JPH0525408A - Underwater antifouling coating composition - Google Patents

Abstract

PURPOSE:To provide the subject composition which contains, as active ingredients, pyridinium tetraphenylborate and 3-(3,4-dichlorophenyl)-1,1- dimethylurea and is suited for vessels, culture nets, etc. CONSTITUTION:The objective composition contains, as active ingredients, pyridinium tetraphenylborate and 3-(3,4-dichlorophenyl)-1,1-dimethylurea.

Description

Detailed Description of the Invention

[0001]

[Object of the Invention]

[0002]

FIELD OF THE INVENTION The present invention has low toxicity and long-term sustainability. For example, ships, aquaculture nets, stationary nets, subsea oilfield excavators, seabed bases, buoys, waterway facilities for power plants, and bridges. The present invention relates to a low-toxicity antifouling coating composition suitable for coating aquatic organisms and the like to prevent aquatic organisms that grow by adhering to the surface of the underwater portion of these constructs. Therefore, the present invention can be widely used in the chemical industry, particularly in the fields of shipbuilding, fishnet manufacturing, and the like.

[0003]

2. Description of the Related Art Various types of aquatic organisms such as barnacles, squirts, serpra, mussels, mussels, hemlock worms, aonori and aosas inhabit the sea or the coast. These aquatic organisms adhere to the surface of the structure in the underwater portion and grow to cause various damages. For example, if aquatic organisms adhere to the hull and grow, the speed of the ship decreases and fuel consumption increases. Further, if aquatic organisms adhere to water or a port facility fixed on the surface of the water, the individual functions of these organisms cannot be sufficiently exerted. Furthermore, when attached to aquaculture nets or stationary nets, the mesh may cause fish to be killed. As a result, economic loss due to the attachment of aquatic organisms to underwater structures has become a major problem.

Conventionally, the problem has been solved by using a highly toxic compound such as an organic tin compound or other metal compound in the paint, against the deterioration of the underwater structure by these aquatic organisms. However, due to the toxicity problem of these metal compounds, it is not preferable in terms of safety and hygiene for workers during the production and construction of the paint. Moreover, since the above-mentioned antifouling agent remains in the area of use as it is, there is a concern that it may contaminate water bodies and accumulate in the body of seafood to have an adverse effect.

Under these circumstances, it is desired to develop an underwater antifouling coating composition that is safe and has a long-lasting effect.

On the other hand, pyridinium tetraphenylborate (hereinafter referred to as "Compound A"), which is the active ingredient of the present invention.
Is an antifouling component of underwater antifouling paint (Japanese Patent Publication No. 54-15
No. 71). The other active ingredient, 3- (3,4-dichlorophenyl) -1,1
-Dimethylurea (hereinafter referred to as "Compound B") is a herbicide that is absorbed from foliage or roots of weeds and accumulates in leaves, and exhibits herbicidal activity by inhibiting photosynthesis ("Agricultural Chemicals Handbook", 1989 version, 1989). November 20, issued by the Japan Plant Protection Association, and has an algae control agent (JP-A-60-223).
No. 874) and a seaweed growth promoting agent (JP-A-3-1237).
No. 10).

However, it is not known to use a mixture of two kinds of compound A and compound B as an underwater antifouling coating composition.

[0008]

[Constitution of the invention]

[0009]

Means for Solving the Problems In order to develop a new underwater antifouling coating composition that meets the above-mentioned needs, the present inventors have tried a wide range of compounds in various tests and examined their physiological activities. did.

As a result, an underwater antifouling coating composition containing a mixture of two kinds of compound A and compound B as an active ingredient is highly safe for humans and animals, and has an excellent antifouling effect against aquatic organisms attached to underwater structures. Found to show. That is, the gist of the present invention resides in an underwater antifouling coating composition characterized by containing Compound A and Compound B as active ingredients.

The coating resin used in the underwater antifouling coating composition of the present invention is one of the substrates for forming an antifouling coating film, and the coating resin conventionally used can be similarly used. .. For example, 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 Examples include resin, phenol resin, synthetic rubber, epoxy resin, silicone rubber, silicone resin, Teflon resin, rosin resin and the like.

