JPH07242841A - Coating compound composition for preventing adhesion of underwater organism - Google Patents

Abstract

PURPOSE:To obtain a coating compound composition useful for preventing adhesion of an underwater organism to a structure in the sea, etc., and its proliferation, having low toxicity and retention, and a strongly antifouling effect continuing for a long period, containing a substituted phenol compound having a specific structure. CONSTITUTION:This composition contains a substituted phenol of the formula [at least one of X<1> to X<5> is a hydroxyl group, at least one of R<1> and R<5> is a functional group selected from amino, methylol, (poly)ethylene glycol and (poly)propylene glycol and the others are H; Y is a 6-12C saturated hydrocarbon or 1-methyl-1-phenylethyl] (e.g. 2-hydroxymethyl-4-nonylphenol). The amount of the composition added to a water system is 0.1-50-ppm, preferably 0.5-30ppm calculated as the substituted phenol compound.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an underwater organism adhesion preventing coating composition used in marine structures, industrial water systems and the like to prevent the aquatic organisms from adhering and being damaged by reproduction.

[0002]

BACKGROUND OF THE INVENTION Underwater structures such as ships, marine structures, aquaculture fishing nets, buoys, and industrial water systems are constantly exposed to the water in which living organisms live, so bacteria, etc. , And organisms such as barnacles, mussels, sea bream, and diatoms adhere. If the surface of an underwater structure is covered by these, corrosion of the part concerned, deterioration of fuel efficiency of the ship due to increase in seawater frictional resistance at the bottom of the ship, mass hay death of seafood due to clogging of fishing nets, buoyancy of buoy Damage caused by sedimentation and work efficiency deterioration due to deterioration.

Further, in industrial water systems such as cooling water using natural water such as river water and lake water, and circulation type cooling devices using inside and tap water, bacteria, diatoms, cyanobacteria, etc. breed and water quality is increased. Cause deterioration of cooling efficiency and deterioration of cooling efficiency due to adherence to vessel walls, blockage of water pipes, decrease in flow rate, etc.

As a method for preventing the attachment of these pests, control has conventionally been carried out by chemicals such as inorganic heavy metal compounds, organic heavy metal compounds, heavy metal salts, inorganic and organic halogen agents. For example, the bottom plate surface of a ship, seawater introduction path,
Conventionally, a method of applying an antifouling paint has been used for fishing nets and the like, and the antifouling paint has mainly used agents such as inorganic copper compounds and organic tin compounds as antifouling agents. In the cooling water system, organic metal agents, inorganic and organic halogen agents,
Drugs such as peroxides have been dissolved or dispersed directly or in the form of being used in combination with a wettable powder and added to an aqueous system.

Control with these agents often does not show sufficient effects at low concentrations of elution and dissolution, and at effective concentrations, it is also highly toxic and highly persistent, so from the viewpoint of environmental protection, This was a problem from the viewpoint of safety and health for workers.

Therefore, there is a technique of using a specific alkyl-substituted phenol compound which has a high effect at a low concentration, has a high degradability in nature and does not cause a problem of persistence for controlling pests in water. Japanese Patent Application Laid-Open No. HEI 4-1992 discloses an antifouling composition for controlling pests in water, which comprises an aromatic substituted phenol compound and further contains a water repellent organic compound.
It is disclosed in Japanese Patent No. 202263. However,
The effect of preventing adhesion of aquatic organisms by these compounds is limited in their sustainability, and there is a problem in maintaining their effectiveness for a long period of time.

[0007]

The object of the present invention is to provide a strong antifouling effect for a long period of time with respect to prevention of adhesion of aquatic organisms, with low toxicity and persistence, without adversely affecting the ecosystem and working environment. An object of the present invention is to provide an underwater biofouling prevention coating composition.

[0008]

The gist of the present invention resides in that an aquatic organism adhesion preventing coating composition is constituted by containing a substituted phenol compound represented by the following general formula (1).

[0009]

[Chemical 2]

In the formula, X ¹ , X ² , X ³ , X ⁴ and X ⁵ are
At least one of them is a hydroxyl group, and at least one is a functional group selected from the group consisting of amino group, methylol group, ethylene glycol group, polyethylene glycol group, propylene glycol group and polypropylene glycol group, If none of the above is mentioned, it is hydrogen. Y is a linear or branched saturated hydrocarbon group having 6 to 12 carbon atoms or a 1-methyl-1-phenylethyl group.

The above-mentioned substituted phenol compound can be prepared by using an aromatic substituted phenol compound such as an alkylphenol or a cumylphenol having an alkyl group having 6 to 12 carbon atoms as a starting material for a usual reaction for introducing an amino group into a phenyl group or It can be synthesized by an alcoholic hydroxyl group introduction reaction. More preferably, the alkyl group has 7 to 12 carbon atoms.

The above-mentioned substituted phenol compounds are prepared by using polyhydric phenol compounds such as alkylresorcinol, alkylcatechol and alkylquinol as starting materials, ethylene oxide, propylene oxide, epichlorohydrin, polyethylene glycol diglycidyl ether,
It can also be synthesized by an addition reaction with an epoxy compound such as polypropylene glycol diglycidyl ether.

