JPH0912414A - Agent for preventing adhesion of aquatic life, coating composition, molded resin article and underwater construction - Google Patents

Abstract

PURPOSE: To obtain an agent for preventing the adhesion of aquatic life, free from heavy metals and harmful elements and accordingly the problem of environmental pollution and safety, exhibiting sufficient adhesion preventing effect by the use of seawater components and useful as an additive for coating material, molded resin article and underwater construction. CONSTITUTION: A calcium compound is used as an active component of this agent. Inorganic salt or complex or organic slat or complex are preferable among the calcium compounds. Especially preferable calcium compound is a compound originated from the component of seawater or marine life. A coating composition is produced by compounding the adhesion preventing agent to a coating material in an amount of 1-200wt.% based on the resin component used as a vehicle. The preventing agent can be formed in the form of a plate, sheet or other desired form by compounding the agent in an amount of 1-55wt.% based on all components used in a molded resin article. An underwater construction is produced by adding 5-15wt.% of the preventing agent to mortar or concrete. The preventing agent can be used in the form of a solution or an emulsion and poured into a water-introducing and discharging channel at a concentration of 0.01-50ppm based on the water stream.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an aquatic organism adhesion preventive agent for preventing adhesion of aquatic organisms to underwater structures such as ships, fishing nets, drainage conduits, etc., and coating compositions and resins using the same. Compositions and underwater structures.

[0002]

2. Description of the Related Art For example, barnacles, squirts, serpras, blue mussels, aonori, in water such as the sea, rivers and lakes
Many aquatic organisms such as Ulva inhabit. Such aquatic organisms adhere to and grow on underwater vessels, buoys, harbor facilities, pipelines, offshore oilfield equipment, power-supply drainage pipes, aquaculture nets and stationary nets, and cause various damages. For example,
When aquatic organisms adhere to the bottom of the ship, frictional resistance with water increases, causing a decrease in navigation speed, and fuel consumption increases to maintain a constant speed. In addition, if aquatic organisms adhere to the drainage conduit of the power plant, it may cause deterioration or blockage of the water flow.
If aquatic organisms attach to the fishing nets for aquaculture, the nets may be closed and the seafood may be killed.

Conventionally, many aquatic organism adhesion preventive agents for preventing adhesion of aquatic organisms to such underwater structures have been provided, but most of them are heavy metals such as copper and tin, chlorine and the like. Since it contains harmful elements such as phosphorus and arsenic, it not only causes water pollution but also presents problems such as accumulation in aquatic organisms and adverse effects on the human body due to the food chain.

[0004]

The ecology of aquatic organisms such as barnacles and blue mussels is completely different from that of terrestrial organisms, and the current situation is that sufficient research has not been conducted on the reactions of these organisms to various odors, colors, etc. Is. Therefore, any substance other than known aquatic organism attachment inhibitors,
At present, it is impossible to predict whether or not it has an effect of preventing the adhesion of these aquatic organisms.

The present inventors intend to solve the above problems and to develop an aquatic organism adhesion-preventing agent which is excellent in the effect of preventing the adhesion of aquatic organisms as described above and which has no problems in pollution and safety. As a result, as a result of earnest research, it was found that a calcium compound is extremely suitable for such a purpose, and the present invention has been completed here. That is, the present invention does not contain heavy metals and harmful elements and has no problems of pollution and safety, and further, an aquatic organism adhesion preventing agent having a sufficient aquatic organism adhesion preventing effect and a coating composition using the same.
A resin composition and an underwater structure are provided.

[0006]

The present invention relates to an aquatic organism adhesion preventive agent containing a calcium compound as an active ingredient. The present invention also relates to a coating composition containing the aquatic organism adhesion preventing agent. The present invention also relates to a resin molded product containing the aquatic organism adhesion preventing agent. The present invention also relates to an underwater structure containing the aquatic organism attachment-preventing agent. The present invention also relates to an underwater structure coated with the coating composition. Furthermore, the present invention relates to an underwater structure in which the resin molded product is attached to the surface.

