ester etc.

In addition to the above-mentioned components, various auxiliary agents such as polyvinyl alcohol (PVA), carboxymethyl cellulose (CMC), arabic rubber, polyvinyl acetate, gelatin, casein, sodium alginate are added to the antifouling paint of the present invention. it can.

The present invention will be described in more detail below with reference to examples. All parts in these examples are parts by weight.

Example 1 10 parts of compound A, 10 parts of compound B, 10 parts of rosin, 15 parts of chlorinated isopropylene rubber, 10 parts of zinc white, red iron oxide
A total of 100 parts of 5 parts, 3 parts of colloidal silica, 8 parts of talc, 10 parts of xylene, 15 parts of methyl isobutyl ketone, and 2 parts of n-butyl alcohol were subjected to a dispersion treatment by tumbling and mixing in a ball mill for 5 hours, and then homogenized. A coating composition was obtained.

Examples 2 to 5 and Comparative Examples 1 to 13 According to the same preparation method as in Example 1, the ingredients were mixed according to the composition shown in Table 1 below, and the coating materials of Examples 2 to 5 and Comparative Example 1 ~ 13 paints were prepared.

[0026]

Test Examples 1 to 5 and Comparative Test Examples 1 to 13 Sandblasted steel sheets were previously coated with an ordinary rust preventive paint, and the dried coating films were applied to Examples 1 to 5 and Comparative Examples 1 to 1. A test plate (100 mm x 100 mm x dry paint film thickness of the antifouling paint was applied by brushing 13 paints twice.
300mm). The test plate thus obtained was immersed in the sea at a depth of 1.5 m in Aburatsubo Bay, Miura City, Kanagawa Prefecture for 24 months, and the aquatic organism adhesion area was measured every month for the period shown in Table 2 below. .. And the antifouling effect was shown by percentage (%) by the following formula. The test results are shown in Table 2.

[0028]

[0029]

As is clear from the results in Table 2, the test plates coated with the paints of Examples 1 to 5 in which the first active ingredient and the second active ingredient were combined according to the present invention were dipped.
Even in the 18th month, the antifouling effect rate remained in the 90 to 100% range, and in the 24th month, the majority was in the 90 to 95% range. On the other hand, Comparative Examples 1 to 6 and 8 to 13 in which only any one of the active ingredients used in the present invention was blended alone.
The comparative test plate coated with the paint of Comparative Example 7 or the paint of Comparative Example 7 in which only the conventional cuprous oxide was mixed as the active ingredient had a predominantly antifouling effect rate of 85% at the 12th month of immersion. Or it fell below that.

[0031]

INDUSTRIAL APPLICABILITY The underwater antifouling paint of the present invention is applied to an underwater structure to adhere aquatic organisms such as barnacles, squirts, serpras, mussels, mussels, hemlock worms, aonori and aosa for a long time. It can be prevented for a long time and can exhibit an excellent antifouling effect. The antifouling effect and the duration of the antifouling effect of the coating composition of the present invention are far superior to those in the case where any one of the antifouling active ingredients used in the present invention is used alone. Further, both the first and second active ingredients contained in the antifouling paint of the present invention have low toxicity to human livestock and seafood, and thus the paint of the present invention can be safely used.

 ─────────────────────────────────────────────────── ─── Continuation of front page (72) Inventor Masayuki Umeno 3 at 521 Chigasaki, Chigasaki City, Kanagawa Prefecture (72) Inventor Mitsuo Hamada 14 (72) Inventor, 2-28, East Asahina, Kanazawa-ku, Yokohama City, Kanagawa Prefecture Yuichiro Kawasaki 19-17 Ikedanaka-cho, Neyagawa-shi, Osaka Japan Paint Co., Ltd. (72) Inventor Emiko Yasuhara 19-17 Ikedanaka-cho, Neyagawa-shi, Osaka Japan Paint Co., Ltd.

Claims (1)

[Claims] 1. Pyridine-triphenylborane as a first active ingredient and 2-methylthio-4-t-butylamino-6-cyclopropylamino-s-triazine, diiodomethylparatolyl sulfone, 2,4. , 6-
An underwater antifouling paint comprising at least one compound selected from trichlorophenylmaleimide, zinc dimer dithiocarbamate and 2,4,5,6-tetrachloroisophthalonitrile as a second active ingredient.