The aquatic organism adhesion preventing coating composition of the present invention comprises
The coating composition is prepared by blending one or more of the above substituted phenol compounds in the range of 0.5 to 80% by weight. The compounding ratio can be arbitrarily determined within the above range according to the required antifouling performance.

If desired, the coating composition for preventing aquatic organisms from adhering may be mixed with a coating resin which is usually used for the purpose of enhancing the strength of the coating film and the adhesion to the undercoat coating. , As an organic solvent system, vinyl chloride resin,
Chlorinated rubber resin, chlorinated polyethylene resin, chlorinated polypropylene resin, acrylic resin, styrene-butadiene resin, polyester resin, epoxy resin, polyamide resin, petroleum resin, silicone resin, silicone rubber resin, wax, paraffin, rosin Examples thereof include esters, rosin-based resins, and resins containing a metal element such as tin, copper, zinc, tellurium in the side chain. Examples of the aqueous system include acrylic emulsion resins, epoxy emulsion resins, vinyl acetate resins, and the like. Can be mentioned. These may be used alone or in combination of two or more.

In the case of preparing the aquatic organism adhesion preventing coating composition of the present invention, a known antifouling agent can be further added as an antifouling auxiliary agent. In addition, a plasticizer, a coloring pigment, an extender pigment and the like which are generally used in coating compositions can be added. Also, a known solvent can be added in an arbitrary ratio. Further, the preparation of the above-mentioned aquatic organism adhesion preventing coating composition can be carried out by a method known in the technical field of coating production.

Since the substituted phenol compound of the present invention itself has an antifouling effect, it can be used by directly dissolving or dispersing it in water such as an industrial water system. In that case,
One or a combination of two or more of the substituted phenol compounds of the general formula (1) is added to water. The addition may be continuous addition or intermittent addition, and can be arbitrarily selected depending on the water system and the generation situation of pests. The amount to be added to the water system is 0.1 to 0.1 as the substituted phenol compound.
50 ppm is preferable, and 0.5 to 30 ppm is more preferable. Even at such a low concentration, an extremely strong antifouling effect can be achieved.

[0017]

The present invention will be described in more detail with reference to the following examples, but the present invention is not limited thereto.

Examples 1 to 12 and Comparative Examples 1 to 3 The substituted phenol compounds shown in Table 1 were blended with other components to form a dispersion coating with a high speed disperser.
.About.12 and Comparative Examples 1 to 3 were used to prepare the underwater organism adhesion preventing coating compositions. The unit of the blending amount in Table 1 is% by weight
Is.

In Table 1, nonylphenol is Sanyo Kasei Co., Ltd., Laroflex MP-45 is a vinyl chloride-vinyl isopropyl ether copolymer manufactured by BASF, liquid paraffin is JIS K2231 ISOVG68 equivalent, and KE-45TS is Shin-Etsu Chemical. One-component room temperature curable silicone rubber manufactured by Kogyo Co., Ltd., SH-510 oil is methylphenyl silicone oil manufactured by Toray Silicone Co., Ltd., and WW rosin is manufactured by Arakawa Chemical Co., Ltd., respectively.

Antifouling Test Commercially available 300 × 100 mm test steel sheets pre-coated with anticorrosion were coated with the underwater organism adhesion preventing coating compositions prepared in Examples 1 to 12 and Comparative Examples 1 to 3 to give a dry film thickness of 60. ~ 80μ
After being coated to a depth of 1 m and dried for 1 day, it was immersed in a test raft off the coast of Tamano City, Okayama Prefecture at a depth of 1 m in the sea to examine the degree of contamination by attached organisms. The results are shown in Table 2. In Comparative Example 4, the coating composition for preventing adhesion of aquatic organisms of the present invention was not coated, and the above steel sheet for anticorrosion coating was used as it was as a sample. The numerical values in Table 2 represent the ratio (%) of the area contaminated by the attached organisms.

[0021]

[Table 1]

[0022]

[Table 2]

[0023]

According to the present invention, toxicity and persistence are low,
It is possible to provide a coating composition for preventing adhesion of aquatic organisms, which has a long-lasting strong antifouling effect with respect to the prevention of adhesion of aquatic organisms, without adversely affecting the ecosystem and working environment.

Claims (1)

[Claims] 1. An aquatic organism adhesion preventing coating composition comprising a substituted phenol compound represented by the following general formula (1). [Chemical 1] In the formula, at least one of X ¹ , X ² , X ³ , X ⁴ , and X ⁵ is a hydroxyl group, and at least one is
A functional group selected from the group consisting of an amino group, a methylol group, an ethylene glycol group, a polyethylene glycol group, a propylene glycol group, and a polypropylene glycol group, and when none of the above, it is hydrogen. Y is a linear or branched saturated hydrocarbon group having 6 to 12 carbon atoms or a 1-methyl-1-phenylethyl group.