The calcium compound used in the present invention may be an inorganic salt or complex or an organic salt or complex. Calcium compound which is an inorganic salt or complex is excellent in that it also has properties as a bulking agent, and as such a calcium compound, for example,
Calcium fluoride, calcium peroxide, calcium hydroxide, calcium sulfide, calcium sulfite, calcium sulfate, calcium phosphonate monohydrate, calcium phosphate, calcium hydrogen phosphate, calcium diphosphate, calcium metaphosphate, calcium carbonate, magnesium calcium carbonate, silica Examples thereof include calcium acidate, calcium metasilicate, calcium tetraborate hexahydrate, and hydroxyapatite. The calcium compound which is an organic salt or complex is excellent in that it has both properties as a lubricant of a thermoplastic resin and as a stabilizer when kneaded with a vinyl chloride resin, and as such a calcium compound, , For example, calcium lactate, calcium citrate, calcium tartrate, calcium oxalate monohydrate, calcium benzoate trihydrate, calcium citrate tetrahydrate,
Calcium glutamate, calcium aspartate,
Examples thereof include calcium palmitate, calcium myristate, calcium stearate and the like. Among these, calcium hydroxide, calcium sulfate, calcium carbonate, hydroxyapatite, calcium oxalate, calcium glutamate, and calcium aspartate are preferable because of their great effect of preventing adhesion of aquatic organisms.

The present invention aims to develop an aquatic organism adhesion preventive agent which is free from pollution and safety problems. Therefore, the calcium compound used in the present invention is a component in seawater or a marine organism. It is preferably a compound of origin. Examples of the calcium compound which is a component in seawater or a compound derived from marine organisms include calcium hydroxide, calcium sulfate, calcium phosphate, calcium carbonate, hydroxyapatite, calcium oxalate, calcium glutamate and calcium aspartate. . Among the calcium compounds that are components in seawater or compounds derived from marine organisms, the effect of preventing the adhesion of aquatic organisms is extremely large, and for components that are components in seawater, a large amount in seawater. From the viewpoint of existing salts, calcium sulfate, calcium carbonate, phosphorous calcium hydroxide and calcium glutamate are preferable. The anti-biofouling agent of the present invention,
They can be used alone or in combination of two or more. In addition, other components, for example, various known aquatic organism adhesion preventing agents may be contained to the extent that the effects of the present invention are not impaired.

The aquatic organism adhesion preventive agent of the present invention can be used for various substances used in water. Specific examples thereof include paint compositions such as antifouling paints, resin molded products, and underwater structures. First, the coating composition will be described. The coating composition includes, in addition to the aquatic organism adhesion preventing agent, a resin component used as a vehicle, a solvent, a colorant, an extender, a plasticizer, and other aquatic organism adhesion preventing agents used as necessary. . The resin component used as a vehicle includes various natural resins and synthetic resins. Specifically, rosin, boil oil, chlorinated rubber resin (chloroprene rubber, etc.), vinyl chloride resin (vinyl chloride, etc.), phenol resin, alkyd Resins, various modified alkyd resins, vinyl resins (vinyl acetate, etc.), acrylic resins, olefin resins such as polybutene, various synthetic rubbers, epoxy resins, polyester resins, polyurethane resins, polyamide resins, polyacetal resins, polyimide resins, synthetic resin emulsions Liquid (ethyl acrylate-styrene copolymer resin, methyl acrylate-vinyl acetate copolymer resin, etc.), synthetic rubber emulsion (styrene-butadiene copolymer rubber, acrylonitrile-butadiene copolymer rubber, methyl methacrylate-butadiene copolymer rubber, etc.) ) Etc. .

The solvent to be used is not particularly limited as long as it has no reactivity with the resin and can dissolve or disperse the resin. For example, a ketone solvent (acetone, methyl ethyl ketone, methyl butyl ketone, methyl isobutyl ketone, Diisobutyl ketone, cyclohexanone, etc.), ester solvents (ethyl acetate, butyl acetate, ethyl propionate, etc.), aromatic hydrocarbon solvents (toluene, xylene, etc.), aliphatic hydrocarbon solvents (hexane, cyclohexane, etc.), Cyclic ether solvents (tetrahydrofuran, dioxane, etc.), chain ether solvents (ethylene glycol diethyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, etc.),
Alcohol-based solvent (methanol, ethanol, butanol, etc.), chloroform, halogen-based solvent (methylene chloride, carbon tetrachloride, etc.), aprotic polar solvent (dimethyl sulfoxide, dimethylformamide, N-methyl-2)
-Pyrrolidone, etc.) can be used. These solvents are
They can be used alone or in combination of two or more.

As the colorant, for example, an inorganic pigment (eg red iron oxide, titanium oxide, iron oxide, carbon black) or an organic pigment (azo type, cyanine type, phthalocyanine type, quinacridone type) or the like can be used. As the extender, for example, an extender pigment (barium sulfate, magnesium oxide, alumina, zeolite, etc.) can be used. These extenders can be used alone or in combination of two or more kinds. The plasticizer is not particularly limited as long as it has no reactivity with the resin, for example,
Ethyl palmitate, ethyl stearate, dioctyl phthalate, dibutyl phthalate, triphenyl phosphate, tricresyl phosphate, trioctylphosphine oxide,
Triphenylphosphine oxide, trioctyl phosphate, etc. can be used. These plasticizers can be used alone or in combination of two or more kinds.