In the underwater antifouling coating composition of the present invention, the compounding amount of compound A and compound B is 0.1 to 350 parts by weight, preferably about 1 to 100 parts by weight of the coating resin.
150 parts by weight is suitable.

The compounding ratio of the compound A and the compound B is not particularly limited, but is 1 to 90 or 90.
They can be mixed in a ratio of ˜1.

Further, the plasticizer is preferably added in an amount of 20 parts by weight or less per 100 parts by weight of the coating resin.

The underwater antifouling coating composition of the present invention contains a coloring material (eg, titanium white, red iron oxide, carbon, cyanine blue, cyanine green, etc.) or an extender pigment (eg, talc, barita, zinc white, etc.) as required. Can be added, and water or an organic solvent can be used to adjust the viscosity of the coating material.

The type of organic solvent used is not particularly limited as long as it can dissolve or disperse the coating resin or each composition. For example, water, alcohols (methyl alcohol, ethyl alcohol, n-propyl alcohol, isopropyl 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, acrylonitrile, etc.), sulfoxides (dimethyl sulfoxide, etc.), alcohol Ethers (ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, etc.), amines (ethylamine,
Dimethylamine, triethylamine, isobutylamine, etc.), aliphatic or alicyclic hydrocarbons (n-hexane, cyclohexane, etc.), industrial gasoline (petroleum ether, solvent naphtha, etc.) and petroleum fractions (paraffins, kerosene, light oil) Etc.), etc.

A surfactant is used in the formulation of the underwater antifouling coating composition of the present invention for the purpose of emulsification, dispersion, wetting, foaming and spreading. Examples of such a surfactant include those shown below, but the surfactants are not limited to these examples.

Non-ionic type (polyoxyethylene alkyl ether, polyoxyethylene alkyl ester, polyoxyethylene sorbitan alkyl ester, sorbitan alkyl ester, etc.), anionic type (alkylbenzene sulfonate, alkyl sulfosuccinate, alkyl sulfate, Polyoxyethylene alkyl sulphate, aryl sulphonate etc.), cationic type [alkyl amines (lauryl amine, stearyl trimethyl ammonium chloride, alkyl dimethyl benzyl ammonium chloride etc.)], amphoteric type (betaine type) sulfuric acid ester etc. Besides, polyvinyl alcohol (PVA), carboxymethyl cellulose (CMC), gum arabic, polyvinyl acetate, gelatin, cold Down, sodium alginate,
Various auxiliary agents such as can be used.

The underwater antifouling coating composition of the present invention comprises the compound A
And two kinds of the compound B are used as active ingredients, a sufficient effect is exhibited, but if necessary, general antifouling and antifungal agents such as 2- (4-thiazolyl) benzimidazole and parachlorometa Xylenol, benzyl bromoacetate, 2,3,5,6-tetrachloro-4-methylsulfonylpyridine, N-dichlorofluoromethyl-N
', N'-dimethyl-N-sulfamide, 2-benzisothiazolin-3-one, 2,4,5,6-tetrachloroisophthalonitrile, 2-methylthio-4,6-bis (ethylamine) 5-triazine, 2-methylthio-4
1-tetrabutyl-6-cyclopropylamino-s-triazine, 2,6-dichlorobenzonitrile, 2,4-dichlorophenoxyacetic acid, 2-methyl-4-isothiazolin-3-one and salts or esters thereof One kind or two kinds may be used in combination.

The present invention will be further described below with reference to examples.

[0021]

【Example】

Example 1 10 parts of compound A, 10 parts of compound B, rosin 12
Parts, chlorinated isopropylene rubber 15 parts, zinc white 10
Parts, red iron oxide 5 parts, colloidal silica 3 parts, talc 8 parts, xylene 10 parts, methyl isobutyl ketone
A total of 100 parts of 15 parts and 2 parts of butanol were dispersed in a ball mill for 5 hours to obtain a coating composition.