The amount of the aquatic organism adhesion preventing agent of the present invention added to the coating composition is preferably 1 to 200% by weight based on the resin component used as a vehicle, and the effect of the aquatic organism adhesion preventing agent is good. From the viewpoint of the balance of the formation of a coating film, it is more preferably 5 to 80% by weight.
It is more preferable that the amount is ˜50% by weight. If it is less than 1% by weight, the effect as an aquatic organism adhesion preventing agent tends to be hardly exhibited, and if it exceeds 200% by weight, a good coating film tends to be hardly formed. The amount of the solvent used is not particularly limited, but from the viewpoint of various properties as a coating composition, it is preferably used in the range of 0.25 to 99 times the resin component used as the vehicle on a weight basis. The amount of the colorant used is not particularly limited, but when used, it is preferably 200% by weight or less based on the resin component used as the vehicle in the coating composition. If it exceeds 200% by weight, the stability of the coating film tends to be poor.

The amount of the extender used is not particularly limited,
When used, it is preferably 100% by weight or less based on the resin component used as the vehicle in the coating composition. If it exceeds 100% by weight, the stability of the coating film tends to be poor. The plasticizer is preferably used in the range of 1 to 200% by weight based on the resin component used as the vehicle in the coating composition, and from the viewpoint of the balance between the effect of addition and the stability as a coating film, it is 5 to 50%. It is more preferable to use it in the range of% by weight. If it is less than 1% by weight, the effect of addition tends not to be sufficiently exhibited, and if it exceeds 200% by weight, the stability as a coating film tends to be poor. The coating composition can be applied or impregnated as an antifouling coating on an underwater structure such as a ship, a fishing net, or a conduit pipe.

Next, the resin molded product will be described. Examples of the resin molded product of the present invention include those obtained by mixing the aquatic organism attachment-preventing agent of the present invention with a thermoplastic resin or a thermosetting resin, and molding the mixture into a plate, a sheet, an object shape or the like. Specifically, there are resin plates or sheets for surface sticking of underwater structures and the like, and molded products (such as buoys for displaying water areas or wave power generation) used for applications having a portion that is always in contact with water. Examples of the thermoplastic resin or thermosetting resin, for example, chlorinated rubber resin, vinyl chloride resin, phenol resin,
Alkyd resin, various modified alkyd resins, urea resin, melamine resin, vinyl resin (vinyl acetate, etc.), acrylic resin, olefin resin (polybutene, polyethylene, etc.),
Examples thereof include various synthetic rubbers, epoxy resins, polyester resins, unsaturated polyester resins, polyurethane resins, polyamide resins, polyacetal resins, polyimide resins and amino resins.

The addition amount of the aquatic organism adhesion preventing agent in the thermoplastic and thermosetting resins is preferably 1 to 55% by weight based on the weight of all components used in the resin molded product,
From the viewpoint of the balance between the effect of the aquatic organism adhesion preventing agent and the required physical properties such as mechanical strength of the resin molded product, it is more preferably 5 to 30% by weight. If it is less than 1% by weight, the effect as an aquatic organism adhesion preventing agent tends to be hardly exhibited, and if it exceeds 55% by weight, the required physical properties such as mechanical strength of the resin molded product tend to be deteriorated. Further, the resin molded product of the present invention,
Additives such as a plasticizer may be contained to the extent that the effects of the present invention are not impaired. The method for producing the resin molded product is not particularly limited, and any known method may be used, and the resin molded product may be mixed with a thermoplastic or thermosetting resin to form a molded product.
The resin molded product of the present invention may be used alone in water as it is, or may be used by being attached to the surface of various underwater structures.

Next, the underwater structure will be described. Examples of the underwater structure of the present invention include a structure formed by directly mixing the aquatic organism attachment-preventing agent of the present invention into mortar or concrete, and having a portion which is constantly in contact with water. Specifically, it is an auxiliary facility of a dam, an auxiliary facility of an offshore oilfield, an underwater structure in a port facility or the like, or a water intake channel for a heat exchanger of a petrochemical plant. Water anti-biofouling agent addition amount of the mortar or concrete is the total components excluding water of the ingredients used in the underwater structure 1
It is preferably from 30 to 30% by weight, and more preferably from 5 to 15% by weight from the viewpoint of the balance between the effect of the aquatic organism adhesion preventing agent and the required physical properties such as the mechanical strength of the underwater structure.
If it is less than 1% by weight, the effect as an aquatic organism adhesion preventing agent tends to be hardly exhibited, and if it exceeds 30% by weight, required physical properties such as mechanical strength of an underwater structure tend to be deteriorated. The underwater structure of the present invention can be manufactured by a known manufacturing method for an underwater structure.

Further, for the purpose of preventing the adhesion and propagation of aquatic organisms, the agent for preventing aquatic organism adhesion of the present invention in the form of a solution or emulsion may be directly flowed into the drainage conduit. In the water drainage pipe for cooling water, when injecting the aquatic organism adhesion preventing agent of the present invention into the pipe, from the viewpoint of obtaining a sufficient aquatic organism adhesion preventing effect, the injection of the aquatic organism adhesion preventing agent The concentration is preferably 0.01 to 50 ppm with respect to running water, more preferably 0.03 to 10 ppm, and 0.03 from the viewpoint of the balance between the added amount of the aquatic organism adhesion preventing agent and the effect thereof. It is more preferable that the content be ˜3 ppm. If it is less than 0.01 ppm, the effect as an aquatic organism adhesion preventing agent tends to be hardly obtained, and if it exceeds 50 ppm, the effect of the aquatic organism adhesion preventing agent tends to reach a ceiling.

Further, when the aquatic organism adhesion preventing agent of the present invention is directly injected into the conduit tube in the form of a solution or emulsion, a surfactant is used to disperse or emulsify the aquatic organism adhesion preventing agent. Can be appropriately selected and used.
As the surfactant used at that time, for example, polyoxyethylene alkyl ethers, polyoxyethylene alkyl esters, polyoxyethylene-polyoxypropylene block copolymers, alkyl betaines,
An alkyl trimethyl ammonium salt etc. are mentioned.

[0019]

Next, the present invention will be described by way of examples. Example 1 10 parts by weight of calcium sulfate was mixed with 100 parts by weight of polyethylene (degree of polymerization: 1100), and this was extruded (molded) into a sheet (130 ° C., 200 kg / c).
m ² ) and a test plate (100 mm × 200 mm × 2 mm) were prepared. Example 2 Polyvinyl chloride (polymerization degree 800) 3 parts by weight, methyl isobutyl ketone 30 parts by weight, rosin (trade name Hyper,
Arakawa Chemical Industry Co., Ltd.) 19 parts by weight, talc 10 parts by weight,
Brush with a coating composition consisting of 10 parts by weight of red iron oxide and 28 parts by weight of calcium sulfate on both sides of coated steel (100 mm x 200 mm x 1 mm) to which a rust preventive coating has been applied in advance so that the dry film thickness is 100 μm on one side. Coating was performed twice, and naturally dried at room temperature for 3 days to prepare a test plate.

Example 3 8 parts by weight of chloroprene rubber (polymerization degree: 600), 8 parts by weight of rosin (trade name: Hyper, manufactured by Arakawa Chemical Industry Co., Ltd.),
5 parts by weight of dioctyl phthalate, 25 parts by weight of xylene,
Methyl isobutyl ketone 44 parts by weight, calcium sulfate 1
The coating composition consisting of 0 parts by weight was sufficiently impregnated into a fishing net of Section 11 (3.03 cm mesh) made of amide fiber (trade name Amilan, manufactured by Toray Industries, Inc.) as a material, and air-dried for 12 hours. To produce a test net. Example 4 2 parts by weight of portal cement, river sand (particle size 5 mm or less) 4
1 part by weight of water, 1 part by weight of water and 0.36 part by weight of calcium sulfate are mixed to form a mold (2
(00 mm × 300 mm × 40 mm), and dried naturally for 3 days to prepare a test plate.

Comparative Example 1 In Example 1, a sheet made of polyethylene alone was molded to prepare a test plate (100 mm × 200 mm × 2 mm). Comparative Example 2 From 4 parts by weight of polyvinyl chloride (degree of polymerization: 1100), 44 parts by weight of methyl isobutyl ketone, 26 parts by weight of rosin (trade name: Hyper, manufactured by Arakawa Chemical Industry Co., Ltd.), 13 parts by weight of talc, and 13 parts by weight of red iron oxide. The coating composition is coated steel (100 mm × 200 mm × 1
(mm) was coated twice with a brush so that the dry film thickness was 100 μm on one side, and naturally dried at room temperature for 3 days to prepare a test plate.