According to the same method as in Example 1, the coating compositions of Examples 2-3 and Comparative Examples 1 to 3 having the compositions shown in Table 1 were prepared and tested.

[0023]

[Table 1] Paint formulation Next, Test Examples 1 and 2 are shown to show the usefulness of the underwater antifouling coating composition of the present invention.

Test Example 1 The paints of Examples 1 to 3 and Comparative Examples 1 to 3 were applied in advance to a sandblasted steel sheet with an anticorrosive paint, and then brushed twice to give a dry paint film thickness of about 100 μm. I made a test board. The test plate thus obtained was completely immersed in the sea at a depth of 1.5 m in Aioi Bay, Hyogo Prefecture, and the adhesion area (%) of the aquatic organism was measured to determine the control effect (%). The results are shown in Table 2.
It was shown to.

[0025]

[Table 2]

[0026]

EFFECTS OF THE INVENTION By applying the underwater antifouling coating composition of the present invention to an underwater structure, barnacles, squirts,
Serpula, mussel, mussel, hemlock beetle,
It is possible to prevent the adhesion of blue sea bream, blue sea bream, etc. for a long period of time. And, the antifouling effect and the duration thereof are far superior to the single use of the active ingredient used in the present invention.

The active ingredient of the present invention has low toxicity to humans and livestock, and can be used with confidence.

[Procedure amendment]

[Submission date] June 26, 1992

[Procedure Amendment 1]

[Document name to be amended] Statement

[Name of item to be corrected] 0019

[Correction method] Change

[Correction content]

The underwater antifouling coating composition of the present invention comprises the compound A
And two kinds of the compound B are used as active ingredients, a sufficient effect is exhibited, but if necessary, general antifouling and antifungal agents such as 2- (4-thiazolyl) benzimidazole and parachlorometa Xylenol, benzyl bromoacetate, 2,3,5,6-tetrachloro-4-methylsulfonylpyridine, N-dimethyl-N'-phenyl-
(N'-florodichloromethylthio) -sulfamide ,
1,2-benzisothiazolin-3-one, 2,4
5,6-Tetrachloroisophthalonitrile, 2,6-dichlorobenzonitrile, 2-methyl-4-isothiazolin-3-one, Manganese ethylene bisdithiocarba
Mate, zinc methyldithiocarbamate, 4,5-di
Chloro-2-n-octyl-3 (2H) isothiazolo
2-pyridinethiol-1-oxide (zinc salt),
Tetramethyl thiuram disulfide, 2,4,6-to
Lichlorophenylmaleimide, 3-iodo-2-propa
Gilbutyl Carbamate, Diiodomethyl Paratrilus
Lufon, bisdimethyldithiocarbamoyl zinc acetate
Bisdithiocarbamate, phenyl (bispyridine)
Bismuth dichloride, 4-chlorophenyl-3-io
Dopropargyl formal, 1,2-dibromo-2,4-
Dicyanobutane, N- (trichloromethylthio) -4-
Cyclohexane-1,2-dicarboximide, 2-
(Methoxycarbonylamino) benzimidazole, do
Decylbenzene sulfonic acid, parachlormetacreso
2- (4-thiocyanomethylthio) benzothiazo
Le, 2-methylthio-4,6-bis (ethylamino) -
s-triazine, 2,4-dichlorophenoxyacetic acid, 2
-Methylthio-4-tert-butylamino-6-cyclop
One or two kinds of ropylamino-s-triazine and salts or esters thereof may be used in combination. In addition, these antifouling and antifungal algae inhibitors are
Book 1976 edition "Japan Plant Protection Association
Issued on October 18, 1976, "April 1985 Edition"
Issued January 30, 1986 and antibacterial and antifungal agent encyclopedia
Antifungal Encyclopedia Publishing Committee, August 22, 1986 Japan
It is a compound described in the Society of Antibacterial and Antifungal.

Claims (1)

Claims: Pyridinium tetraphenylborate and 3
An underwater antifouling coating composition containing-(3,4-dichlorophenyl) -1,1-dimethylurea as an active ingredient