Comparative Example 3 9 parts by weight of chloroprene rubber (polymerization degree: 600), 9 parts by weight of rosin (trade name: Hyper, manufactured by Arakawa Chemical Industry Co., Ltd.)
6 parts by weight of dioctyl phthalate, 28 parts by weight of xylene,
A coating composition consisting of 48 parts by weight of methyl isobutyl ketone was sufficiently impregnated into a fishing net of section 11 (3.03 cm mesh) made of amide fiber (trade name: Amilan, manufactured by Toray Industries, Inc.) as a material. A test net was prepared by air-drying for an hour. Comparative Example 4 Portoral cement 2 parts by weight, river sand (particle size 5 mm or less) 4
By weight, 5 parts by weight of river gravel (particle size 20 mm or less) and 1 part by weight of water were mixed, poured into a mold (200 mm × 300 mm × 40 mm), and naturally dried for 3 days to prepare a test plate.

The test plates and test nets produced in Examples 1 to 4 and Comparative Examples 1 to 4 were attached to an immersion raft installed in Hitachi Port, Hitachi City, Ibaraki Prefecture, immersed in the sea, and attached organisms on the test plate ( The number of barnacles adhered was observed over time. Table 1 shows the results.

[0024]

[Table 1]

As is apparent from Table 1, a test plate, which is a resin molded product containing the aquatic organism adhesion preventing agent of the present invention, was obtained by applying a coating composition containing the aquatic organism adhesion preventing agent of the present invention on the surface. The test plate, the test plate impregnated with the coating composition containing the aquatic organism adhesion preventing agent of the present invention, and the test plate which is an underwater structure containing the aquatic organism adhesion preventing agent of the present invention are the aquatic organisms of the present invention. Compared with the test plate and the test net produced without adding the anti-adhesion agent, only a small amount of the biological adhesion was observed, and it was found that the biological adhesion preventing effect was excellent.

[0026]

The aquatic organism adhesion-preventing agent according to claim 1 is
To provide a material for underwater structures that does not contain heavy metals or harmful elements and therefore has no pollution or safety problems and can be mixed with synthetic resins and paints to maintain an excellent biofouling prevention effect for a long period of time. You can The aquatic organism adhesion preventing agent according to claim 2 is excellent in that it exhibits the effect of the aquatic organism adhesion preventing agent according to claim 1 and also has the property as an extender. The aquatic organism adhesion preventing agent according to claim 3 exhibits the effect of the aquatic organism adhesion preventing agent according to claim 1,
Further, it is excellent in that it has both the properties of a thermoplastic resin as a lubricant and the properties of a stabilizer when kneaded with a vinyl chloride resin. The aquatic organism adhesion preventive agent according to claim 4 exhibits the effect of the aquatic organism adhesion preventive agent according to claim 1, 2 or 3, and further exerts an influence on an ecosystem of aquatic organisms because a component in seawater is used. It is excellent in that it does not need to be considered. The aquatic organism attachment-preventing agent according to claim 5,
It is excellent in that it has the effect of the aquatic organism adhesion preventive agent described in 2 or 3, and that it is not necessary to consider the effect on the ecosystem of aquatic organisms because a compound derived from marine organisms is used. The coating composition according to claim 6 provides a coating film capable of maintaining an excellent biofouling prevention effect for a long period of time. The resin molded product according to claim 7 can maintain an excellent biofouling prevention effect for a long period of time. The underwater structure according to claim 8 can maintain an excellent biofouling prevention effect for a long period of time. The underwater structure according to claim 9 can maintain an excellent effect of preventing biofouling for a long period of time due to the coating film on the surface. The underwater structure according to claim 10 can maintain an excellent biofouling-preventing effect for a long period of time by the resin molding adhered to the surface.

Claims (10)

[Claims] 1. An aquatic organism adhesion preventing agent comprising a calcium compound as an active ingredient. 2. The aquatic organism adhesion preventing agent according to claim 1, wherein the calcium compound is an inorganic salt or complex. 3. The aquatic organism adhesion preventing agent according to claim 1, wherein the calcium compound is an organic salt or complex. 4. The aquatic organism adhesion preventing agent according to claim 1, 2 or 3, wherein the calcium compound is a component in seawater. 5. The aquatic organism adhesion preventing agent according to claim 1, 2 or 3, wherein the calcium compound is a compound derived from a marine organism. 6. A coating composition comprising the aquatic organism adhesion preventing agent according to claim 1. 7. A resin molded product containing the aquatic organism adhesion preventing agent according to claim 1. 8. An underwater structure comprising the aquatic organism attachment-preventing agent according to any one of claims 1 to 5. 9. An underwater structure coated with the coating composition according to claim 6. 10. An underwater structure having the surface of the resin molded product according to claim 7.